@article{terracciano_poly2-oxazoline-based_2024,
	title = {Poly(2-oxazoline)-{Based} {Thermoresponsive} {Stomatocytes}},
	volume = {25},
	issn = {1525-7797},
	doi = {10.1021/acs.biomac.4c00726},
	abstract = {The design of biocompatible and biodegradable nanostructures with controlled morphological features remains a predominant challenge in medical research. Stimuli-responsive vesicles offer significant advantages in drug delivery, biomedical applications, and diagnostic techniques. The combination of poly(2-oxazoline)s with biodegradable polymers could provide exceptional biocompatibility properties and be proposed as a versatile platform for the development of new medicines. Therefore, poly(2-ethyl-2-oxazoline) (PEtOx) and poly(2-isopropyl-2-oxazoline) (PiPrOx) possessing a hydroxy terminal group that acts as an initiator for the ring-opening polymerization of d,l-lactide (DLLA) have been utilized in this study. The resulting amphiphilic block polymers were used to create polymersomes, which undergo solvent-dependent reorganization into bowl-shaped vesicles or stomatocytes. By blending PEtOx-b-PDLLA and PiPrOx-b-PDLLA copolymers, a thermoresponsive stomatocyte was generated, where the opening narrowed and irreversibly closed with a slight increase in the temperature. Detailed transmission electron microscopy analysis reveals the formation of both closed and fused stomatocytes upon heating the sample above the critical solution temperature of PiPrOx.},
	number = {9},
	urldate = {2024-08-21},
	journal = {BIOMACROMOLECULES},
	author = {Terracciano, Roberto and Liu, Yuechi and Varanaraja, Zivani and Godzina, Magdalena and Yilmaz, Gokhan and van Hest, Jan C. M. and Becer, C. Remzi},
	month = aug,
	year = {2024},
	pages = {6050--6059},
}

The design of biocompatible and biodegradable nanostructures with controlled morphological features remains a predominant challenge in medical research. Stimuli-responsive vesicles offer significant advantages in drug delivery, biomedical applications, and diagnostic techniques. The combination of poly(2-oxazoline)s with biodegradable polymers could provide exceptional biocompatibility properties and be proposed as a versatile platform for the development of new medicines. Therefore, poly(2-ethyl-2-oxazoline) (PEtOx) and poly(2-isopropyl-2-oxazoline) (PiPrOx) possessing a hydroxy terminal group that acts as an initiator for the ring-opening polymerization of d,l-lactide (DLLA) have been utilized in this study. The resulting amphiphilic block polymers were used to create polymersomes, which undergo solvent-dependent reorganization into bowl-shaped vesicles or stomatocytes. By blending PEtOx-b-PDLLA and PiPrOx-b-PDLLA copolymers, a thermoresponsive stomatocyte was generated, where the opening narrowed and irreversibly closed with a slight increase in the temperature. Detailed transmission electron microscopy analysis reveals the formation of both closed and fused stomatocytes upon heating the sample above the critical solution temperature of PiPrOx.

@article{ryan_small_2024,
	title = {Small molecule organic eutectics as candidates to replace plastics},
	issn = {2041-6520},
	doi = {10.1039/d4sc02574a},
	abstract = {Legislative change and shifting consumer sentiment drive a need to replace polymers in certain products. Herein, we highlight that eutectic molecular glasses and liquids are promising but underutilized candidate materials. We formulate a series of hydrophobic eutectic molecular liquids and glasses by mixing their crystalline components. The eutectic composition of each mixture was determined by both differential scanning calorimetry (DSC) and UV-vis spectroscopic measurements, which were processed and analyzed using a trained partial least squares regression model. With product shelf-life in mind, the long-term stability (up to 14 months) of the amorphous materials towards crystallization was proven using powder X-ray diffraction (PXRD). Molecular dynamics (MD) simulations put forward potential design rules in terms of the physical stability of these glasses. Rheological properties were investigated from the perspective of processability. Low fragility indices were found for all liquids, aiding processability through glassblowing, fiber pulling, film formation and molding. We show that properties can be tailored by blending two different eutectic systems or simply adding a plasticizer. To demonstrate a potential application area, the 4-hydroxychalcone and bifonazole eutectic system was used as a matrix for controlled release studies of a model active ingredient.Mixing small organic crystalline molecules produces eutectic glasses and liquids with "polymer-like" physical properties.},
	urldate = {2024-08-22},
	journal = {CHEMICAL SCIENCE},
	author = {Ryan, Joshua L. and Sosso, Gabriele C. and Bon, Stefan A. F.},
	month = aug,
	year = {2024},
}

Legislative change and shifting consumer sentiment drive a need to replace polymers in certain products. Herein, we highlight that eutectic molecular glasses and liquids are promising but underutilized candidate materials. We formulate a series of hydrophobic eutectic molecular liquids and glasses by mixing their crystalline components. The eutectic composition of each mixture was determined by both differential scanning calorimetry (DSC) and UV-vis spectroscopic measurements, which were processed and analyzed using a trained partial least squares regression model. With product shelf-life in mind, the long-term stability (up to 14 months) of the amorphous materials towards crystallization was proven using powder X-ray diffraction (PXRD). Molecular dynamics (MD) simulations put forward potential design rules in terms of the physical stability of these glasses. Rheological properties were investigated from the perspective of processability. Low fragility indices were found for all liquids, aiding processability through glassblowing, fiber pulling, film formation and molding. We show that properties can be tailored by blending two different eutectic systems or simply adding a plasticizer. To demonstrate a potential application area, the 4-hydroxychalcone and bifonazole eutectic system was used as a matrix for controlled release studies of a model active ingredient.Mixing small organic crystalline molecules produces eutectic glasses and liquids with "polymer-like" physical properties.

@article{colwell_self-reinforced_2024,
	title = {Self-reinforced biodegradable thermoplastic composites},
	volume = {7},
	issn = {2522-0128},
	doi = {10.1007/s42114-024-00939-x},
	abstract = {Improvements in the mechanical performance of biodegradable plastics are required to facilitate replacement of commodity plastics as part of a global push for the use of more sustainable materials. Reinforcing biodegradable plastics with fillers or fibres to create composite materials is an obvious choice for increasing mechanical properties but may affect recyclability and biodegradability. To avoid these issues, self-reinforced polymer composites (SRPCs), where the polymer matrix is reinforced with highly oriented films, fibres, or particles of the same polymer may be used. However, the use of biodegradable thermoplastics in SRPCs is currently limited to a few polymers, mostly focusing on poly(lactic acid) (PLA). Here, we have assessed the potential for a broader range of biodegradable thermoplastics to replace commercially available commodity-plastic-based SRPCs. This assessment was done using literature data for the oriented and isotropic bulk mechanical properties of commercially relevant biodegradable thermoplastics, along with properties for their SRPCs where available. It was found that despite polycaprolactone (PCL), poly(butylene succinate) (PBS), poly(butylene succinate adipate) (PBSA), and poly(butylene adipate terephthalate) (PBAT) not being suitable replacements for current commercially available SRPCs, they nonetheless exhibit increased modulus and strength after orientation. PLA, polyhydroxyalkanoates (PHAs), and poly(glycolic acid) (PGA) have more potential, with PGA being the most promising, although PLA and PHAs appear to offer potentially more sustainable alternatives to commercially available SRPCs and a wider range of end-of-life disposal options.},
	number = {4},
	urldate = {2024-08-01},
	journal = {ADVANCED COMPOSITES AND HYBRID MATERIALS},
	author = {Colwell, John and Halley, Peter and Varley, Russell and Heidarian, Pejman and Mcnally, Tony and Peijs, Ton and Vandi, Luigi},
	month = aug,
	year = {2024},
}

Improvements in the mechanical performance of biodegradable plastics are required to facilitate replacement of commodity plastics as part of a global push for the use of more sustainable materials. Reinforcing biodegradable plastics with fillers or fibres to create composite materials is an obvious choice for increasing mechanical properties but may affect recyclability and biodegradability. To avoid these issues, self-reinforced polymer composites (SRPCs), where the polymer matrix is reinforced with highly oriented films, fibres, or particles of the same polymer may be used. However, the use of biodegradable thermoplastics in SRPCs is currently limited to a few polymers, mostly focusing on poly(lactic acid) (PLA). Here, we have assessed the potential for a broader range of biodegradable thermoplastics to replace commercially available commodity-plastic-based SRPCs. This assessment was done using literature data for the oriented and isotropic bulk mechanical properties of commercially relevant biodegradable thermoplastics, along with properties for their SRPCs where available. It was found that despite polycaprolactone (PCL), poly(butylene succinate) (PBS), poly(butylene succinate adipate) (PBSA), and poly(butylene adipate terephthalate) (PBAT) not being suitable replacements for current commercially available SRPCs, they nonetheless exhibit increased modulus and strength after orientation. PLA, polyhydroxyalkanoates (PHAs), and poly(glycolic acid) (PGA) have more potential, with PGA being the most promising, although PLA and PHAs appear to offer potentially more sustainable alternatives to commercially available SRPCs and a wider range of end-of-life disposal options.

@article{booth_phase_2024,
	title = {Phase change material nanocapsules for latent function thermal fluids with tuneable thermal energy storage profiles},
	volume = {15},
	issn = {1759-9954},
	doi = {10.1039/d4py00789a},
	abstract = {Phase change materials (PCMs) can capture and release thermal energy in the form of latent heat and PCMs as liquid dispersions are known as latent function thermal fluids. For these dispersions, the PCMs are encapsulated to warrant colloidal stability. Here, capsule formation of mini-emulsions of various methacrylates in the presence of trimethylolpropane trimethacrylate (TMA) as a crosslinker, and n-hexadecane (HD), n-octadecane (OCT), and n-docosane (DOC) as PCM was investigated. An omega-unsaturated poly(n-butyl methacrylate-b-[(methacrylic acid)-co-(methyl methacrylate)]) macromonomer was used as a reactive macromolecular emulsifier. The mini-emulsion polymerizations, capsule fabrication and performance were optimized. The resulting latent function thermal fluids and their dried equivalents were studied with differential scanning calorimetry (DSC). A challenge of these materials is matching the temperature range of the application to that of their phase change. The performance of a thermal fluid of DOC nanocapsules was tested against the base fluid water with promising results. As a tunability concept, crosslinked poly(methyl methacrylate) nanocapsules of n-octadecane (OCT) and n-docosane (DOC) were blended as a tuneable latent function thermal fluid.Blends of water-based dispersions of Phase Change Material (PCM) nanocapsules made by mini-emulsion polymerization function as tuneable latent function thermal fluids.},
	number = {33},
	urldate = {2024-08-06},
	journal = {POLYMER CHEMISTRY},
	author = {Booth, Joshua R. and Davies, Joshua D. and Bon, Stefan A. F.},
	month = aug,
	year = {2024},
	pages = {3359--3377},
}

Phase change materials (PCMs) can capture and release thermal energy in the form of latent heat and PCMs as liquid dispersions are known as latent function thermal fluids. For these dispersions, the PCMs are encapsulated to warrant colloidal stability. Here, capsule formation of mini-emulsions of various methacrylates in the presence of trimethylolpropane trimethacrylate (TMA) as a crosslinker, and n-hexadecane (HD), n-octadecane (OCT), and n-docosane (DOC) as PCM was investigated. An omega-unsaturated poly(n-butyl methacrylate-b-[(methacrylic acid)-co-(methyl methacrylate)]) macromonomer was used as a reactive macromolecular emulsifier. The mini-emulsion polymerizations, capsule fabrication and performance were optimized. The resulting latent function thermal fluids and their dried equivalents were studied with differential scanning calorimetry (DSC). A challenge of these materials is matching the temperature range of the application to that of their phase change. The performance of a thermal fluid of DOC nanocapsules was tested against the base fluid water with promising results. As a tunability concept, crosslinked poly(methyl methacrylate) nanocapsules of n-octadecane (OCT) and n-docosane (DOC) were blended as a tuneable latent function thermal fluid.Blends of water-based dispersions of Phase Change Material (PCM) nanocapsules made by mini-emulsion polymerization function as tuneable latent function thermal fluids.

@article{zhang_hypotoxic_2024,
	title = {Hypotoxic amphiphilic polymers with high fluoride content as oxygen carriers enhance photodynamic therapy against hypoxic tumors},
	volume = {15},
	issn = {1759-9954},
	doi = {10.1039/d4py00598h},
	abstract = {Photodynamic therapy (PDT) eradicates cancer cells by transforming tumor oxygen into highly reactive singlet oxygen (1O2) through a photosensitizer. However, pre-existing hypoxia within tumors and oxygen consumption during PDT can cause insufficient oxygen supply, hence hindering the effectiveness of this treatment modality. Fluorides, renowned for their excellent biocompatibility and oxygen affinity, have been widely applied in medical environments as carriers. In this study, a hypotoxic amphiphilic fluorinated polymer (PEGAF) was synthesized using polyethylene glycol methyl ether acrylate (PEGA) and perfluorooctyl acrylate (PFOEA) as monomers through the atomic transfer radical polymerization (ATRP) technology and used as carriers for oxygen and the photosensitizer chlorin e6 (Ce6). Experimental results demonstrated that PEGAF@Ce6-O2 substantially improved the hypoxic microenvironment of tumors and significantly inhibited tumor growth, markedly enhancing the outcome compared to sole PDT application. This study proposes a new strategy for enhancing the efficacy of PDT.Synthesis of the amphiphilic fluorinated polymer PEGA-PFOEA (PEGAF) and its application in enhancing photodynamic therapy.},
	number = {32},
	urldate = {2024-08-01},
	journal = {POLYMER CHEMISTRY},
	author = {Zhang, Jun-an and Sheng, Jiang-feng and Haddleton, David and Wilson, Paul and Mo, Yong-jie and Li, Hong-li and Zhao, Hong-lei and Zhu, Lin-hua and Dai, Chun-yan and Zhao, Lin-lu},
	month = aug,
	year = {2024},
	note = {Jiangsu Jitri Carbon Fiber \& Composite Applicat Te
Hainan Liansu Ind Technol Co Ltd},
	pages = {3266--3278},
}

Photodynamic therapy (PDT) eradicates cancer cells by transforming tumor oxygen into highly reactive singlet oxygen (1O2) through a photosensitizer. However, pre-existing hypoxia within tumors and oxygen consumption during PDT can cause insufficient oxygen supply, hence hindering the effectiveness of this treatment modality. Fluorides, renowned for their excellent biocompatibility and oxygen affinity, have been widely applied in medical environments as carriers. In this study, a hypotoxic amphiphilic fluorinated polymer (PEGAF) was synthesized using polyethylene glycol methyl ether acrylate (PEGA) and perfluorooctyl acrylate (PFOEA) as monomers through the atomic transfer radical polymerization (ATRP) technology and used as carriers for oxygen and the photosensitizer chlorin e6 (Ce6). Experimental results demonstrated that PEGAF@Ce6-O2 substantially improved the hypoxic microenvironment of tumors and significantly inhibited tumor growth, markedly enhancing the outcome compared to sole PDT application. This study proposes a new strategy for enhancing the efficacy of PDT.Synthesis of the amphiphilic fluorinated polymer PEGA-PFOEA (PEGAF) and its application in enhancing photodynamic therapy.

@article{heidarian_poly3-hydroxybutyrate-co-3-hydroxyvalerate_2024,
	title = {Poly(3-{Hydroxybutyrate}-co-3-{Hydroxyvalerate}) {Self}-{Reinforced} {Composites} via {Solvent}-{Induced} {Interfiber} {Welding} of {Nanofibers}},
	volume = {25},
	issn = {1525-7797},
	doi = {10.1021/acs.biomac.4c00441},
	abstract = {In this study, we explore an approach to enhance the mechanical performance of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) by utilizing the self-reinforcing effect of beta-phase-induced PHBV electrospun nanofiber mats. This involves electrospinning combined with low-temperature postspun vapor solvent interfiber welding. Scanning electron microscopy imaging confirmed fiber alignment, while XRD diffraction revealed the presence of both alpha and beta crystalline phases under optimized electrospinning conditions. The resulting composite exhibited significant improvements in mechanical properties attributed to the formation of more perfectly structured alpha and beta polymorphs and enhanced interfacial adhesion of electrospun nanofibers after vapor solvent treatment. This approach offers entirely recyclable and biodegradable materials, presenting the potential for a new family of sustainable bioplastics.},
	number = {8},
	urldate = {2024-08-14},
	journal = {BIOMACROMOLECULES},
	author = {Heidarian, Pejman and Aziz, Shazed and Halley, Peter J. and McNally, Tony and Peijs, Ton and Vandi, Luigi-Jules and Varley, Russell J.},
	month = jul,
	year = {2024},
	pages = {5039--5047},
}

In this study, we explore an approach to enhance the mechanical performance of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) by utilizing the self-reinforcing effect of beta-phase-induced PHBV electrospun nanofiber mats. This involves electrospinning combined with low-temperature postspun vapor solvent interfiber welding. Scanning electron microscopy imaging confirmed fiber alignment, while XRD diffraction revealed the presence of both alpha and beta crystalline phases under optimized electrospinning conditions. The resulting composite exhibited significant improvements in mechanical properties attributed to the formation of more perfectly structured alpha and beta polymorphs and enhanced interfacial adhesion of electrospun nanofibers after vapor solvent treatment. This approach offers entirely recyclable and biodegradable materials, presenting the potential for a new family of sustainable bioplastics.

@article{salisbury_photo-cross-linked_2024,
	title = {Photo-{Cross}-linked {Gelatin} {Methacryloyl} {Hydrogels} {Enable} the {Growth} of {Primary} {Human} {Endometrial} {Stromal} {Cells} and {Epithelial} {Gland} {Organoids}},
	volume = {16},
	issn = {1944-8244},
	doi = {10.1021/acsami.4c08763},
	abstract = {In vitro three-dimensional (3D) models are better able to replicate the complexity of real organs and tissues than 2D monolayer models. The human endometrium, the inner lining of the uterus, undergoes complex changes during the menstrual cycle and pregnancy. These changes occur in response to steroid hormone fluctuations and elicit crosstalk between the epithelial and stromal cell compartments, and dysregulations are associated with a variety of pregnancy disorders. Despite the importance of the endometrium in embryo implantation and pregnancy establishment, there is a lack of in vitro models that recapitulate tissue structure and function and as such a growing demand for extracellular matrix hydrogels that can support 3D cell culture. To be physiologically relevant, an in vitro model requires mechanical and biochemical cues that mimic those of the ECM found in the native tissue. We report a semisynthetic gelatin methacryloyl (GelMA) hydrogel that combines the bioactive properties of natural hydrogels with the tunability and reproducibility of synthetic materials. We then describe a simple protocol whereby cells can quickly be encapsulated in GelMA hydrogels. We investigate the suitability of GelMA hydrogel to support the development of an endometrial model by culturing the main endometrial cell types: stromal cells and epithelial cells. We also demonstrate how the mechanical and biochemical properties of GelMA hydrogels can be tailored to support the growth and maintenance of epithelial gland organoids that emerge upon 3D culturing of primary endometrial epithelial progenitor cells in a defined chemical medium. We furthermore demonstrate the ability of GelMA hydrogels to support the viability of stromal cells and their function measured by monitoring decidualization in response to steroid hormones. This study describes the first steps toward the development of a hydrogel matrix-based model that recapitulates the structure and function of the native endometrium and could support applications in understanding reproductive failure.},
	number = {30},
	urldate = {2024-07-27},
	journal = {ACS APPLIED MATERIALS \& INTERFACES},
	author = {Salisbury, Emma and Rawlings, Thomas M. and Efstathiou, Spyridon and Tryfonos, Maria and Makwana, Komal and Fitzgerald, Harriet C. and Gargett, Caroline E. and Cameron, Neil R. and Haddleton, David M. and Brosens, Jan J. and Eissa, Ahmed M.},
	month = jul,
	year = {2024},
	pages = {39140--39152},
}

In vitro three-dimensional (3D) models are better able to replicate the complexity of real organs and tissues than 2D monolayer models. The human endometrium, the inner lining of the uterus, undergoes complex changes during the menstrual cycle and pregnancy. These changes occur in response to steroid hormone fluctuations and elicit crosstalk between the epithelial and stromal cell compartments, and dysregulations are associated with a variety of pregnancy disorders. Despite the importance of the endometrium in embryo implantation and pregnancy establishment, there is a lack of in vitro models that recapitulate tissue structure and function and as such a growing demand for extracellular matrix hydrogels that can support 3D cell culture. To be physiologically relevant, an in vitro model requires mechanical and biochemical cues that mimic those of the ECM found in the native tissue. We report a semisynthetic gelatin methacryloyl (GelMA) hydrogel that combines the bioactive properties of natural hydrogels with the tunability and reproducibility of synthetic materials. We then describe a simple protocol whereby cells can quickly be encapsulated in GelMA hydrogels. We investigate the suitability of GelMA hydrogel to support the development of an endometrial model by culturing the main endometrial cell types: stromal cells and epithelial cells. We also demonstrate how the mechanical and biochemical properties of GelMA hydrogels can be tailored to support the growth and maintenance of epithelial gland organoids that emerge upon 3D culturing of primary endometrial epithelial progenitor cells in a defined chemical medium. We furthermore demonstrate the ability of GelMA hydrogels to support the viability of stromal cells and their function measured by monitoring decidualization in response to steroid hormones. This study describes the first steps toward the development of a hydrogel matrix-based model that recapitulates the structure and function of the native endometrium and could support applications in understanding reproductive failure.

@article{brendel_outstanding_2024,
	title = {Outstanding {Reviewers} for {Polymer} {Chemistry} in 2023},
	volume = {15},
	issn = {1759-9954},
	doi = {10.1039/d4py90071e},
	abstract = {We would like to take this opportunity to thank all of Polymer Chemistry's reviewers for helping to preserve quality and integrity in chemical science literature. We would also like to highlight the Outstanding Reviewers for Polymer Chemistry in 2023.},
	number = {28},
	urldate = {2024-07-26},
	journal = {POLYMER CHEMISTRY},
	author = {Brendel, Johannes and De, Priyadarsi and Guerre, Marc and Jian, Zhongbao and Kamigaito, Masami and Lorandi, Francesca and Ohnsorg, Monica and Tran, Helen and Wilson, Paul and Barner-Kowollik, Christopher and Southall, Maria},
	month = jul,
	year = {2024},
	pages = {2799--2799},
}

We would like to take this opportunity to thank all of Polymer Chemistry's reviewers for helping to preserve quality and integrity in chemical science literature. We would also like to highlight the Outstanding Reviewers for Polymer Chemistry in 2023.

@article{lee_vat_2024,
	title = {Vat photopolymerization using catalytic chain transfer polymerization ({CCTP}) derived reactive oligomers to influence mechanical properties},
	volume = {15},
	issn = {1759-9954},
	doi = {10.1039/d4py00482e},
	abstract = {omega-Vinyl terminated reactive oligomers of 2-ethylhexyl methacrylate and poly(ethylene glycol)methacrylate (PEGMA) were synthesized via catalytic chain transfer polymerization (CCTP) and subsequent addition-fragmentation chain transfer (AFCT) polymerization. The reactive oligomers were then incorporated into 3D-printing resins composed of isobornyl acrylate and poly(ethylene glycol)diacrylate (PEGDA). The formulations were used in digital light processing (DLP) 3D printing, and the mechanical properties of the printed parts evaluated. The effects of concentration, molecular weight and chemistry of the reactive oligomers additives were investigated. It was found that EHMA based reactive oligomers acted as plasticizers resulting in the weakening of the printed objects, whereas PEGMA based reactive oligomers transformed the objects from stiff and brittle to ductile elastomer-like materials.omega-Vinyl terminated reactive oligomers of 2-ethylhexyl methacrylate and poly(ethylene glycol)methacrylate (PEGMA) were synthesized via CCTP and subsequent addition-fragmentation chain transfer (AFCT) polymerization.},
	number = {29},
	urldate = {2024-07-16},
	journal = {POLYMER CHEMISTRY},
	author = {Lee, Wai Hin and Wan, Zhongyuan and Shegiwal, Ataulla and Haddleton, David},
	month = jul,
	year = {2024},
	note = {Halcyon3D Ltd},
	pages = {2959--2969},
}

omega-Vinyl terminated reactive oligomers of 2-ethylhexyl methacrylate and poly(ethylene glycol)methacrylate (PEGMA) were synthesized via catalytic chain transfer polymerization (CCTP) and subsequent addition-fragmentation chain transfer (AFCT) polymerization. The reactive oligomers were then incorporated into 3D-printing resins composed of isobornyl acrylate and poly(ethylene glycol)diacrylate (PEGDA). The formulations were used in digital light processing (DLP) 3D printing, and the mechanical properties of the printed parts evaluated. The effects of concentration, molecular weight and chemistry of the reactive oligomers additives were investigated. It was found that EHMA based reactive oligomers acted as plasticizers resulting in the weakening of the printed objects, whereas PEGMA based reactive oligomers transformed the objects from stiff and brittle to ductile elastomer-like materials.omega-Vinyl terminated reactive oligomers of 2-ethylhexyl methacrylate and poly(ethylene glycol)methacrylate (PEGMA) were synthesized via CCTP and subsequent addition-fragmentation chain transfer (AFCT) polymerization.

@article{aljuaid_thermoreversible_2024,
	title = {Thermoreversible [2+2] {Photodimers} of {Monothiomaleimides} and {Intrinsically} {Recyclable} {Covalent} {Networks} {Thereof}},
	volume = {146},
	issn = {0002-7863},
	doi = {10.1021/jacs.4c04193},
	abstract = {The development of intrinsically recyclable cross-linked materials remains challenged by the inherently unfavorable chemical equilibrium that dictates the efficiency of the reversible covalent bonding/debonding chemistry. Rather than having to (externally) manipulate the bonding equilibrium, we here introduce a new reversible chemistry platform based on monosubstituted thiomaleimides that can undergo complete and independent light-activated covalent bonding and on-demand thermal debonding above 120 degrees C. Specifically, repeated bonding/debonding of a small-molecule thiomaleimide [2 + 2] photodimer is demonstrated over five heat/light cycles with full conversion in both directions, thereby regenerating its initial monothiomaleimide constituents. This motivated the synthesis of multifunctional thiomaleimide reagents as precursors for the design of covalently cross-linked networks that display intrinsic switching between a monomeric and polymeric state. The resulting materials are shown to covalently dissociate and depolymerize upon heating both in solution and in bulk, thus transforming the densely photo-cross-linked material back into a viscous liquid. Temperature-regulated photorheology evidenced the intrinsic recyclability of the thiomaleimide-based thermosets during multiple cycles of UV cross-linking and thermal de-cross-linking. The thermally reversible photodimerization of thiomaleimides presents a new addition to the designer playground of dynamic polymer networks, providing interesting opportunities for the reprocessing and closed-loop recycling of covalently cross-linked materials.},
	number = {28},
	urldate = {2024-07-10},
	journal = {JOURNAL OF THE AMERICAN CHEMICAL SOCIETY},
	author = {Aljuaid, Mohammed and Chang, Yujing and Haddleton, David M. and Wilson, Paul and Houck, Hannes A.},
	month = jul,
	year = {2024},
	pages = {19177--19182},
}

The development of intrinsically recyclable cross-linked materials remains challenged by the inherently unfavorable chemical equilibrium that dictates the efficiency of the reversible covalent bonding/debonding chemistry. Rather than having to (externally) manipulate the bonding equilibrium, we here introduce a new reversible chemistry platform based on monosubstituted thiomaleimides that can undergo complete and independent light-activated covalent bonding and on-demand thermal debonding above 120 degrees C. Specifically, repeated bonding/debonding of a small-molecule thiomaleimide [2 + 2] photodimer is demonstrated over five heat/light cycles with full conversion in both directions, thereby regenerating its initial monothiomaleimide constituents. This motivated the synthesis of multifunctional thiomaleimide reagents as precursors for the design of covalently cross-linked networks that display intrinsic switching between a monomeric and polymeric state. The resulting materials are shown to covalently dissociate and depolymerize upon heating both in solution and in bulk, thus transforming the densely photo-cross-linked material back into a viscous liquid. Temperature-regulated photorheology evidenced the intrinsic recyclability of the thiomaleimide-based thermosets during multiple cycles of UV cross-linking and thermal de-cross-linking. The thermally reversible photodimerization of thiomaleimides presents a new addition to the designer playground of dynamic polymer networks, providing interesting opportunities for the reprocessing and closed-loop recycling of covalently cross-linked materials.

@article{beres_kinetic_2024,
	title = {Kinetic investigation of photoiniferter-{RAFT} polymerization in continuous flow using inline {NMR} analysis},
	volume = {15},
	issn = {1759-9954},
	doi = {10.1039/d4py00409d},
	abstract = {Photo reversible deactivation radical polymerization and, in particular, photoiniferter-reversible addition-fragmentation chain transfer (PI-RAFT) polymerization have become popular approaches to polymer synthesis in recent years. There is, however, a lack of fundamental investigations concerning the mechanism and kinetics of such reactions. Herein, we apply an automated continuous flow platform featuring inline NMR analysis that allows for rapid kinetic screening via transient timesweep experiments for detailed investigation of the PI-RAFT of two model monomers with different propagation rates and radical stabilities-methyl acrylate (MA) and methyl methacrylate (MMA). The effect of the structure of the RAFT agent on polymerization kinetics is studied. For the polymerization of MA, RAFT agents with a more stabilised R group lead to an induction period whose extent can be tuned by varying the light intensity. Faster polymerization of MA with xanthates than with trithiocarbonates suggests the important role of reversible termination in the PI-RAFT mechanism. The slower apparent rate of propagation for the polymerization of acrylates compared to polymerization of methacrylates, when mediated by trithiocarbonate RAFT agents, indicates that polymerization of MA is retarded due to the lower radical stability of the propagating radical compared to methacrylic radicals.Photo reversible deactivation radical polymerization and, in particular, photoiniferter-reversible addition-fragmentation chain transfer (PI-RAFT) polymerization have become popular approaches to polymer synthesis in recent years.},
	number = {31},
	urldate = {2024-07-22},
	journal = {POLYMER CHEMISTRY},
	author = {Beres, Magdalena A. and Zhang, Bo and Junkers, Tanja and Perrier, Sebastien},
	month = aug,
	year = {2024},
	pages = {3166--3175},
}

Photo reversible deactivation radical polymerization and, in particular, photoiniferter-reversible addition-fragmentation chain transfer (PI-RAFT) polymerization have become popular approaches to polymer synthesis in recent years. There is, however, a lack of fundamental investigations concerning the mechanism and kinetics of such reactions. Herein, we apply an automated continuous flow platform featuring inline NMR analysis that allows for rapid kinetic screening via transient timesweep experiments for detailed investigation of the PI-RAFT of two model monomers with different propagation rates and radical stabilities-methyl acrylate (MA) and methyl methacrylate (MMA). The effect of the structure of the RAFT agent on polymerization kinetics is studied. For the polymerization of MA, RAFT agents with a more stabilised R group lead to an induction period whose extent can be tuned by varying the light intensity. Faster polymerization of MA with xanthates than with trithiocarbonates suggests the important role of reversible termination in the PI-RAFT mechanism. The slower apparent rate of propagation for the polymerization of acrylates compared to polymerization of methacrylates, when mediated by trithiocarbonate RAFT agents, indicates that polymerization of MA is retarded due to the lower radical stability of the propagating radical compared to methacrylic radicals.Photo reversible deactivation radical polymerization and, in particular, photoiniferter-reversible addition-fragmentation chain transfer (PI-RAFT) polymerization have become popular approaches to polymer synthesis in recent years.

@article{liu_radical_2024,
	title = {Radical polymerisation and thiol-ene post-polymerisation functionalisation of terpenoid acrylates in conventional and renewably sourced organic solvents},
	volume = {15},
	issn = {1759-9954},
	doi = {10.1039/d4py00340c},
	abstract = {Geranyl acrylate has been synthesized and polymerized by various radical polymerisation techniques. Due to the structural diversity, a number of post polymerisation functionalization options were explored. Monomer conversion, polymer structure and the molecular weight were assessed by NMR, FT-IR and size exclusion chromatography (SEC). Free radical polymerization and Cu-mediated reversible deactivation radical polymerization (RDRP) were used to synthesise poly(geranyl acrylate) of various molecular weight in both conventional petro-derived organic and bio-based renewably sourced solvents. Cu0 wire-mediated RDRP was found to be a suitable polymerisation method when compared to CuII-mediated photoinduced RDRP giving the optimal living radical polymerisation method for the synthesis of poly(geranyl acrylate) in Cyrene (Mn, SEC = 3000, \& Dstrok;SEC = 1.25). The residual allylic double bonds provided a useful option for post-polymerization modification. Poly(geranyl acrylate) was subjected to photoinduced thiol-ene reactions, using different thiols with a variety of functional groups. The success of the functionalization reaction was evaluated by NMR, FT-IR spectroscopy, and SEC. In addition, differential scanning calorimetry was used to investigate changes in the thermal properties of the polymer, before and after thiol-ene functionalization.Geranyl acrylate has been synthesized and polymerized by various radical polymerisation techniques.},
	number = {28},
	urldate = {2024-07-08},
	journal = {POLYMER CHEMISTRY},
	author = {Liu, Huizhe and Maugein, Vincent A. and Haddleton, David M.},
	month = jul,
	year = {2024},
	pages = {2862--2872},
}

Geranyl acrylate has been synthesized and polymerized by various radical polymerisation techniques. Due to the structural diversity, a number of post polymerisation functionalization options were explored. Monomer conversion, polymer structure and the molecular weight were assessed by NMR, FT-IR and size exclusion chromatography (SEC). Free radical polymerization and Cu-mediated reversible deactivation radical polymerization (RDRP) were used to synthesise poly(geranyl acrylate) of various molecular weight in both conventional petro-derived organic and bio-based renewably sourced solvents. Cu0 wire-mediated RDRP was found to be a suitable polymerisation method when compared to CuII-mediated photoinduced RDRP giving the optimal living radical polymerisation method for the synthesis of poly(geranyl acrylate) in Cyrene (Mn, SEC = 3000, & Dstrok;SEC = 1.25). The residual allylic double bonds provided a useful option for post-polymerization modification. Poly(geranyl acrylate) was subjected to photoinduced thiol-ene reactions, using different thiols with a variety of functional groups. The success of the functionalization reaction was evaluated by NMR, FT-IR spectroscopy, and SEC. In addition, differential scanning calorimetry was used to investigate changes in the thermal properties of the polymer, before and after thiol-ene functionalization.Geranyl acrylate has been synthesized and polymerized by various radical polymerisation techniques.

@article{korpidou_glycooligomer-functionalized_2024,
	title = {Glycooligomer-{Functionalized} {Catalytic} {Nanocompartments} {Co}-{Loaded} with {Enzymes} {Support} {Parallel} {Reactions} and {Promote} {Cell} {Internalization}},
	volume = {25},
	issn = {1525-7797},
	doi = {10.1021/acs.biomac.4c00526},
	abstract = {A major shortcoming associated with the application of enzymes in drug synergism originates from the lack of site-specific, multifunctional nanomedicine. This study introduces catalytic nanocompartments (CNCs) made of a mixture of PDMS-b-PMOXA diblock copolymers, decorated with glycooligomer tethers comprising eight mannose-containing repeating units and coencapsulating two enzymes, providing multifunctionality by their in situ parallel reactions. Beta-glucuronidase (GUS) serves for local reactivation of the drug hymecromone, while glucose oxidase (GOx) induces cell starvation through glucose depletion and generation of the cytotoxic H2O2. The insertion of the pore-forming peptide, melittin, facilitates diffusion of substrates and products through the membranes. Increased cell-specific internalization of the CNCs results in a substantial decrease in HepG2 cell viability after 24 h, attributed to simultaneous production of hymecromone and H2O2. Such parallel enzymatic reactions taking place in nanocompartments pave the way to achieve efficient combinatorial cancer therapy by enabling localized drug production along with reactive oxygen species (ROS) elevation.},
	number = {7},
	urldate = {2024-07-02},
	journal = {BIOMACROMOLECULES},
	author = {Korpidou, Maria and Becker, Jonas and Tarvirdipour, Shabnam and Dinu, Ionel Adrian and Becer, C. Remzi and Palivan, Cornelia G.},
	month = jun,
	year = {2024},
	note = {NCCR Mol Syst Engn},
	pages = {4492--4509},
}

A major shortcoming associated with the application of enzymes in drug synergism originates from the lack of site-specific, multifunctional nanomedicine. This study introduces catalytic nanocompartments (CNCs) made of a mixture of PDMS-b-PMOXA diblock copolymers, decorated with glycooligomer tethers comprising eight mannose-containing repeating units and coencapsulating two enzymes, providing multifunctionality by their in situ parallel reactions. Beta-glucuronidase (GUS) serves for local reactivation of the drug hymecromone, while glucose oxidase (GOx) induces cell starvation through glucose depletion and generation of the cytotoxic H2O2. The insertion of the pore-forming peptide, melittin, facilitates diffusion of substrates and products through the membranes. Increased cell-specific internalization of the CNCs results in a substantial decrease in HepG2 cell viability after 24 h, attributed to simultaneous production of hymecromone and H2O2. Such parallel enzymatic reactions taking place in nanocompartments pave the way to achieve efficient combinatorial cancer therapy by enabling localized drug production along with reactive oxygen species (ROS) elevation.

@article{brogden_water-based_2024,
	title = {Water-based polymer colloids with a branched chain architecture as low-gel pressure-sensitive adhesives},
	volume = {15},
	issn = {1759-9954},
	doi = {10.1039/d4py00522h},
	abstract = {The performance of water-based acrylic pressure-sensitive adhesives, in which the latex particles had minimal gel content of typically less than a few percent and the polymer chains had a branched architecture, were investigated. A series of semi-batch emulsion copolymerizations of 2-octyl acrylate, isobornyl acrylate and acrylic acid was carried out in the presence of ethylene glycol dimethacrylate as crosslinker. The molecular weight distributions and branched chain topology were regulated by using 2-ethylhexyl thioglycolate as a chain-transfer agent. The monomers and chain-transfer agent were selected as these were already available as bio-based feedstocks, or had a realistic potential to become available from non-petrochemical resources. Adhesive films cast from the polymer dispersions demonstrated good peel, shear strength and tack adhesion energies. This is attributed to polymer chain branching, which unlocks a broader window for the design rules for pressure-sensitive adhesives. Detailed rheological studies of the viscoelastic materials were conducted to support the adhesive test results.The performance of water-based acrylic pressure-sensitive adhesives was investigated. The latex particles had minimal gel content, typically below a few percent, and the polymer chains exhibited a branched architecture.},
	number = {28},
	urldate = {2024-07-10},
	journal = {POLYMER CHEMISTRY},
	author = {Brogden, Emily M. and Bon, Stefan A. F.},
	month = jul,
	year = {2024},
	pages = {2849--2861},
}

The performance of water-based acrylic pressure-sensitive adhesives, in which the latex particles had minimal gel content of typically less than a few percent and the polymer chains had a branched architecture, were investigated. A series of semi-batch emulsion copolymerizations of 2-octyl acrylate, isobornyl acrylate and acrylic acid was carried out in the presence of ethylene glycol dimethacrylate as crosslinker. The molecular weight distributions and branched chain topology were regulated by using 2-ethylhexyl thioglycolate as a chain-transfer agent. The monomers and chain-transfer agent were selected as these were already available as bio-based feedstocks, or had a realistic potential to become available from non-petrochemical resources. Adhesive films cast from the polymer dispersions demonstrated good peel, shear strength and tack adhesion energies. This is attributed to polymer chain branching, which unlocks a broader window for the design rules for pressure-sensitive adhesives. Detailed rheological studies of the viscoelastic materials were conducted to support the adhesive test results.The performance of water-based acrylic pressure-sensitive adhesives was investigated. The latex particles had minimal gel content, typically below a few percent, and the polymer chains exhibited a branched architecture.

@article{mackinnon_exploring_2024,
	title = {Exploring {Polymeric} {Diene}-{Dienophile} {Pairs} for {Thermoreversible} {Diels}-{Alder} {Reactions}},
	issn = {0024-9297},
	doi = {10.1021/acs.macromol.4c00832},
	abstract = {The thermoreversible Diels-Alder (DA) reaction provides access to reversible thermosets and thus a pathway to their circular recycling. However, the known thermoreversible diene-dienophile DA pairs are very limited and primarily involve the furan-maleimide pair; hence, there is a need to investigate novel pairs that can provide thermal reversibility in chemical binding at higher and lower temperatures. Hence, a set of 24 diene-dienophile pairs are screened for their tendency to undergo a Diels-Alder (DA) reaction at temperatures up to 140 degrees C. Of the 21 viable DA pairs, 16 DA pairs then successfully underwent gelation in an analogous polymer cross-linking system. The viability of the thermoreversible retro-Diels-Alder (rDA) reaction at elevated temperatures was then studied via a dissolution study, dynamic scanning calorimetry, and dynamic mechanical analysis. Two novel pairs were shown to undergo rDA degelation for the first time in a polymeric system. [Anthracene-9-methanol + citraconimide] and [anthracene-9-methanol + monomethyl fumarate amide] underwent degelation at 277 and 247 degrees C, respectively. Several additional novel gels showed dissolution at temperatures up to 250 degrees C, suggesting that their rDA processes may be accessible, albeit at higher temperatures. The partial self-healing of these two thermoreversible gels at temperatures of 100 and 150 degrees C, significantly below their degelation temperatures, is also demonstrated.},
	urldate = {2024-06-27},
	journal = {MACROMOLECULES},
	author = {Mackinnon, Daniel J. and Drain, Ben and Becer, C. Remzi},
	month = jun,
	year = {2024},
}

The thermoreversible Diels-Alder (DA) reaction provides access to reversible thermosets and thus a pathway to their circular recycling. However, the known thermoreversible diene-dienophile DA pairs are very limited and primarily involve the furan-maleimide pair; hence, there is a need to investigate novel pairs that can provide thermal reversibility in chemical binding at higher and lower temperatures. Hence, a set of 24 diene-dienophile pairs are screened for their tendency to undergo a Diels-Alder (DA) reaction at temperatures up to 140 degrees C. Of the 21 viable DA pairs, 16 DA pairs then successfully underwent gelation in an analogous polymer cross-linking system. The viability of the thermoreversible retro-Diels-Alder (rDA) reaction at elevated temperatures was then studied via a dissolution study, dynamic scanning calorimetry, and dynamic mechanical analysis. Two novel pairs were shown to undergo rDA degelation for the first time in a polymeric system. [Anthracene-9-methanol + citraconimide] and [anthracene-9-methanol + monomethyl fumarate amide] underwent degelation at 277 and 247 degrees C, respectively. Several additional novel gels showed dissolution at temperatures up to 250 degrees C, suggesting that their rDA processes may be accessible, albeit at higher temperatures. The partial self-healing of these two thermoreversible gels at temperatures of 100 and 150 degrees C, significantly below their degelation temperatures, is also demonstrated.

@article{song_dicobaltii_2024,
	title = {Dicobalt({II}) helices kill colon cancer cells via enantiomer-specific mechanisms; {DNA} damage or microtubule disruption},
	volume = {15},
	issn = {2041-6520},
	doi = {10.1039/d4sc02541e},
	abstract = {Highly diastereoselective self-assembly reactions give both enantiomers (Lambda and Delta) of anti-parallel triple-stranded bimetallic Co(ii) and Co(iii) cationic helices, without the need for resolution; the first such reaction for Co. The complexes are water soluble and stable, even in the case of Co(ii). Studies in a range of cancer and healthy cell lines indicate high activity and selectivity, and substantial differences between enantiomers. The oxidation state has little effect, and correspondingly, Co(iii) compounds are reduced to Co(ii) e.g. by glutathione. In HCT116 colon cancer cells the Lambda enantiomer induces dose-dependent G2-M arrest in the cell cycle and disrupts microtubule architectures. This Co(ii) Lambda enantiomer is ca. five times more potent than the isostructural Fe(ii) compound. Since the measured cellular uptakes are similar this implies a higher affinity of the Co system for the intracellular target(s); while the two systems are isostructural they have substantially different charge distributions as shown by calculated hydrophobicity maps. In contrast to the Lambda enantiomer, Delta-Co(ii) induces G1 arrest in HCT116 cells, efficiently inhibits the topoisomerase I-catalyzed relaxation of supercoiled plasmid DNA, and, unlike the isostructural Fe(ii) system, causes DNA damage. It thus seems very likely that redox chemistry plays a role in the latter.},
	number = {28},
	urldate = {2024-06-27},
	journal = {CHEMICAL SCIENCE},
	author = {Song, Hualong and Kostrhunova, Hana and Cervinka, Jakub and Macpherson, Julie and Malina, Jaroslav and Rajan, Teena and Phillips, Roger and Postings, Miles and Shepherd, Samantha and Zhang, Xuejian and Brabec, Viktor and Rogers, Nicola J. and Scott, Peter},
	month = jul,
	year = {2024},
	pages = {11029--11037},
}

Highly diastereoselective self-assembly reactions give both enantiomers (Lambda and Delta) of anti-parallel triple-stranded bimetallic Co(ii) and Co(iii) cationic helices, without the need for resolution; the first such reaction for Co. The complexes are water soluble and stable, even in the case of Co(ii). Studies in a range of cancer and healthy cell lines indicate high activity and selectivity, and substantial differences between enantiomers. The oxidation state has little effect, and correspondingly, Co(iii) compounds are reduced to Co(ii) e.g. by glutathione. In HCT116 colon cancer cells the Lambda enantiomer induces dose-dependent G2-M arrest in the cell cycle and disrupts microtubule architectures. This Co(ii) Lambda enantiomer is ca. five times more potent than the isostructural Fe(ii) compound. Since the measured cellular uptakes are similar this implies a higher affinity of the Co system for the intracellular target(s); while the two systems are isostructural they have substantially different charge distributions as shown by calculated hydrophobicity maps. In contrast to the Lambda enantiomer, Delta-Co(ii) induces G1 arrest in HCT116 cells, efficiently inhibits the topoisomerase I-catalyzed relaxation of supercoiled plasmid DNA, and, unlike the isostructural Fe(ii) system, causes DNA damage. It thus seems very likely that redox chemistry plays a role in the latter.

@article{varanaraja_utilization_2024,
	title = {Utilization of {Anthracene}-{Functionalized} {Poly}(2-oxazolines) as a {Dispersant} of {Carbon} {Black} in {Water} and {Dodecane}},
	volume = {57},
	issn = {0024-9297},
	doi = {10.1021/acs.macromol.4c00843},
	abstract = {Poly(2-oxazoline)s (POxs) offer an unparalleled degree of functionalization in the fabrication of smart, functional polymers for a wide range of applications. By utilizing 2-ethyl-2-oxazoline and a unique hydrophobic 2-oxazoline monomer, 2-isostearyl-2-oxazoline, we report the synthesis of a library of functionalized poly(2-ethyl-2-oxazoline)s (PEtOxs) and poly(2-isostearyl-2-oxazoline)s (PiStOxs) that show incredible potential as dispersants of carbon black (CB) in water and dodecane. The initiation and termination of 2-oxazoline polymerizations by direct end-capping can be exploited to introduce a variety of end-groups. Herein, we utilize this methodology to report the efficient synthesis of anthracene-end-capped PEtOx and PiStOx. A small library of 9-(chloromethyl)anthracene-initiated polymers was also synthesized to increase the aromaticity to investigate its influence on the dispersion of CB. The solution behavior of the polymers in aqueous and nonaqueous media is studied via turbidity measurement, and their ability to disperse CB in water and dodecane systems is assessed by a UV-vis spectrophotometer. PEtOx and PiStOx both display characteristics of a good dispersant, and PiStOx exhibits better performance than a commercially available dispersant, presenting superior results than previously reported for POx.},
	number = {12},
	urldate = {2024-06-17},
	journal = {MACROMOLECULES},
	author = {Varanaraja, Zivani and Terracciano, Roberto and Hollingsworth, Nathan and Green, Ross and Beament, James and Becer, C. Remzi},
	month = jun,
	year = {2024},
	note = {Infineum UK Ltd},
	pages = {5769--5779},
}

Poly(2-oxazoline)s (POxs) offer an unparalleled degree of functionalization in the fabrication of smart, functional polymers for a wide range of applications. By utilizing 2-ethyl-2-oxazoline and a unique hydrophobic 2-oxazoline monomer, 2-isostearyl-2-oxazoline, we report the synthesis of a library of functionalized poly(2-ethyl-2-oxazoline)s (PEtOxs) and poly(2-isostearyl-2-oxazoline)s (PiStOxs) that show incredible potential as dispersants of carbon black (CB) in water and dodecane. The initiation and termination of 2-oxazoline polymerizations by direct end-capping can be exploited to introduce a variety of end-groups. Herein, we utilize this methodology to report the efficient synthesis of anthracene-end-capped PEtOx and PiStOx. A small library of 9-(chloromethyl)anthracene-initiated polymers was also synthesized to increase the aromaticity to investigate its influence on the dispersion of CB. The solution behavior of the polymers in aqueous and nonaqueous media is studied via turbidity measurement, and their ability to disperse CB in water and dodecane systems is assessed by a UV-vis spectrophotometer. PEtOx and PiStOx both display characteristics of a good dispersant, and PiStOx exhibits better performance than a commercially available dispersant, presenting superior results than previously reported for POx.

@article{lefley_self-assembly_2024,
	title = {Self-{Assembly} {Behavior} of {Amphiphilic} {Poly}(2-ethyl-2-oxazoline)-b-poly(2-isostearyl-2-oxazoline) {Block} {Copolymers}},
	volume = {57},
	issn = {0024-9297},
	doi = {10.1021/acs.macromol.4c00833},
	abstract = {By utilizing a unique hydrophobic 2-oxazoline monomer, we report the facile and efficient synthesis of a novel poly(2-ethyl-2-oxazoline)-block-poly(2-isostearyl-2-oxazoline) copolymer library via cationic ring-opening polymerization. Varying the hydrophilic-hydrophobic block ratios of the copolymers afforded good control over thermal properties such as the glass transition temperature, leading to an increase from 0 to 60 degrees C as the volume fraction of the 2-ethyl-2-oxazoline block increased. A solvent-free self-assembly method was employed to study the self-assembly behavior of the copolymer library. Thus, using thin film hydration, a wide range of self-assembled structures were obtained in aqueous solution. Structures such as micelles, short and long worms, and unilamellar and multilamellar vesicles were observed and characterized via dynamic light scattering and electron microscopy analysis. All structures exhibited excellent stability in solution at ambient temperatures over a 2 month period and showed thermoresponsive behavior.},
	number = {12},
	urldate = {2024-06-16},
	journal = {MACROMOLECULES},
	author = {Lefley, James and Terracciano, Roberto and Varanaraja, Zivani and Beament, James and Becer, C. Remzi},
	month = jun,
	year = {2024},
	note = {Infineum UK Ltd},
	pages = {5881--5891},
}

By utilizing a unique hydrophobic 2-oxazoline monomer, we report the facile and efficient synthesis of a novel poly(2-ethyl-2-oxazoline)-block-poly(2-isostearyl-2-oxazoline) copolymer library via cationic ring-opening polymerization. Varying the hydrophilic-hydrophobic block ratios of the copolymers afforded good control over thermal properties such as the glass transition temperature, leading to an increase from 0 to 60 degrees C as the volume fraction of the 2-ethyl-2-oxazoline block increased. A solvent-free self-assembly method was employed to study the self-assembly behavior of the copolymer library. Thus, using thin film hydration, a wide range of self-assembled structures were obtained in aqueous solution. Structures such as micelles, short and long worms, and unilamellar and multilamellar vesicles were observed and characterized via dynamic light scattering and electron microscopy analysis. All structures exhibited excellent stability in solution at ambient temperatures over a 2 month period and showed thermoresponsive behavior.

@article{tooley_real-time_2024,
	title = {Real-{Time} {Determination} of {Molecular} {Weight}: {Use} of {MaDDOSY} ({Mass} {Determination} {Diffusion} {Ordered} {Spectroscopy}) to {Monitor} the {Progress} of {Polymerization} {Reactions}},
	volume = {4},
	issn = {2694-2453},
	doi = {10.1021/acspolymersau.4c00020},
	abstract = {Knowledge of molecular weight is an integral factor in polymer synthesis, and while many synthetic strategies have been developed to help control this, determination of the final molecular weight is often only measured at the end of the reaction. Herein, we provide a technique for the online determination of polymer molecular weight using a universal, solvent-independent diffusion ordered spectroscopy (DOSY) calibration and evidence its use in a variety of polymerization reactions.},
	number = {4},
	urldate = {2024-05-24},
	journal = {ACS POLYMERS AU},
	author = {Tooley, Owen and Pointer, William and Radmall, Rowan and Hall, Mia and Swift, Thomas and Town, James and Aydogan, Cansu and Junkers, Tanja and Wilson, Paul and Lester, Daniel and Haddleton, David},
	month = may,
	year = {2024},
	pages = {311--319},
}

Knowledge of molecular weight is an integral factor in polymer synthesis, and while many synthetic strategies have been developed to help control this, determination of the final molecular weight is often only measured at the end of the reaction. Herein, we provide a technique for the online determination of polymer molecular weight using a universal, solvent-independent diffusion ordered spectroscopy (DOSY) calibration and evidence its use in a variety of polymerization reactions.

@article{lee_exploiting_2024,
	title = {Exploiting a branched radical polymerization strategy to enhance the degree of grafting onto graphene oxide},
	volume = {15},
	issn = {1759-9954},
	doi = {10.1039/d4py00300d},
	abstract = {The synthesis of polymer-grafted graphene oxide (GO) using a branched radical polymerization strategy is described. A methacrylate-based macromonomer is used as a chain-transfer agent to enhance the degree of grafting and prevent macroscopic gel formation. A methacrylic acid-based macromonomer was first synthesized via aqueous solution catalytic chain transfer polymerization. The resultant macromonomer was used as a chain transfer agent in the radical polymerization of poly(ethylene glycol) methacrylate (PEGMA) in the presence of a dispersion of GO in a water/DMF mixture (50 : 50 w/w). The degree of grafting was determined using thermogravimetric analyses and infrared spectroscopy, and the geometrical evolution was investigated using atomic force microscopy. The grafting efficiency increased with the degree of branching.The synthesis of polymer-grafted graphene oxide (GO) using a branched radical polymerization strategy is described.},
	number = {21},
	urldate = {2024-05-20},
	journal = {POLYMER CHEMISTRY},
	author = {Lee, Wai Hin and Bon, Stefan A. F.},
	month = may,
	year = {2024},
	pages = {2199--2211},
}

The synthesis of polymer-grafted graphene oxide (GO) using a branched radical polymerization strategy is described. A methacrylate-based macromonomer is used as a chain-transfer agent to enhance the degree of grafting and prevent macroscopic gel formation. A methacrylic acid-based macromonomer was first synthesized via aqueous solution catalytic chain transfer polymerization. The resultant macromonomer was used as a chain transfer agent in the radical polymerization of poly(ethylene glycol) methacrylate (PEGMA) in the presence of a dispersion of GO in a water/DMF mixture (50 : 50 w/w). The degree of grafting was determined using thermogravimetric analyses and infrared spectroscopy, and the geometrical evolution was investigated using atomic force microscopy. The grafting efficiency increased with the degree of branching.The synthesis of polymer-grafted graphene oxide (GO) using a branched radical polymerization strategy is described.

@article{hernandez-serrano_effect_2024,
	title = {Effect of transdermal drug delivery patches on the stratum corneum: in vivo inspection with a handheld terahertz probe},
	volume = {15},
	issn = {2156-7085},
	doi = {10.1364/BOE.513557},
	abstract = {Transdermal drug delivery patches are a good alternative to hypodermic drug injection. The drug delivery efficiency depends strongly on the hydration of the skin under treatment, and therefore, it is essential to study the effects on the skin induced by the application of these medical -grade patches. Terahertz (THz) spectroscopy shows great promise for non-invasive skin evaluation due to its high sensitivity to subtle changes in water content, low power and non -ionizing properties. In this work, we study the effects of transdermal drug delivery patches (three fully occlusive and three partially occlusive) applied on the upper arms of ten volunteers for a maximum period of 28 h. Three different levels of propylene glycol (0 \%, 3 \% and 6 \%) are added to the patches as excipient. By performing multilayer analysis, we successfully retrieve the water content of the stratum corneum (SC) which is the outermost layer of skin, as well as its thickness at different times before and after applying the patches. This study demonstrates the potential of using THz sensing for non invasive skin monitoring and has wide applications for skin evaluation as well as the development of skin products. Published by Optica Publishing Group under the terms of the Creative Commons Attribution 4.0 License. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI.},
	number = {5},
	urldate = {2024-07-04},
	journal = {BIOMEDICAL OPTICS EXPRESS},
	author = {Hernandez-serrano, Arturo I. and Ding, Xuefei and Costa, Goncalo and Nurumbetov, Gabit and Haddleton, David M. and Pickwell-Macpherson, Emma},
	month = may,
	year = {2024},
	pages = {3064--3075},
}

Transdermal drug delivery patches are a good alternative to hypodermic drug injection. The drug delivery efficiency depends strongly on the hydration of the skin under treatment, and therefore, it is essential to study the effects on the skin induced by the application of these medical -grade patches. Terahertz (THz) spectroscopy shows great promise for non-invasive skin evaluation due to its high sensitivity to subtle changes in water content, low power and non -ionizing properties. In this work, we study the effects of transdermal drug delivery patches (three fully occlusive and three partially occlusive) applied on the upper arms of ten volunteers for a maximum period of 28 h. Three different levels of propylene glycol (0 %, 3 % and 6 %) are added to the patches as excipient. By performing multilayer analysis, we successfully retrieve the water content of the stratum corneum (SC) which is the outermost layer of skin, as well as its thickness at different times before and after applying the patches. This study demonstrates the potential of using THz sensing for non invasive skin monitoring and has wide applications for skin evaluation as well as the development of skin products. Published by Optica Publishing Group under the terms of the Creative Commons Attribution 4.0 License. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI.

@article{ren_thermo-oxidative_2024,
	title = {Thermo-oxidative degradation behavior of natural rubber vulcanized by different curing systems},
	volume = {295},
	issn = {0009-2509},
	doi = {10.1016/j.ces.2024.120147},
	abstract = {In this work, the effects of three types of curing systems: conventional vulcanization (CV), semi-efficient vulcanization (SEV) and efficient vulcanization (EV) on the degradation efficiency of sulfur cured natural rubber (NR) were investigated. NR vulcanizates were prepared and degraded at 210 degrees C in air for different periods of time. The sol fraction, molecular weight, element contents and degradation kinetics were studied in detail. The degradation efficiency of the NR vulcanizates was decreased in the order of CV, SEV and EV cured NR, which was caused by the lower crosslink density, apparent activation energy and bond dissociation energy of polysulfide bonds formed in the NR vulcanizates with CV, as compared to others. The results of Horikx theory and contents of carbonyl and sulfone group in degraded rubber indicated both sulfide scission and main chain scission occurred in the NR vulcanizates prepared with CV and SEV. Both the type of sulfidic crosslinks and crosslink density affect the degradative efficiency and products. The type of sulfidic crosslinks was the main factor affecting the degradation degree of NR vulcanizates, while the crosslink density mainly influenced the sol molecular weight of the degraded products. Moreover, the degradation mechanism of the three types of NR vulcanizates was proposed. This work demonstrated that the thermo-oxidative degradation efficiency of vulcanized rubber is affected by curing systems, which may provide guidance for upcycling waste rubber effectively.},
	urldate = {2024-06-06},
	journal = {CHEMICAL ENGINEERING SCIENCE},
	author = {Ren, Teng and Wan, Chaoying and Song, Pan and Rodrigue, Denis and Zhang, Yuxin and Wang, Shifeng},
	month = aug,
	year = {2024},
}

In this work, the effects of three types of curing systems: conventional vulcanization (CV), semi-efficient vulcanization (SEV) and efficient vulcanization (EV) on the degradation efficiency of sulfur cured natural rubber (NR) were investigated. NR vulcanizates were prepared and degraded at 210 degrees C in air for different periods of time. The sol fraction, molecular weight, element contents and degradation kinetics were studied in detail. The degradation efficiency of the NR vulcanizates was decreased in the order of CV, SEV and EV cured NR, which was caused by the lower crosslink density, apparent activation energy and bond dissociation energy of polysulfide bonds formed in the NR vulcanizates with CV, as compared to others. The results of Horikx theory and contents of carbonyl and sulfone group in degraded rubber indicated both sulfide scission and main chain scission occurred in the NR vulcanizates prepared with CV and SEV. Both the type of sulfidic crosslinks and crosslink density affect the degradative efficiency and products. The type of sulfidic crosslinks was the main factor affecting the degradation degree of NR vulcanizates, while the crosslink density mainly influenced the sol molecular weight of the degraded products. Moreover, the degradation mechanism of the three types of NR vulcanizates was proposed. This work demonstrated that the thermo-oxidative degradation efficiency of vulcanized rubber is affected by curing systems, which may provide guidance for upcycling waste rubber effectively.

@article{mohammed_plug-and-play_2024,
	title = {'{Plug}-and-play' aqueous electrochemical atom transfer radical polymerization of acrylamide},
	volume = {211},
	issn = {0014-3057},
	doi = {10.1016/j.eurpolymj.2024.113028},
	abstract = {Copper-mediated reversible deactivation radical polymerization of the acrylamide monomer has been found to be a challenging process. It has generally not been explored in great detail, despite the many commercial applications of polyacrylamide (PAm). In addition, the recently reported 'plug-and-play ' methodology enabled by the Electrasyn Pro 2.0 device has not yet been widely adopted. Herein, the controlled aqueous electrochemical atom transfer radical polymerization (eATRP) of acrylamide in pure aqueous media is demonstrated using our potentiostatic 'plug-and-play ' methodology. It was found that in the presence of high concentrations of electrolyte (0.5 M KNO3) there is good control over molecular weight and dispersity, but little electrochemical control over the reaction kinetics. Upon decreasing the concentration of KNO3 (0.1 M) and adding NaBr (6.9 mM), good control over molecular weight and dispersity was retained e.g. when targeting DPn,th = 100, 91 \% conversion was obtained within 7 h yielding polyacrylamide (PAm) with M-n,M-SEC = 5300 gmol(-1) (M-n,M-th = 6500 gmol(-1) ) and (D) over bar (m) = 1.24. Furthermore, under these conditions, the desirable electrochemical control over the reaction was observed. The ability to target different chain lengths (D-Pn,D-th = 25 -100) was also demonstrated, with good agreement between M-n,M-SEC and M-n,M-th exemplifying the use of the 'plug-and-play ' eATRP methodology for controlled polymerization of acrylamide.},
	urldate = {2024-05-30},
	journal = {EUROPEAN POLYMER JOURNAL},
	author = {Mohammed, Mahir and Wilson, Paul},
	month = may,
	year = {2024},
}

Copper-mediated reversible deactivation radical polymerization of the acrylamide monomer has been found to be a challenging process. It has generally not been explored in great detail, despite the many commercial applications of polyacrylamide (PAm). In addition, the recently reported 'plug-and-play ' methodology enabled by the Electrasyn Pro 2.0 device has not yet been widely adopted. Herein, the controlled aqueous electrochemical atom transfer radical polymerization (eATRP) of acrylamide in pure aqueous media is demonstrated using our potentiostatic 'plug-and-play ' methodology. It was found that in the presence of high concentrations of electrolyte (0.5 M KNO3) there is good control over molecular weight and dispersity, but little electrochemical control over the reaction kinetics. Upon decreasing the concentration of KNO3 (0.1 M) and adding NaBr (6.9 mM), good control over molecular weight and dispersity was retained e.g. when targeting DPn,th = 100, 91 % conversion was obtained within 7 h yielding polyacrylamide (PAm) with M-n,M-SEC = 5300 gmol(-1) (M-n,M-th = 6500 gmol(-1) ) and (D) over bar (m) = 1.24. Furthermore, under these conditions, the desirable electrochemical control over the reaction was observed. The ability to target different chain lengths (D-Pn,D-th = 25 -100) was also demonstrated, with good agreement between M-n,M-SEC and M-n,M-th exemplifying the use of the 'plug-and-play ' eATRP methodology for controlled polymerization of acrylamide.

@article{lei_supra-fluorophores_2024,
	title = {Supra-{Fluorophores}: {Ultrabright} {Fluorescent} {Supramolecular} {Assemblies} {Derived} from {Conventional} {Fluorophores} in {Water}},
	volume = {36},
	issn = {0935-9648},
	doi = {10.1002/adma.202401346},
	abstract = {Fluorescent organic nanoparticles (NPs) with exceptional brightness hold significant promise for demanding fluorescence bioimaging applications. Although considerable efforts are invested in developing novel organic dyes with enhanced performance, augmenting the brightness of conventional fluorophores is still one of the biggest challenges to overcome. This study presents a supramolecular strategy for constructing ultrabright fluorescent nanoparticles in aqueous media (referred to as "Supra-fluorophores") derived from conventional fluorophores. To achieve this, this course has employed a cylindrical nanoparticle with a hydrophobic microdomain, assembled by a cyclic peptide-diblock copolymer conjugate in water, as a supramolecular scaffold. The noncovalent dispersion of fluorophore moieties within the hydrophobic microdomain of the scaffold effectively mitigates the undesired aggregation-caused quenching and fluorescence quenching by water, resulting in fluorescent NPs with high brightness. This strategy is applicable to a broad spectrum of fluorophore families, covering polyaromatic hydrocarbons, coumarins, boron-dipyrromethenes, cyanines, xanthenes, and squaraines. The resulting fluorescent NPs demonstrate high fluorescence quantum yield ({\textgreater}30\%) and brightness per volume (as high as 12 060 m-1 cm-1 nm-3). Moreover, high-performance NPs with emission in the NIR region are constructed, showcasing up to 20-fold increase in both brightness and photostability. This Supra-fluorophore strategy offers a versatile and effective method for transforming existing fluorophores into ultrabright fluorescent NPs in aqueous environments, for applications such as bioimaging.},
	number = {25},
	urldate = {2024-04-07},
	journal = {ADVANCED MATERIALS},
	author = {Lei, Yuqing and Wang, Yuqian and Hill, Sophie K. and Cheng, Zihe and Song, Qiao and Perrier, Sebastien},
	month = jun,
	year = {2024},
}

Fluorescent organic nanoparticles (NPs) with exceptional brightness hold significant promise for demanding fluorescence bioimaging applications. Although considerable efforts are invested in developing novel organic dyes with enhanced performance, augmenting the brightness of conventional fluorophores is still one of the biggest challenges to overcome. This study presents a supramolecular strategy for constructing ultrabright fluorescent nanoparticles in aqueous media (referred to as "Supra-fluorophores") derived from conventional fluorophores. To achieve this, this course has employed a cylindrical nanoparticle with a hydrophobic microdomain, assembled by a cyclic peptide-diblock copolymer conjugate in water, as a supramolecular scaffold. The noncovalent dispersion of fluorophore moieties within the hydrophobic microdomain of the scaffold effectively mitigates the undesired aggregation-caused quenching and fluorescence quenching by water, resulting in fluorescent NPs with high brightness. This strategy is applicable to a broad spectrum of fluorophore families, covering polyaromatic hydrocarbons, coumarins, boron-dipyrromethenes, cyanines, xanthenes, and squaraines. The resulting fluorescent NPs demonstrate high fluorescence quantum yield (\textgreater30%) and brightness per volume (as high as 12 060 m-1 cm-1 nm-3). Moreover, high-performance NPs with emission in the NIR region are constructed, showcasing up to 20-fold increase in both brightness and photostability. This Supra-fluorophore strategy offers a versatile and effective method for transforming existing fluorophores into ultrabright fluorescent NPs in aqueous environments, for applications such as bioimaging.

@article{yuan_experimental_2024,
	title = {Experimental process characterisation for high-volume compression moulding of hybrid-architecture composites},
	volume = {181},
	issn = {1359-835X},
	doi = {10.1016/j.compositesa.2024.108137},
	abstract = {Compression moulding of woven fabric prepreg and sheet moulding compound (SMC) in a single-shot process combines the superior mechanical properties of continuous fibre composites and the high design flexibility of discontinuous fibre composites. This experimental study presents insights into the moulding characteristics of prepreg and SMC and explores the interaction between these two materials during manufacturing of hybridarchitecture composites. All tests were performed under typical compression moulding conditions using a squeeze flow testing rig. The response of each material was interpreted through proposed material models applied to the data acquired from single architecture tests. Critical interaction mechanisms were identified from hybrid architecture tests, alongside some additional deformation mechanisms, such as high level of in-plane fibre tow deformation not observed in single-architecture tests. Novel experimental methods were also introduced to quantify the change in meso-scale fibre architecture in the prepreg induced by the flow of SMC. The outcomes of this study not only shed light on the essential interaction mechanisms of hybrid-architecture composites but also provide valuable insights into deformation mechanisms not apparent in isolated material studies. Ultimately, these findings will facilitate the future development of a numerical simulation model for hybrid moulding processes.},
	urldate = {2024-04-27},
	journal = {COMPOSITES PART A-APPLIED SCIENCE AND MANUFACTURING},
	author = {Yuan, Hao and Khan, Muhammad and Peijs, Ton and Qian, Connie},
	month = jun,
	year = {2024},
}

Compression moulding of woven fabric prepreg and sheet moulding compound (SMC) in a single-shot process combines the superior mechanical properties of continuous fibre composites and the high design flexibility of discontinuous fibre composites. This experimental study presents insights into the moulding characteristics of prepreg and SMC and explores the interaction between these two materials during manufacturing of hybridarchitecture composites. All tests were performed under typical compression moulding conditions using a squeeze flow testing rig. The response of each material was interpreted through proposed material models applied to the data acquired from single architecture tests. Critical interaction mechanisms were identified from hybrid architecture tests, alongside some additional deformation mechanisms, such as high level of in-plane fibre tow deformation not observed in single-architecture tests. Novel experimental methods were also introduced to quantify the change in meso-scale fibre architecture in the prepreg induced by the flow of SMC. The outcomes of this study not only shed light on the essential interaction mechanisms of hybrid-architecture composites but also provide valuable insights into deformation mechanisms not apparent in isolated material studies. Ultimately, these findings will facilitate the future development of a numerical simulation model for hybrid moulding processes.

@article{efstathiou_moisture-cured_2024,
	title = {Moisture-cured solvent free silylated poly(ether-urea) pressure-sensitive adhesives ({PSAs}) for use as skin adhesives for application in transdermal drug delivery ({TDD})},
	volume = {5},
	issn = {2633-5409},
	doi = {10.1039/d3ma01104f},
	abstract = {Improving the adhesion and tack of pressure-sensitive adhesives (PSAs) remains an ongoing challenge. Polyureas often have stronger hydrogen bonding relative to, the more commonly used, polyurethanes which are quite common in adhesive applications. An increased adhesion can reduce the requirements for additives such as tackifier resins and fillers to achieve high levels of adhesion required in certain applications. This approach not only necessitates tedious optimisations but also introduces compatibility issues especially in drug-in-adhesive formulation development. In this work, novel silylated polyurea moisture-curable PSAs are introduced with moisture curing of silyl terminated polyether-urea prepolymers. Prepolymer variants were synthesised using a solvent and catalyst-free step-growth polymerisation by reacting the commercially available polyetheramine Jeffamine (R) D-4000 with isophorone diisocyanate (IPDI) to yield diprimaryamino-terminated polymers. The polymers' average molecular weight was controlled by adjusting the -NCO/-NH2 molar ratio. Subsequently, the amino terminal ends were post-functionalised with 3-isocyanatopropyltrimethoxysilane (IPTMS) to attain the silylated moisture-curable prepolymer variant crosslinkers (PUXL). The variants were able to cure to form (-Si-O-Si-) crosslinked PSA gels in the presence of a titanium catalyst and moisture. These materials were characterised by a range of techniques including rheology and thermal characterisation. Although their thermal properties remained unaltered, their adhesion and tack increased by increasing the -NCO/-NH2 molar ratio exceeding the borders of the Chang's classification windows for removable PSAs. This was achieved without the requirement for any additional tackifyer resins. Peel test and rolling ball tack tests agreed with variants demonstrating superior adhesion compared to commercially available transdermal adhesive products. Finally, no cold flow effects were noticed a result of the crosslinked network/gel.Improving the adhesion and tack of pressure-sensitive adhesives (PSAs) in the absence of tackifier resins or fillers remains an ongoing challenge.},
	number = {8},
	urldate = {2024-03-26},
	journal = {MATERIALS ADVANCES},
	author = {Efstathiou, Spyridon and Nurumbetov, Gabit and Ross, Andrew and Li, Yongguang and Haddleton, David M.},
	month = apr,
	year = {2024},
	pages = {3396--3410},
}

Improving the adhesion and tack of pressure-sensitive adhesives (PSAs) remains an ongoing challenge. Polyureas often have stronger hydrogen bonding relative to, the more commonly used, polyurethanes which are quite common in adhesive applications. An increased adhesion can reduce the requirements for additives such as tackifier resins and fillers to achieve high levels of adhesion required in certain applications. This approach not only necessitates tedious optimisations but also introduces compatibility issues especially in drug-in-adhesive formulation development. In this work, novel silylated polyurea moisture-curable PSAs are introduced with moisture curing of silyl terminated polyether-urea prepolymers. Prepolymer variants were synthesised using a solvent and catalyst-free step-growth polymerisation by reacting the commercially available polyetheramine Jeffamine (R) D-4000 with isophorone diisocyanate (IPDI) to yield diprimaryamino-terminated polymers. The polymers' average molecular weight was controlled by adjusting the -NCO/-NH2 molar ratio. Subsequently, the amino terminal ends were post-functionalised with 3-isocyanatopropyltrimethoxysilane (IPTMS) to attain the silylated moisture-curable prepolymer variant crosslinkers (PUXL). The variants were able to cure to form (-Si-O-Si-) crosslinked PSA gels in the presence of a titanium catalyst and moisture. These materials were characterised by a range of techniques including rheology and thermal characterisation. Although their thermal properties remained unaltered, their adhesion and tack increased by increasing the -NCO/-NH2 molar ratio exceeding the borders of the Chang's classification windows for removable PSAs. This was achieved without the requirement for any additional tackifyer resins. Peel test and rolling ball tack tests agreed with variants demonstrating superior adhesion compared to commercially available transdermal adhesive products. Finally, no cold flow effects were noticed a result of the crosslinked network/gel.Improving the adhesion and tack of pressure-sensitive adhesives (PSAs) in the absence of tackifier resins or fillers remains an ongoing challenge.

@article{zhang_ph-responsive_2024,
	title = {{pH}-{Responsive} {Amphiphilic} {Triblock} {Fluoropolymers} as {Assemble} {Oxygen} {Nanoshuttles} for {Enhancing} {PDT} against {Hypoxic} {Tumor}},
	volume = {35},
	issn = {1043-1802},
	doi = {10.1021/acs.bioconjchem.4c00029},
	abstract = {Photodynamic therapy (PDT) is a cancer treatment strategy that utilizes photosensitizers to convert oxygen within tumors into reactive singlet oxygen (O-1(2)) to lyse tumor cells. Nevertheless, pre-existing tumor hypoxia and oxygen consumption during PDT can lead to an insufficient oxygen supply, potentially reducing the photodynamic efficacy. In response to this issue, we have devised a pH-responsive amphiphilic triblock fluorinated polymer (PDP) using copper-mediated RDRP. This polymer, composed of poly(ethylene glycol) methyl ether acrylate, 2-(diethylamino)ethyl methacrylate, and (perfluorooctyl)ethyl acrylate, self-assembles in an aqueous environment. Oxygen, chlorine e6 (Ce6), and doxorubicin (DOX) can be codelivered efficiently by PDP. The incorporation of perfluorocarbon into the formulation enhances the oxygen-carrying capacity of PDP, consequently extending the lifetime of O-1(2). This increased lifetime, in turn, amplifies the PDT effect and escalates the cellular cytotoxicity. Compared with PDT alone, PDP@Ce6-DOX-O-2 NPs demonstrated significant inhibition of tumor growth. This study proposes a novel strategy for enhancing the efficacy of PDT.},
	number = {3},
	urldate = {2024-02-28},
	journal = {BIOCONJUGATE CHEMISTRY},
	author = {Zhang, Jun-an and Haddleton, David and Wilson, Paul and Zhu, Lin-hua and Dai, Chun-yan and Zhao, Lin-lu},
	month = feb,
	year = {2024},
	note = {Trop Funct Polymer Mat Engn Res Ctr Hainan},
	pages = {400--411},
}

Photodynamic therapy (PDT) is a cancer treatment strategy that utilizes photosensitizers to convert oxygen within tumors into reactive singlet oxygen (O-1(2)) to lyse tumor cells. Nevertheless, pre-existing tumor hypoxia and oxygen consumption during PDT can lead to an insufficient oxygen supply, potentially reducing the photodynamic efficacy. In response to this issue, we have devised a pH-responsive amphiphilic triblock fluorinated polymer (PDP) using copper-mediated RDRP. This polymer, composed of poly(ethylene glycol) methyl ether acrylate, 2-(diethylamino)ethyl methacrylate, and (perfluorooctyl)ethyl acrylate, self-assembles in an aqueous environment. Oxygen, chlorine e6 (Ce6), and doxorubicin (DOX) can be codelivered efficiently by PDP. The incorporation of perfluorocarbon into the formulation enhances the oxygen-carrying capacity of PDP, consequently extending the lifetime of O-1(2). This increased lifetime, in turn, amplifies the PDT effect and escalates the cellular cytotoxicity. Compared with PDT alone, PDP@Ce6-DOX-O-2 NPs demonstrated significant inhibition of tumor growth. This study proposes a novel strategy for enhancing the efficacy of PDT.

@article{tooley_maddosy_2024,
	title = {{MaDDOSY} ({Mass} {Determination} {Diffusion} {Ordered} {Spectroscopy}) using an 80 {MHz} {Bench} {Top} {NMR} for the {Rapid} {Determination} of {Polymer} and {Macromolecular} {Molecular} {Weight}},
	volume = {45},
	issn = {1022-1336},
	doi = {10.1002/marc.202300692},
	abstract = {Measurement of molecular weight is an integral part of macromolecular and polymer characterization which usually has limitations. Herein, this article presents the use of a bench-top 80 MHz Nuclear Magnetic Resonance (NMR) spectrometer for diffusion-ordered spectroscopy as a practical and rapid approach for the determination of molecular weight/size using a novel solvent and polymer-independent universal calibration.Using diffusion-ordered spectroscopy (DOSY) on an 80 MHz benchtop NMR system, a solvent and polymer-independent calibration is presented for the determination of the molecular weight of macromolecules without the use of deuterated solvents or cryogens. The applicability of this system in a variety of different polymers and the agreement between the DOSY measurement and conventional techniques are shown. image},
	number = {8},
	urldate = {2024-02-18},
	journal = {MACROMOLECULAR RAPID COMMUNICATIONS},
	author = {Tooley, Owen and Pointer, William and Radmall, Rowan and Hall, Mia and Beyer, Valentin and Stakem, Kieran and Swift, Thomas and Town, James and Junkers, Tanja and Wilson, Paul and Lester, Daniel and Haddleton, David},
	month = apr,
	year = {2024},
}

Measurement of molecular weight is an integral part of macromolecular and polymer characterization which usually has limitations. Herein, this article presents the use of a bench-top 80 MHz Nuclear Magnetic Resonance (NMR) spectrometer for diffusion-ordered spectroscopy as a practical and rapid approach for the determination of molecular weight/size using a novel solvent and polymer-independent universal calibration.Using diffusion-ordered spectroscopy (DOSY) on an 80 MHz benchtop NMR system, a solvent and polymer-independent calibration is presented for the determination of the molecular weight of macromolecules without the use of deuterated solvents or cryogens. The applicability of this system in a variety of different polymers and the agreement between the DOSY measurement and conventional techniques are shown. image

@article{buatip_piezo-tribo-electric_2024,
	title = {Piezo-tribo-electric nanogenerator based on {BCZT}/{MCNTs}/{PDMS} piezoelectric composite for compressive energy harvesting},
	volume = {173},
	issn = {0025-5408},
	doi = {10.1016/j.materresbull.2024.112686},
	abstract = {Background: This work has developed a novel piezo-tribo-electric nanogenerator (P-TENG) that is capable of converting mechanical energy into electrical energy when operating in compressive mode. Methods: An arch-shaped P-TENG device was formed using an optimal piezoelectric polymer composite, which was fabricated using a polydimethylsiloxane (PDMS) matrix that was modified with piezoelectric (Ba0.85Ca0.15) (Ti0.90Zr0.10)O3 (BCZT) ceramic particles and electrically conductive multi-walled carbon nanotubes (MCNTs). A high filler loading of BCZT (40, 50, 60 wt\%) and 3 wt\% of MCNTs was formed into a 0-3 connectivity composite. Results: The P-TENG device containing 50 wt\% BCZT exhibited the highest electrical output (VOC - 39.7 V, ISC 1.9 mu A, and maximum power - 157.7 mu W), compared to the other composites, when subjected to an alternating compressive load of 500 N at a 1 Hz frequency. Conclusions: This research provides new composite formulations for elastomeric-based energy generators that are responsive to low frequency mechanical oscillations.},
	urldate = {2024-03-02},
	journal = {MATERIALS RESEARCH BULLETIN},
	author = {Buatip, Natthawadi and Munthala, Dhanunjaya and Amonpattaratkit, Penphitcha and Pakawanit, Phakkhananan and Hu, Xiao and Jongpinit, Watcharin and Janphuang, Pattanaphong and Wan, Chaoying and Bowen, Chris and Pojprapai, Soodkhet},
	month = may,
	year = {2024},
	note = {Synchrotron Light Res Inst
Biodyne Co Ltd},
}

Background: This work has developed a novel piezo-tribo-electric nanogenerator (P-TENG) that is capable of converting mechanical energy into electrical energy when operating in compressive mode. Methods: An arch-shaped P-TENG device was formed using an optimal piezoelectric polymer composite, which was fabricated using a polydimethylsiloxane (PDMS) matrix that was modified with piezoelectric (Ba0.85Ca0.15) (Ti0.90Zr0.10)O3 (BCZT) ceramic particles and electrically conductive multi-walled carbon nanotubes (MCNTs). A high filler loading of BCZT (40, 50, 60 wt%) and 3 wt% of MCNTs was formed into a 0-3 connectivity composite. Results: The P-TENG device containing 50 wt% BCZT exhibited the highest electrical output (VOC - 39.7 V, ISC 1.9 mu A, and maximum power - 157.7 mu W), compared to the other composites, when subjected to an alternating compressive load of 500 N at a 1 Hz frequency. Conclusions: This research provides new composite formulations for elastomeric-based energy generators that are responsive to low frequency mechanical oscillations.

@article{beres_photoiniferter-raft_2024,
	title = {Photoiniferter-{RAFT} polymerization mediated by bis(trithiocarbonate) disulfides},
	volume = {15},
	issn = {1759-9954},
	doi = {10.1039/d3py01307c},
	abstract = {Photoiniferter reversible addition fragmentation chain transfer (PI-RAFT) polymerization has gained significant attention; however, scalable methodologies are still lacking. Here, we investigate the use of a RAFT agent precursor, butyltrithiocarbonate disulfide (BisTTC), as an iniferter agent for the polymerization of two model monomers - methyl acrylate (MA) and methyl methacrylate (MMA). Different wavelengths of light were screened to optimise polymerization conditions for both monomers. While BisTTC can photodissociate and initiate polymerization, its activation under visible light is slow and competes with photodegradation. As for methyl acrylate, degradation only occurs during the induction period, so efficient initiation minimises potential side reactions, but the poly(methyl methacrylate)trithiocarbonate end group continues to degrade during polymerization due to the increased lifetime and stability of the propagating radical. Higher energy blue light gives poorer control than green light for the polymerization of MMA, due to increased photodegradation, whilst methyl acrylate polymerization is retarded under green light and requires conditions that strongly favour initiation.Photoiniferter reversible addition fragmentation chain transfer (PI-RAFT) polymerization has gained significant attention; however, scalable methodologies are still lacking.},
	number = {6},
	urldate = {2024-01-20},
	journal = {POLYMER CHEMISTRY},
	author = {Beres, Magdalena A. and Rho, Julia Y. and Kerr, Andrew and Smith, Timothy and Perrier, Sebastien},
	month = feb,
	year = {2024},
	pages = {522--533},
}

Photoiniferter reversible addition fragmentation chain transfer (PI-RAFT) polymerization has gained significant attention; however, scalable methodologies are still lacking. Here, we investigate the use of a RAFT agent precursor, butyltrithiocarbonate disulfide (BisTTC), as an iniferter agent for the polymerization of two model monomers - methyl acrylate (MA) and methyl methacrylate (MMA). Different wavelengths of light were screened to optimise polymerization conditions for both monomers. While BisTTC can photodissociate and initiate polymerization, its activation under visible light is slow and competes with photodegradation. As for methyl acrylate, degradation only occurs during the induction period, so efficient initiation minimises potential side reactions, but the poly(methyl methacrylate)trithiocarbonate end group continues to degrade during polymerization due to the increased lifetime and stability of the propagating radical. Higher energy blue light gives poorer control than green light for the polymerization of MMA, due to increased photodegradation, whilst methyl acrylate polymerization is retarded under green light and requires conditions that strongly favour initiation.Photoiniferter reversible addition fragmentation chain transfer (PI-RAFT) polymerization has gained significant attention; however, scalable methodologies are still lacking.

@article{bazazzadeh_improving_2024,
	title = {Improving damage resistance of solid-state battery cathodes with block copolymers: {A} non-linear diffusion-mechanics study at the microscale},
	volume = {264},
	issn = {0020-7403},
	doi = {10.1016/j.ijmecsci.2023.108808},
	abstract = {Minimizing interfacial failure in the composite cathode remains a crucial challenge to unravel the full potential of all solid-state batteries (ASSBs). Polymer-based ASSBs offer promising means of minimizing those damage effects due to their high ductility. However, multicomponent polymers such as block copolymers (BCPs) are needed to meet requirements for both ionic conductivity and mechanical resistance. This study aims to provide a new insight into the combined effects of block copolymer composition (soft-to-hard phase ratio) and interfacial strength on the coupled diffusion-mechanics response of an ASSB cathode, achieved by proposing a non-linear computational micromechanics approach. The approach combines a pressure-dependent diffusion process, interfacial gap-dependent diffusivity, and advanced elasto-viscoplastic constitutive model for a BCP, and it is implemented numerically within a non-linear finite element framework. Two cathode design concepts are explored here, with and without the BCP coating. Results from these case studies suggest that there is a strong interplay between the interface strength (between active particles and the BCP matrix), the BCP material composition, and the interfacial diffusivity. It is found that interfacial damage can be minimized by increasing both the interfacial strength and the amount of the soft component in the BCP system. If the diffusivity across the interface is damage-dependent, the latter is reduced when the BCP is predominantly made of the hard phase. Ultimately, a simple sensitivity analysis reveals that interfacial strength plays a vital role in minimizing interfacial damage, while the coating thickness is the least influential design parameter.},
	urldate = {2024-02-02},
	journal = {INTERNATIONAL JOURNAL OF MECHANICAL SCIENCES},
	author = {Bazazzadeh, Soheil and Pasta, Mauro and Figiel, Lukasz},
	month = feb,
	year = {2024},
}

Minimizing interfacial failure in the composite cathode remains a crucial challenge to unravel the full potential of all solid-state batteries (ASSBs). Polymer-based ASSBs offer promising means of minimizing those damage effects due to their high ductility. However, multicomponent polymers such as block copolymers (BCPs) are needed to meet requirements for both ionic conductivity and mechanical resistance. This study aims to provide a new insight into the combined effects of block copolymer composition (soft-to-hard phase ratio) and interfacial strength on the coupled diffusion-mechanics response of an ASSB cathode, achieved by proposing a non-linear computational micromechanics approach. The approach combines a pressure-dependent diffusion process, interfacial gap-dependent diffusivity, and advanced elasto-viscoplastic constitutive model for a BCP, and it is implemented numerically within a non-linear finite element framework. Two cathode design concepts are explored here, with and without the BCP coating. Results from these case studies suggest that there is a strong interplay between the interface strength (between active particles and the BCP matrix), the BCP material composition, and the interfacial diffusivity. It is found that interfacial damage can be minimized by increasing both the interfacial strength and the amount of the soft component in the BCP system. If the diffusivity across the interface is damage-dependent, the latter is reduced when the BCP is predominantly made of the hard phase. Ultimately, a simple sensitivity analysis reveals that interfacial strength plays a vital role in minimizing interfacial damage, while the coating thickness is the least influential design parameter.

@article{morozov_stability_2024,
	title = {Stability of chemical reaction fronts in solids: {Analytical} and numerical approaches},
	volume = {104},
	issn = {0997-7538},
	doi = {10.1016/j.euromechsol.2023.105211},
	abstract = {Localized chemical reactions in deformable solids are considered. A chemical transformation is accompanied by the transformation strain and emerging mechanical stresses, which affect the kinetics of the chemical reaction front to the reaction arrest. A chemo-mechanical coupling via the chemical affinity tensor is used, in which the stresses affect the reaction rate. The emphasis is made on the stability of the propagating reaction front in the vicinity of the blocked state. There are two major novel contributions. First, it is shown that for a planar reaction front, the diffusion of the gaseous-type reactant does not influence the stability of the reaction front - the stability is governed only by the mechanical properties of solid reactants and stresses induced by the transformation strain and the external loading, which corresponds to the mathematically analogous phase transition problem. Second, the comparison of two computational approaches to model the reaction front propagation is performed - the standard finite-element method with a remeshing technique to resolve the moving interface is compared to the cut-finite-element-based approach, which allows the interface to cut through the elements and to move independently of the finite-element mesh. For stability problems considered in the present paper, the previously-developed implementation of the cut-element approach has been extended with the additional post-processing procedure that obtains more accurate stresses and strains, relying on the fact that the structured grid is used in the implementation. The approaches are compared using a range of chemo-mechanical problems with stable and unstable reaction fronts.},
	urldate = {2024-01-29},
	journal = {EUROPEAN JOURNAL OF MECHANICS A-SOLIDS},
	author = {Morozov, A. and Poluektov, M. and Freidin, A. B. and Figiel, L. and Mueller, W. H.},
	month = apr,
	year = {2024},
}

Localized chemical reactions in deformable solids are considered. A chemical transformation is accompanied by the transformation strain and emerging mechanical stresses, which affect the kinetics of the chemical reaction front to the reaction arrest. A chemo-mechanical coupling via the chemical affinity tensor is used, in which the stresses affect the reaction rate. The emphasis is made on the stability of the propagating reaction front in the vicinity of the blocked state. There are two major novel contributions. First, it is shown that for a planar reaction front, the diffusion of the gaseous-type reactant does not influence the stability of the reaction front - the stability is governed only by the mechanical properties of solid reactants and stresses induced by the transformation strain and the external loading, which corresponds to the mathematically analogous phase transition problem. Second, the comparison of two computational approaches to model the reaction front propagation is performed - the standard finite-element method with a remeshing technique to resolve the moving interface is compared to the cut-finite-element-based approach, which allows the interface to cut through the elements and to move independently of the finite-element mesh. For stability problems considered in the present paper, the previously-developed implementation of the cut-element approach has been extended with the additional post-processing procedure that obtains more accurate stresses and strains, relying on the fact that the structured grid is used in the implementation. The approaches are compared using a range of chemo-mechanical problems with stable and unstable reaction fronts.

@article{dedola_sialic_2024,
	title = {Sialic acids in infection and their potential use in detection and protection against pathogens},
	volume = {5},
	issn = {2633-0679},
	doi = {10.1039/d3cb00155e},
	abstract = {In structural terms, the sialic acids are a large family of nine carbon sugars based around an alpha-keto acid core. They are widely spread in nature, where they are often found to be involved in molecular recognition processes, including in development, immunology, health and disease. The prominence of sialic acids in infection is a result of their exposure at the non-reducing terminus of glycans in diverse glycolipids and glycoproteins. Herein, we survey representative aspects of sialic acid structure, recognition and exploitation in relation to infectious diseases, their diagnosis and prevention or treatment. Examples covered span influenza virus and Covid-19, Leishmania and Trypanosoma, algal viruses, Campylobacter, Streptococci and Helicobacter, and commensal Ruminococci.An overview of sialic acid involvement in infection and exploitation in diagnostics and therapeutics.},
	number = {3},
	urldate = {2024-01-23},
	journal = {RSC CHEMICAL BIOLOGY},
	author = {Dedola, Simone and Ahmadipour, Sanaz and de Andrade, Peterson and Baker, Alexander N. and Boshra, Andrew N. and Chessa, Simona and Gibson, Matthew I. and Hernando, Pedro J. and Ivanova, Irina M. and Lloyd, Jessica E. and Marin, Maria J. and Munro-Clark, Alexandra J. and Pergolizzi, Giulia and Richards, Sarah-Jane and Ttofi, Iakovia and Wagstaff, Ben A. and Field, Robert A.},
	month = mar,
	year = {2024},
	note = {Norwich Res Pk},
	pages = {167--188},
}

In structural terms, the sialic acids are a large family of nine carbon sugars based around an alpha-keto acid core. They are widely spread in nature, where they are often found to be involved in molecular recognition processes, including in development, immunology, health and disease. The prominence of sialic acids in infection is a result of their exposure at the non-reducing terminus of glycans in diverse glycolipids and glycoproteins. Herein, we survey representative aspects of sialic acid structure, recognition and exploitation in relation to infectious diseases, their diagnosis and prevention or treatment. Examples covered span influenza virus and Covid-19, Leishmania and Trypanosoma, algal viruses, Campylobacter, Streptococci and Helicobacter, and commensal Ruminococci.An overview of sialic acid involvement in infection and exploitation in diagnostics and therapeutics.

@article{magee_polyelectrolyte_2024,
	title = {Polyelectrolyte {Complexation} of {Chitosan} and {WS2} {Nanotubes}},
	volume = {11},
	issn = {2196-7350},
	doi = {10.1002/admi.202300501},
	abstract = {The inclusion of tungsten disulphide nanotubes (WS2 NTs) in chitosan, plasticized with glycerol, facilitates the formation of a polyelectrolyte complex. The glycerol interrupts the intramolecular hydrogen bonding between chitosan chains allowing positively charged protonated amines of chitosan to form a complex with negatively charged oxygen ions chemisorbed to the tungsten atoms in defects. These interactions, with the unique mechanical and chemical properties of WS2 NTs, result in a chitosan film with superior properties relative to unfilled chitosan. Even at low WS2 NT loadings ({\textless}= 1 wt\%), the Young's modulus (E) increases by 59\%, tensile strength (sigma) by 40\% and tensile toughness by 74\%, compared to neat chitosan, without sacrificing ductility. Addition of highly dispersed WS2 NTs significantly improves the gas barrier properties of chitosan, with a 50\% reduction in oxygen permeability, while the addition of both glycerol and WS2 NTs to chitosan effectively reduces the carbon dioxide permeability by 80\% and the water vapor transmission rate by 90\%. The intrinsic antimicrobial efficacy of chitosan against both Gram-positive and Gram-negative bacteria is enhanced on inclusion of WS2 NTs. Polyelectrolyte complexation of WS2 NTs and glycerol-plasticized chitosan provides a cost-effective, sustainable route to biodegradable films with desirable mechanical, gas barrier properties, and antimicrobial efficacy suitable for food packaging applications.},
	number = {6},
	urldate = {2024-01-13},
	journal = {ADVANCED MATERIALS INTERFACES},
	author = {Magee, Eimear and Xie, Fengwei and Farris, Stefano and Dsouza, Andrea and Constantinidou, Chrystala and Zak, Alla and Tenne, Reshef and Mcnally, Tony},
	month = feb,
	year = {2024},
	note = {Holon Inst Technol},
}

The inclusion of tungsten disulphide nanotubes (WS2 NTs) in chitosan, plasticized with glycerol, facilitates the formation of a polyelectrolyte complex. The glycerol interrupts the intramolecular hydrogen bonding between chitosan chains allowing positively charged protonated amines of chitosan to form a complex with negatively charged oxygen ions chemisorbed to the tungsten atoms in defects. These interactions, with the unique mechanical and chemical properties of WS2 NTs, result in a chitosan film with superior properties relative to unfilled chitosan. Even at low WS2 NT loadings (\textless= 1 wt%), the Young's modulus (E) increases by 59%, tensile strength (sigma) by 40% and tensile toughness by 74%, compared to neat chitosan, without sacrificing ductility. Addition of highly dispersed WS2 NTs significantly improves the gas barrier properties of chitosan, with a 50% reduction in oxygen permeability, while the addition of both glycerol and WS2 NTs to chitosan effectively reduces the carbon dioxide permeability by 80% and the water vapor transmission rate by 90%. The intrinsic antimicrobial efficacy of chitosan against both Gram-positive and Gram-negative bacteria is enhanced on inclusion of WS2 NTs. Polyelectrolyte complexation of WS2 NTs and glycerol-plasticized chitosan provides a cost-effective, sustainable route to biodegradable films with desirable mechanical, gas barrier properties, and antimicrobial efficacy suitable for food packaging applications.

@article{lee_branched_2024,
	title = {Branched polymer grafted graphene oxide ({GO}) as a {2D} template for calcium phosphate growth},
	volume = {675},
	issn = {0021-9797},
	url = {https://www.sciencedirect.com/science/article/pii/S0021979724014693},
	doi = {10.1016/j.jcis.2024.06.221},
	abstract = {Hypothesis
Graphene Oxide (GO)-templated deposition of inorganic materials through synthesis on dispersed single sheets of GO is often complicated by the loss of the desired 2D morphology owing to the coagulation of GO sheets at high salt concentrations and non-templated homogenous nucleation. Modifying GO with anionic polymer is expected to solve both problems by i) enhancing electrostatic(steric) stabilization upon exposure to high concentrations of the ionic precursors, and ii) offering additional nucleation sites at the grafted anionic moieties to avoid homogeneous secondary nucleation.
Experiments
GO was grafted with branched copolymers of poly(ethylene glycol) methacrylate (PEGMA 500) and diethylene glycol dimethacrylate (DEGDMA) and ω-vinyl terminated methacrylic acid macromonomer (P(MAA)), the latter serving as an addition-fragmentation chain transfer agent. The colloidal stability of GO dispersions in water toward salt was evaluated before and after modification. Precipitation of calcium phosphate (CaP) was performed by incubating modified GO in the precursor solutions. The conditions were optimized to maximize the nucleation selectively onto GO without homogeneous CaP nucleation and coagulation of the GO-sheets.
Findings
The copolymer grafted GO-sheets shows superior colloidal stability when dispersed in water. No aggregation occurs in the incubating ionic CaP precursor solutions. The optimum templated deposition of CaP onto the GO sheets by precipitation is to add a second shot of precursors after the nucleation stage to obtain GO sheets fully decorated with calcium phosphate nanorods without self-nucleation. Via the careful design on the GO modification and incubation process, the growth of calcium phosphate nanorods were confined in the desired 2D order exclusively, hereby achieving the goal of an efficient GO-templated synthesis.},
	urldate = {2024-09-14},
	journal = {Journal of Colloid and Interface Science},
	author = {Lee, Wai Hin and Bon, Stefan A. F.},
	month = dec,
	year = {2024},
	keywords = {Branched polymer, Calcium phosphate, Colloidal stability, Graphene oxide, Templated synthesis},
	pages = {438--450},
}

Hypothesis Graphene Oxide (GO)-templated deposition of inorganic materials through synthesis on dispersed single sheets of GO is often complicated by the loss of the desired 2D morphology owing to the coagulation of GO sheets at high salt concentrations and non-templated homogenous nucleation. Modifying GO with anionic polymer is expected to solve both problems by i) enhancing electrostatic(steric) stabilization upon exposure to high concentrations of the ionic precursors, and ii) offering additional nucleation sites at the grafted anionic moieties to avoid homogeneous secondary nucleation. Experiments GO was grafted with branched copolymers of poly(ethylene glycol) methacrylate (PEGMA 500) and diethylene glycol dimethacrylate (DEGDMA) and ω-vinyl terminated methacrylic acid macromonomer (P(MAA)), the latter serving as an addition-fragmentation chain transfer agent. The colloidal stability of GO dispersions in water toward salt was evaluated before and after modification. Precipitation of calcium phosphate (CaP) was performed by incubating modified GO in the precursor solutions. The conditions were optimized to maximize the nucleation selectively onto GO without homogeneous CaP nucleation and coagulation of the GO-sheets. Findings The copolymer grafted GO-sheets shows superior colloidal stability when dispersed in water. No aggregation occurs in the incubating ionic CaP precursor solutions. The optimum templated deposition of CaP onto the GO sheets by precipitation is to add a second shot of precursors after the nucleation stage to obtain GO sheets fully decorated with calcium phosphate nanorods without self-nucleation. Via the careful design on the GO modification and incubation process, the growth of calcium phosphate nanorods were confined in the desired 2D order exclusively, hereby achieving the goal of an efficient GO-templated synthesis.

@article{xia_effective_2023,
	title = {Effective and {Fast}-{Screening} {Route} to {Evaluate} {Dynamic} {Elastomer}-{Filler} {Network} {Reversibility} for {Sustainable} {Rubber} {Composite} {Design}},
	volume = {11},
	issn = {2168-0485},
	doi = {10.1021/acssuschemeng.3c06752},
	abstract = {The introduction of self-healing and reprocessability into conventional vulcanized rubbers has been recognized as a promising strategy to promote elastomer circularity. However, the reversibility and recovery of cross-linking polymer networks have often been assessed by static mechanical testing, which highly limits the understanding of the underlying microscale mechanisms. In this work, we investigated the network recovery of natural rubber (NR)/carbon black (CB) nanocomposites using Fourier transform (FT) rheology coupled with large amplitude oscillation shear (LAOS) technology across linear and nonlinear regimes (0.01-500\%). The self-healing process of the rubber composite networks was monitored by using a programmed time-temperature oscillation shear measurement. The role of CB particle size in the filler network recovery was also discussed from the perspective of strain-induced crystallization of NR. Coupling FT-rheology and LAOS analysis, two distinct nonlinear enhancement behaviors beyond the linear viscoelastic regime were detected in the rubber nanocomposites, which were ascribed to the filler network disruption followed by the polymer network deformation. The relationship of the nonlinearity parameter I (3/1) as a function of strain amplitude was selected to quantify the nonlinear rheological responses, where the role of the filler and polymer on the network recovery can therefore be differentiated. This work provides an efficient method to evaluate the self-healing and reprocessability of cross-linked rubbers and offers a fast-screen route for formulation development and sustainable rubber composite design.},
	number = {50},
	urldate = {2024-01-06},
	journal = {ACS SUSTAINABLE CHEMISTRY \& ENGINEERING},
	author = {Xia, Tian and Wemyss, Alan M. and Salehiyan, Reza and Heeley, Ellen L. and Hu, Xiao and Tang, Fengzai and Sun, Yuchen and Hughes, Darren J. and Mcnally, Tony and Wan, Chaoying},
	month = dec,
	year = {2023},
	pages = {17857--17869},
}

The introduction of self-healing and reprocessability into conventional vulcanized rubbers has been recognized as a promising strategy to promote elastomer circularity. However, the reversibility and recovery of cross-linking polymer networks have often been assessed by static mechanical testing, which highly limits the understanding of the underlying microscale mechanisms. In this work, we investigated the network recovery of natural rubber (NR)/carbon black (CB) nanocomposites using Fourier transform (FT) rheology coupled with large amplitude oscillation shear (LAOS) technology across linear and nonlinear regimes (0.01-500%). The self-healing process of the rubber composite networks was monitored by using a programmed time-temperature oscillation shear measurement. The role of CB particle size in the filler network recovery was also discussed from the perspective of strain-induced crystallization of NR. Coupling FT-rheology and LAOS analysis, two distinct nonlinear enhancement behaviors beyond the linear viscoelastic regime were detected in the rubber nanocomposites, which were ascribed to the filler network disruption followed by the polymer network deformation. The relationship of the nonlinearity parameter I (3/1) as a function of strain amplitude was selected to quantify the nonlinear rheological responses, where the role of the filler and polymer on the network recovery can therefore be differentiated. This work provides an efficient method to evaluate the self-healing and reprocessability of cross-linked rubbers and offers a fast-screen route for formulation development and sustainable rubber composite design.

@article{kerr_anchor_2023,
	title = {Anchor {Group} {Bottlebrush} {Polymers} as {Oil} {Additive} {Friction} {Modifiers}},
	volume = {15},
	issn = {1944-8244},
	doi = {10.1021/acsami.3c12628},
	abstract = {Surface-tethered polymers have been shown to be an efficient lubrication strategy for boundary and mixed lubrication by providing a solvated film between solid surfaces. We have assessed the performance of various graft copolymers as friction modifier additives in oil and revealed important structure-property relationships for this application. The polymers consisted of an oil-soluble, grafted poly(lauryl acrylate) segment and a polar, linear poly(4-acryloylmorpholine) anchor group. Reversible addition-fragmentation chain transfer polymerization was used to access various architectures with control of the grafting density and position of the anchor group. Macrotribological studies displayed promising results with approximate to 50\% reduction in friction coefficient at low polymer treatment rates. QCM-D experiments, neutron reflectometry, small-angle neutron scattering, and atomic force microscopy were used to gather detailed information on these polymers' surface adsorption characteristics, film structure, and solution behavior.},
	number = {41},
	urldate = {2023-10-28},
	journal = {ACS APPLIED MATERIALS \& INTERFACES},
	author = {Kerr, Andrew and Hakkinen, Satu and Hall, Stephen C. L. and Kirkman, Paul and O'Hora, Paul and Smith, Timothy and Kinane, Christian J. and Caruana, Andrew and Perrier, Sebastien},
	month = oct,
	year = {2023},
	pages = {48574--48583},
}

Surface-tethered polymers have been shown to be an efficient lubrication strategy for boundary and mixed lubrication by providing a solvated film between solid surfaces. We have assessed the performance of various graft copolymers as friction modifier additives in oil and revealed important structure-property relationships for this application. The polymers consisted of an oil-soluble, grafted poly(lauryl acrylate) segment and a polar, linear poly(4-acryloylmorpholine) anchor group. Reversible addition-fragmentation chain transfer polymerization was used to access various architectures with control of the grafting density and position of the anchor group. Macrotribological studies displayed promising results with approximate to 50% reduction in friction coefficient at low polymer treatment rates. QCM-D experiments, neutron reflectometry, small-angle neutron scattering, and atomic force microscopy were used to gather detailed information on these polymers' surface adsorption characteristics, film structure, and solution behavior.

@article{hayes_poly2-oxazolinesarna_2023,
	title = {Poly(2-oxazoline)/{saRNA} {Polyplexes} for {Targeted} and {Nonviral} {Gene} {Delivery}},
	volume = {24},
	issn = {1525-7797},
	doi = {10.1021/acs.biomac.3c00683},
	abstract = {RNA delivery has been demonstrated to be a potent method of vaccine delivery, as demonstrated by the recent success of the COVID-19 vaccines. Polymers have been shown to be effective vehicles for RNA delivery, with poly(ethylene imine) (PEI) being the current gold standard for delivery. Nonetheless, PEI has toxicity concerns, and so finding alternatives is desirable. Poly(2-oxazoline)s are a promising alternative to PEI, as they are generally biocompatible and offer a high degree of control over the polymer structure. Here, we have synthesized an ionizable primary amine 2-oxazoline and combined it with a double bond containing oxazoline to synthesize a small library of charged statistical and block copolymers. The pendant double bonds were reacted further to decorate the polymers with glucose via a thiol-ene click reaction. All polymers were shown to have excellent cell viability, and the synthesized block polymers showed promising complexation efficiencies for the saRNA, demonstrating a clear structure-property relationship. The polymer transfection potential was tested in various cell lines, and a polymer composition with an amine/glucose ratio of 9:27 has demonstrated the best transfection potential across all cell lines tested. Overall, the results suggest that block polymers with a cationic segment and high levels of glycosylation have the best complexation efficiency and RNA expression levels.},
	number = {11},
	urldate = {2023-10-19},
	journal = {BIOMACROMOLECULES},
	author = {Hayes, Graham and Dias-Barbieri, Beatriz and Yilmaz, Gokhan and Shattock, Robin J. and Becer, C. Remzi},
	month = oct,
	year = {2023},
	pages = {5142--5151},
}

RNA delivery has been demonstrated to be a potent method of vaccine delivery, as demonstrated by the recent success of the COVID-19 vaccines. Polymers have been shown to be effective vehicles for RNA delivery, with poly(ethylene imine) (PEI) being the current gold standard for delivery. Nonetheless, PEI has toxicity concerns, and so finding alternatives is desirable. Poly(2-oxazoline)s are a promising alternative to PEI, as they are generally biocompatible and offer a high degree of control over the polymer structure. Here, we have synthesized an ionizable primary amine 2-oxazoline and combined it with a double bond containing oxazoline to synthesize a small library of charged statistical and block copolymers. The pendant double bonds were reacted further to decorate the polymers with glucose via a thiol-ene click reaction. All polymers were shown to have excellent cell viability, and the synthesized block polymers showed promising complexation efficiencies for the saRNA, demonstrating a clear structure-property relationship. The polymer transfection potential was tested in various cell lines, and a polymer composition with an amine/glucose ratio of 9:27 has demonstrated the best transfection potential across all cell lines tested. Overall, the results suggest that block polymers with a cationic segment and high levels of glycosylation have the best complexation efficiency and RNA expression levels.

@article{little_synthesis_2023,
	title = {Synthesis and {Characterization} of {High} {Glycolic} {Acid} {Content} {Poly}(glycolic acid-co-butylene adipate-co-butylene terephthalate) and {Poly}(glycolic acid-co-butylene succinate) {Copolymers} with {Improved} {Elasticity}},
	volume = {8},
	issn = {2470-1343},
	doi = {10.1021/acsomega.3c05932},
	abstract = {Poly(glycolic acid) (PGA) is a biodegradable polymer with high gas barrier properties, mechanical strength, and heat deflection temperature. However, PGA's brittleness severely limits its application in packaging, creating a need to develop PGA-based copolymers with improved elasticity that maintain its barrier properties and hydrolytic degradability. In this work, a series of PGBAT (poly(glycolic acid-co-butylene) adipate-co-butylene terephthalate) copolymers containing 21-92\% glycolic acid (n(GA)) with M-w values of 46,700-50,600 g mol(-1) were synthesized via melt polycondensation, and the effects of altering the n(GA) on PGBAT's thermomechanical properties and hydrolysis rate were investigated. Poly(glycolic acid-co-butylene succinate) (PGBS) and poly(glycolic acid-co-butylene terephthalate) (PGBT) copolymers with high n(GA) were synthesized for comparison. DSC analysis revealed that PGBAT21 (n(GA) = 21\%) and PGBAT92 were semicrystalline, melting between 102.8 and 163.3 degrees C, while PGBAT44, PGBAT86-89, PGBT80, and PGBS90 were amorphous, with T-g values from -19.0 to 23.7 degrees C. These high n(GA) copolymers showed similar rates of hydrolysis to PGA, whereas those containing {\textless}50\% GA showed almost no mass loss over the testing period. Their mechanical properties were highly dependent upon their crystallinity and improved significantly after annealing. Of the high n(GA) copolymers, annealed PGBS90 (M-w 97,000 g mol(-1)) possessed excellent mechanical properties with a modulus of 588 MPa, tensile strength of 30.0 MPa, and elongation at break of 171\%, a significant improvement on PGA's elongation at break of 3\%. This work demonstrates the potential of enhancing PGA's flexibility by introducing minor amounts of low-cost diols and diacids into its synthesis.},
	number = {41},
	urldate = {2023-10-22},
	journal = {ACS OMEGA},
	author = {Little, Alastair and Ma, Shiyue and Haddleton, David M. and Tan, Bowen and Sun, Zhaoyang and Wan, Chaoying},
	month = oct,
	year = {2023},
	note = {PJIM Polymer Sci Co Ltd},
	pages = {38658--38667},
}

Poly(glycolic acid) (PGA) is a biodegradable polymer with high gas barrier properties, mechanical strength, and heat deflection temperature. However, PGA's brittleness severely limits its application in packaging, creating a need to develop PGA-based copolymers with improved elasticity that maintain its barrier properties and hydrolytic degradability. In this work, a series of PGBAT (poly(glycolic acid-co-butylene) adipate-co-butylene terephthalate) copolymers containing 21-92% glycolic acid (n(GA)) with M-w values of 46,700-50,600 g mol(-1) were synthesized via melt polycondensation, and the effects of altering the n(GA) on PGBAT's thermomechanical properties and hydrolysis rate were investigated. Poly(glycolic acid-co-butylene succinate) (PGBS) and poly(glycolic acid-co-butylene terephthalate) (PGBT) copolymers with high n(GA) were synthesized for comparison. DSC analysis revealed that PGBAT21 (n(GA) = 21%) and PGBAT92 were semicrystalline, melting between 102.8 and 163.3 degrees C, while PGBAT44, PGBAT86-89, PGBT80, and PGBS90 were amorphous, with T-g values from -19.0 to 23.7 degrees C. These high n(GA) copolymers showed similar rates of hydrolysis to PGA, whereas those containing \textless50% GA showed almost no mass loss over the testing period. Their mechanical properties were highly dependent upon their crystallinity and improved significantly after annealing. Of the high n(GA) copolymers, annealed PGBS90 (M-w 97,000 g mol(-1)) possessed excellent mechanical properties with a modulus of 588 MPa, tensile strength of 30.0 MPa, and elongation at break of 171%, a significant improvement on PGA's elongation at break of 3%. This work demonstrates the potential of enhancing PGA's flexibility by introducing minor amounts of low-cost diols and diacids into its synthesis.

@article{gauci_power_2023,
	title = {The {Power} of {Action} {Plots}: {Unveiling} {Reaction} {Selectivity} of {Light}-{Stabilized} {Dynamic} {Covalent} {Chemistry}},
	volume = {62},
	issn = {1433-7851},
	doi = {10.1002/anie.202310274},
	abstract = {Exploiting the optimum wavelength of reactivity for efficient photochemical reactions has been well-established based on the development of photochemical action plots. We herein demonstrate the power of such action plots by a remarkable example of the wavelength-resolved photochemistry of two triazolinedione (TAD) substrates, i.e., aliphatic and aromatic substituted, that exhibit near identical absorption spectra yet possess vastly disparate photoreactivity. We present our findings in carefully recorded action plots, from which reaction selectivity is identified. The profound difference in photoreactivity is exploited by designing a 'hybrid' bisfunctional TAD molecule, enabling the formation of a dual-gated reaction manifold that demonstrates the exceptional and site-selective (photo)chemical behavior of both TAD substrates within a single small molecule.},
	number = {40},
	urldate = {2023-11-09},
	journal = {ANGEWANDTE CHEMIE-INTERNATIONAL EDITION},
	author = {Gauci, Steven C. and Du Prez, Filip E. and Holloway, Joshua O. and Houck, Hannes A. and Barner-Kowollik, Christopher},
	month = oct,
	year = {2023},
}

Exploiting the optimum wavelength of reactivity for efficient photochemical reactions has been well-established based on the development of photochemical action plots. We herein demonstrate the power of such action plots by a remarkable example of the wavelength-resolved photochemistry of two triazolinedione (TAD) substrates, i.e., aliphatic and aromatic substituted, that exhibit near identical absorption spectra yet possess vastly disparate photoreactivity. We present our findings in carefully recorded action plots, from which reaction selectivity is identified. The profound difference in photoreactivity is exploited by designing a 'hybrid' bisfunctional TAD molecule, enabling the formation of a dual-gated reaction manifold that demonstrates the exceptional and site-selective (photo)chemical behavior of both TAD substrates within a single small molecule.

@article{concilio_synthesis_2023,
	title = {Synthesis of {Oxazoline}/{Methacrylate}-{Based} {Graft}-{Copolymers} via {Grafting}-{Through} {Method} and {Evaluation} of {Their} {Self}-{Assembly} in {Water} and {Dodecane}},
	volume = {56},
	issn = {0024-9297},
	doi = {10.1021/acs.macromol.3c01308},
	abstract = {Well-defined graft-copolymers of poly(2-ethyl-2-oxazoline)methacrylate macromonomer (PEtOxMM), n-butyl methacrylate, and n-lauryl methacrylate were synthesized via the grafting-through method. The effect of composition on the thermal properties and solution behavior was investigated. Differential scanning calorimetry and thermogravimetric analysis showed little dependency of the thermal properties on the terpolymer composition, while the solution properties were found to be strongly dependent. Varying the PEtOxMM content, the resulting graft- copolymers were found to be soluble in water or n-dodecane. A thermoresponsive behavior was observed only for the graft-copolymers in water, as shown by turbidity measurements and dynamic light scattering analysis. Small-angle X-ray scattering measurements at different temperatures were performed to investigate the self-assembly behavior of the graft-copolymers in both n-dodecane and water. A range of temperature-triggered morphological transitions was observed in both solvents depending on the graft-copolymer composition. These graft-copolymers were able to self-assemble into different morphologies in both n-dodecane and water, exhibiting a high temperature stability.},
	number = {19},
	urldate = {2023-10-14},
	journal = {MACROMOLECULES},
	author = {Concilio, Matilde and Nguyen, Nga and Hall, Stephen C. L. and Huband, Steven and Becer, C. Remzi},
	month = sep,
	year = {2023},
	note = {Infineum USA},
	pages = {7961--7972},
}

Well-defined graft-copolymers of poly(2-ethyl-2-oxazoline)methacrylate macromonomer (PEtOxMM), n-butyl methacrylate, and n-lauryl methacrylate were synthesized via the grafting-through method. The effect of composition on the thermal properties and solution behavior was investigated. Differential scanning calorimetry and thermogravimetric analysis showed little dependency of the thermal properties on the terpolymer composition, while the solution properties were found to be strongly dependent. Varying the PEtOxMM content, the resulting graft- copolymers were found to be soluble in water or n-dodecane. A thermoresponsive behavior was observed only for the graft-copolymers in water, as shown by turbidity measurements and dynamic light scattering analysis. Small-angle X-ray scattering measurements at different temperatures were performed to investigate the self-assembly behavior of the graft-copolymers in both n-dodecane and water. A range of temperature-triggered morphological transitions was observed in both solvents depending on the graft-copolymer composition. These graft-copolymers were able to self-assemble into different morphologies in both n-dodecane and water, exhibiting a high temperature stability.

@article{lefley_amphiphilic_2023,
	title = {Amphiphilic oligo(2-ethyl-2-oxazoline)s via straightforward synthesis and their self-assembly behaviour},
	volume = {14},
	issn = {1759-9954},
	doi = {10.1039/d3py00809f},
	abstract = {The synthesis of poly(2-oxazoline)s offers an unparalleled degree of functionalization when fabricating smart, functional polymers for biomedical uses. The termination of 2-oxazoline polymerisations by direct endcapping can be exploited to introduce a wide variety of end groups and could potentially offer an easier synthetic route to amphiphilic polymers that usually block copolymer synthesis. Herein, we report a facile one-pot synthesis and preparation of dodecyl-end capped oligo(2-ethyl-2-oxazoline)s via direct endcapping and thiol-yne click chemistry. A small set of propargyl tosylate initiated PEtOx oligomers were synthesised and subsequently functionalized with varying equivalents of dodecanethiol. GPC, NMR and MALDI-ToF were utilised for molecular weight analysis and determination of end-group fidelity. Film rehydration was employed to prepare self-assembled nanoparticles due the inexpensive set-up and practical simplicity of the technique. DLS, SAXS and TEM revealed that mono- and di-functionalized PEtOx self-assembled into micelles around 10 nm in diameter whereas tri-functionalized PEtOx was too hydrophobic and precipitated in aqueous solution. All oligomers were screened for their ability to encapsulate a model hydrophobic drug, curcumin, and UV-Vis spectrometry was utilized to determine the encapsulation efficiencies and drug loading capacities. Di-functionalized PEtOx provided the greatest drug loading capacity (8 wt\%) of this study.},
	number = {43},
	urldate = {2023-10-14},
	journal = {POLYMER CHEMISTRY},
	author = {Lefley, James and Varanaraja, Zivani and Drain, Ben and Huband, Steven and Beament, James and Becer, C. Remzi},
	month = nov,
	year = {2023},
	note = {Infineum UK Ltd},
	pages = {4890--4897},
}

The synthesis of poly(2-oxazoline)s offers an unparalleled degree of functionalization when fabricating smart, functional polymers for biomedical uses. The termination of 2-oxazoline polymerisations by direct endcapping can be exploited to introduce a wide variety of end groups and could potentially offer an easier synthetic route to amphiphilic polymers that usually block copolymer synthesis. Herein, we report a facile one-pot synthesis and preparation of dodecyl-end capped oligo(2-ethyl-2-oxazoline)s via direct endcapping and thiol-yne click chemistry. A small set of propargyl tosylate initiated PEtOx oligomers were synthesised and subsequently functionalized with varying equivalents of dodecanethiol. GPC, NMR and MALDI-ToF were utilised for molecular weight analysis and determination of end-group fidelity. Film rehydration was employed to prepare self-assembled nanoparticles due the inexpensive set-up and practical simplicity of the technique. DLS, SAXS and TEM revealed that mono- and di-functionalized PEtOx self-assembled into micelles around 10 nm in diameter whereas tri-functionalized PEtOx was too hydrophobic and precipitated in aqueous solution. All oligomers were screened for their ability to encapsulate a model hydrophobic drug, curcumin, and UV-Vis spectrometry was utilized to determine the encapsulation efficiencies and drug loading capacities. Di-functionalized PEtOx provided the greatest drug loading capacity (8 wt%) of this study.

@article{sinniger_synthesis_2023,
	title = {Synthesis of poly(methyl methacrylate)-b-polyethylene ({PMMA}-b-{PE}) block copolymers via conventional emulsion polymerization},
	volume = {14},
	issn = {1759-9954},
	doi = {10.1039/d3py00897e},
	abstract = {Poly(methyl methacrylate)-b-polyethylene (PMMA-b-PE) block copolymers were recently obtained simply by involving omega-unsaturated PMMA oligomers prepared by CCTP in the radical polymerization of ethylene performed in dimethylcarbonate (DMC) solution (F. Baffie, G. Patias, A. Shegiwal, F. Brunel, V. Monteil, L. Verrieux, L. Perrin, D. M. Haddleton and F. D'Agosto, Angew. Chem., Int. Ed., 2021, 60, 25356-25364). However, omega-unsaturated PMMA oligomers are more effectively obtained as a latex by emulsion CCTP. In the present paper, these resulting latexes were used as seeds in the radical emulsion polymerization of ethylene in water. The effects of the methacrylic oligomer molar mass and the initial solids content of the seeds were investigated. Cryo-TEM analysis enabled demonstration of the formation of stable latexes composed of faceted spherical particles. The increase of molar mass correlated to the consumption of unsaturated oligomers with the polymerization time indicated the formation of block copolymers. The present study successfully transposed the chemistry performed in DMC solution and PMMA-b-PE block copolymers were obtained by a simple post-treatment of a PMMA latex.},
	number = {39},
	urldate = {2023-11-05},
	journal = {POLYMER CHEMISTRY},
	author = {Sinniger, L. and Boyron, O. and Dugas, P. Y. and Patias, G. and Lester, D. and Haddleton, D. M. and Monteil, V. and Lansalot, M. and DAgosto, F.},
	month = oct,
	year = {2023},
	pages = {4569--4579},
}

Poly(methyl methacrylate)-b-polyethylene (PMMA-b-PE) block copolymers were recently obtained simply by involving omega-unsaturated PMMA oligomers prepared by CCTP in the radical polymerization of ethylene performed in dimethylcarbonate (DMC) solution (F. Baffie, G. Patias, A. Shegiwal, F. Brunel, V. Monteil, L. Verrieux, L. Perrin, D. M. Haddleton and F. D'Agosto, Angew. Chem., Int. Ed., 2021, 60, 25356-25364). However, omega-unsaturated PMMA oligomers are more effectively obtained as a latex by emulsion CCTP. In the present paper, these resulting latexes were used as seeds in the radical emulsion polymerization of ethylene in water. The effects of the methacrylic oligomer molar mass and the initial solids content of the seeds were investigated. Cryo-TEM analysis enabled demonstration of the formation of stable latexes composed of faceted spherical particles. The increase of molar mass correlated to the consumption of unsaturated oligomers with the polymerization time indicated the formation of block copolymers. The present study successfully transposed the chemistry performed in DMC solution and PMMA-b-PE block copolymers were obtained by a simple post-treatment of a PMMA latex.

@article{courtney_polymer_2023,
	title = {Polymer {Functionalization} by {RAFT} {Interchange}},
	volume = {12},
	issn = {2161-1653},
	doi = {10.1021/acsmacrolett.3c00495},
	abstract = {Here, we report a simple approach for end group functionalization of linear polymers and graft copolymers via an interchange process of reversible addition-fragmentation chain transfer (RAFT) polymerization chain transfer agents (CTAs). The high functional group tolerance of the RAFT process allows a library of functionalities to be introduced. Moreover, this approach allows multiple functional groups to be installed simultaneously. Furthermore, as an alternative to end group analysis, we report the utility of the supernatant of the reaction mixture to determine the degree of functionalization.},
	number = {10},
	urldate = {2023-10-10},
	journal = {ACS MACRO LETTERS},
	author = {Courtney, Owen Reid and Clouthier, Samantha Marie and Perrier, Sebastien and Tanaka, Joji and You, Wei},
	month = sep,
	year = {2023},
	pages = {1306--1310},
}

Here, we report a simple approach for end group functionalization of linear polymers and graft copolymers via an interchange process of reversible addition-fragmentation chain transfer (RAFT) polymerization chain transfer agents (CTAs). The high functional group tolerance of the RAFT process allows a library of functionalities to be introduced. Moreover, this approach allows multiple functional groups to be installed simultaneously. Furthermore, as an alternative to end group analysis, we report the utility of the supernatant of the reaction mixture to determine the degree of functionalization.

@article{song_supramolecular_2023,
	title = {Supramolecular peptide nanotubes as artificial enzymes for catalysing ester hydrolysis},
	volume = {14},
	issn = {1759-9954},
	doi = {10.1039/d3py00993a},
	abstract = {Peptide-based artificial enzymes are attracting significant interest because of their remarkable resemblance in both composition and structure to native enzymes. Herein, we report the construction of histidine-containing cyclic peptide-based supramolecular polymeric nanotubes to function as artificial enzymes for ester hydrolysis. The optimized catalyst shows a ca. 70-fold increase in reaction rate compared to the un-catalysed reaction when using 4-nitrophenyl acetate as a model substrate. Furthermore, the amphiphilic nature of the supramolecular catalysts enables an enhanced catalytic activity towards hydrophobic substrates. By incorporating an internal hydrophobic region within the self-assembled polymeric nanotube, we achieve a 55.4-fold acceleration in hydrolysis rate towards a more hydrophobic substrate, 4-nitrophenyl butyrate. This study introduces supramolecular peptide nanotubes as an innovative class of supramolecular scaffolds for fabricating artificial enzymes with better structural and chemical stability, catalysing not only ester hydrolysis, but also a broader spectrum of catalytic reactions.Histidine-containing cyclic peptide-based supramolecular peptide nanotubes were constructed to function as artificial enzymes for catalysing ester hydrolysis.},
	number = {41},
	urldate = {2023-11-29},
	journal = {POLYMER CHEMISTRY},
	author = {Song, Qiao and Cheng, Zihe and Perrier, Sebastien},
	month = oct,
	year = {2023},
	pages = {4712--4718},
}

Peptide-based artificial enzymes are attracting significant interest because of their remarkable resemblance in both composition and structure to native enzymes. Herein, we report the construction of histidine-containing cyclic peptide-based supramolecular polymeric nanotubes to function as artificial enzymes for ester hydrolysis. The optimized catalyst shows a ca. 70-fold increase in reaction rate compared to the un-catalysed reaction when using 4-nitrophenyl acetate as a model substrate. Furthermore, the amphiphilic nature of the supramolecular catalysts enables an enhanced catalytic activity towards hydrophobic substrates. By incorporating an internal hydrophobic region within the self-assembled polymeric nanotube, we achieve a 55.4-fold acceleration in hydrolysis rate towards a more hydrophobic substrate, 4-nitrophenyl butyrate. This study introduces supramolecular peptide nanotubes as an innovative class of supramolecular scaffolds for fabricating artificial enzymes with better structural and chemical stability, catalysing not only ester hydrolysis, but also a broader spectrum of catalytic reactions.Histidine-containing cyclic peptide-based supramolecular peptide nanotubes were constructed to function as artificial enzymes for catalysing ester hydrolysis.

@article{concilio_mechanism_2023,
	title = {Mechanism of {Action} of {Oxazoline}-{Based} {Antimicrobial} {Polymers} {Against} {Staphylococcus} aureus: {In} {Vivo} {Antimicrobial} {Activity} {Evaluation}},
	volume = {12},
	issn = {2192-2640},
	doi = {10.1002/adhm.202301961},
	abstract = {Antimicrobial-resistant pathogens have reached alarming levels, becoming one of the most pressing global health issues. Hence, new treatments are necessary for the fight against antimicrobial resistance. Synthetic nanoengineered antimicrobial polymers (SNAPs) have emerged as a promising alternative to antimicrobial peptides, overcoming some of their limitations while keeping their key features. Herein, a library of amphiphilic oxazoline-based SNAPs using cationic ring-opening polymerization (CROP) is designed. Amphipathic compounds with 70\% cationic content exhibit the highest activity against clinically relevant Staphylococcus aureus isolates, maintaining good biocompatibility in vitro and in vivo. The mechanism of action of the lead compounds against S. aureus is assessed using various microscopy techniques, indicating cell membrane disruption, while the cell wall remains unaffected. Furthermore, a potential interaction of the compounds with bacterial DNA is shown, with possible implications on bacterial division. Finally, one of the compounds exhibits high efficacy in vivo in an insect infection model.},
	number = {29},
	urldate = {2023-09-27},
	journal = {ADVANCED HEALTHCARE MATERIALS},
	author = {Concilio, Matilde and Maset, Ramon Garcia and Lemonche, Laia Pasquina and Kontrimas, Vito and Song, Ji-Inn and Rajendrakumar, Santhosh Kalash and Harrison, Freya and Becer, C. Remzi and Perrier, Sebastien},
	month = nov,
	year = {2023},
}

Antimicrobial-resistant pathogens have reached alarming levels, becoming one of the most pressing global health issues. Hence, new treatments are necessary for the fight against antimicrobial resistance. Synthetic nanoengineered antimicrobial polymers (SNAPs) have emerged as a promising alternative to antimicrobial peptides, overcoming some of their limitations while keeping their key features. Herein, a library of amphiphilic oxazoline-based SNAPs using cationic ring-opening polymerization (CROP) is designed. Amphipathic compounds with 70% cationic content exhibit the highest activity against clinically relevant Staphylococcus aureus isolates, maintaining good biocompatibility in vitro and in vivo. The mechanism of action of the lead compounds against S. aureus is assessed using various microscopy techniques, indicating cell membrane disruption, while the cell wall remains unaffected. Furthermore, a potential interaction of the compounds with bacterial DNA is shown, with possible implications on bacterial division. Finally, one of the compounds exhibits high efficacy in vivo in an insect infection model.

@article{barker_monitoring_2023,
	title = {Monitoring the {Terahertz} {Response} of {Skin} {Beneath} {Transdermal} {Drug} {Delivery} {Patches} {Using} {Sparse} {Deconvolution}},
	volume = {13},
	issn = {2156-342X},
	doi = {10.1109/TTHZ.2023.3292546},
	abstract = {Terahertz (THz) spectroscopy is a technique proving extremely useful for investigating various biomedical applications by virtue of its high sensitivity in the measurement of water content and its nonionizing nature. By combining this with sparse deconvolution, the THz response of skin directly underneath transdermal drug delivery (TDD) patches was isolated and reconstructed to determine the skin water content in vivo. Verification for this method was given by a comparison of skin measured through patches using sparse deconvolution and skin measurements immediately following patch removal processed with standard approaches. It was found that patches with a nonpermeable film backing hydrated the skin to a greater extent than permeable woven polyester fiber backed patches and that this hydration effect primarily occurs within the first 30 min of patch application and lasts for at least 24 h given that the patch remains applied. We demonstrate the effectiveness of this sparse reconstruction method to track hydration levels through layers such as patches and identify the scope for further applications including TDD patch development and wound healing techniques and monitoring.},
	number = {5},
	urldate = {2023-10-06},
	journal = {IEEE TRANSACTIONS ON TERAHERTZ SCIENCE AND TECHNOLOGY},
	author = {Barker, Xavier E. Ramirez and Costa, Goncalo and Stantchev, Rayko I. and Hernandez-Serrano, Arturo I. and Nurumbetov, Gabit and Haddleton, David M. and Pickwell-MacPherson, Emma},
	month = sep,
	year = {2023},
	pages = {503--510},
}

Terahertz (THz) spectroscopy is a technique proving extremely useful for investigating various biomedical applications by virtue of its high sensitivity in the measurement of water content and its nonionizing nature. By combining this with sparse deconvolution, the THz response of skin directly underneath transdermal drug delivery (TDD) patches was isolated and reconstructed to determine the skin water content in vivo. Verification for this method was given by a comparison of skin measured through patches using sparse deconvolution and skin measurements immediately following patch removal processed with standard approaches. It was found that patches with a nonpermeable film backing hydrated the skin to a greater extent than permeable woven polyester fiber backed patches and that this hydration effect primarily occurs within the first 30 min of patch application and lasts for at least 24 h given that the patch remains applied. We demonstrate the effectiveness of this sparse reconstruction method to track hydration levels through layers such as patches and identify the scope for further applications including TDD patch development and wound healing techniques and monitoring.

@article{huang_high-throughput_2023,
	title = {High-throughput screening of amorphous polymers with high intrinsic thermal conductivity via automated physical feature engineering},
	volume = {11},
	issn = {2050-7488},
	doi = {10.1039/d3ta03370h},
	abstract = {The informatics algorithm-driven approach overcomes the high-cost and time-consuming drawbacks of conventional trial-and-error procedures and enables efficient exploration of polymers with desired properties. Intrinsically thermally conductive polymers are highly in demand for effective thermal management of energy devices, flexible electronics and power modules, from the perspective of heat dissipation, operation reliability, and service lifetime of the devices. However, since most polymers are thermally insulating, the exploration of intrinsically thermally conductive polymers and understanding the relationship between molecular structures and thermal conduction are essential yet challenging tasks. In this work, we proposed and developed a hybrid framework that combines automated physical feature engineering and symbolic regression for exploring amorphous polymers with desired thermal conductivity. The feature engineering approach constructed 325 initial physical descriptors based on information from atoms, electrons, and charges in monomers, together with bond and non-bond interactions in amorphous systems. 25 optimized descriptors are finally figured out through statistical coefficient filtering and machine learning model selection. The relationship between the macromolecular structure and thermal conductivity was established with high accuracy, which outperforms other molecular representations of Morgan fingerprints, molecular access systems, and the dimensionality reduction technique of principal component analysis. Machine learning models based on optimized descriptors recommended 104 polymer candidates with good thermal conductivity out of over 790 000 polymers, of which 54.8\% have thermal conductivities above 0.35 W m(-1) K-1, significantly higher than those found in the training dataset. Furthermore, the feature importance ranking coupled with the explicit analytical models fitted by symbolic regression suggests that the conjugated molecular structure, chain stiffness, and maximum relative atomic mass in polymers have a strong influence on thermal conductivity. Our proposed approach provides a valuable tool for effectively exploring the relationship between macromolecular structures and thermal properties.},
	number = {38},
	urldate = {2023-10-12},
	journal = {JOURNAL OF MATERIALS CHEMISTRY A},
	author = {Huang, Xiang and Ma, Shengluo and Wu, Yunwen and Wan, Chaoying and Zhao, C. Y. and Wang, Hong and Ju, Shenghong},
	month = oct,
	year = {2023},
	pages = {20539--20548},
}

The informatics algorithm-driven approach overcomes the high-cost and time-consuming drawbacks of conventional trial-and-error procedures and enables efficient exploration of polymers with desired properties. Intrinsically thermally conductive polymers are highly in demand for effective thermal management of energy devices, flexible electronics and power modules, from the perspective of heat dissipation, operation reliability, and service lifetime of the devices. However, since most polymers are thermally insulating, the exploration of intrinsically thermally conductive polymers and understanding the relationship between molecular structures and thermal conduction are essential yet challenging tasks. In this work, we proposed and developed a hybrid framework that combines automated physical feature engineering and symbolic regression for exploring amorphous polymers with desired thermal conductivity. The feature engineering approach constructed 325 initial physical descriptors based on information from atoms, electrons, and charges in monomers, together with bond and non-bond interactions in amorphous systems. 25 optimized descriptors are finally figured out through statistical coefficient filtering and machine learning model selection. The relationship between the macromolecular structure and thermal conductivity was established with high accuracy, which outperforms other molecular representations of Morgan fingerprints, molecular access systems, and the dimensionality reduction technique of principal component analysis. Machine learning models based on optimized descriptors recommended 104 polymer candidates with good thermal conductivity out of over 790 000 polymers, of which 54.8% have thermal conductivities above 0.35 W m(-1) K-1, significantly higher than those found in the training dataset. Furthermore, the feature importance ranking coupled with the explicit analytical models fitted by symbolic regression suggests that the conjugated molecular structure, chain stiffness, and maximum relative atomic mass in polymers have a strong influence on thermal conductivity. Our proposed approach provides a valuable tool for effectively exploring the relationship between macromolecular structures and thermal properties.

@article{bui_stretchable_2023,
	title = {Stretchable, healable, and weldable vitrimer ionogel for ionotronic applications},
	volume = {474},
	issn = {1385-8947},
	doi = {10.1016/j.cej.2023.145533},
	abstract = {The ionogels represents a class of materials consisting of ionic liquid confined in a polymer network. The mobile ions provide ionic conductivity while the polymer network enables flexibility and stretchability. They can exhibit healing, welding, reshaping, and recycling abilities when they are gifted with vitrimer properties, which make them promising candidates for sustainable soft electronics. Herein, vitrimer ionogel based on transesterification was synthesized via the epoxy ring-opening reaction with carboxylic acids of functionalized poly (ethylene glycol) (PEG) and triglycidyl ether crosslinkers in the presence of the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIm TFSI). The ionogel with 50 wt\% EMIm TFSI exhibits good maximum strain (300 \%), low elastic modulus (60 kPa) and high conductivity (2.6 x 10-4 S cm- 1), owing to the plasticizing effect and the introduction of mobile ions. Also, the presence of EMIm TFSI increases the chain mobility, overcoming the dilution effect and consequently facilitating the transesterification reaction of exchangeable beta-hydroxy ester linkages. Thus, the ionogel shows fast network rearrangement and full recovery of both tensile strength and conductivity properties. The ionogels were applied as strain sensor, soft electrode, and ionic cable, respectively. When used as a piezoresistive strain sensor, the ionogel exhibits high sensitivity (Gauge factor = 2.8), low hysteresis (3 \%), low response time delay of 0.5 s and fully recovered its performance after healing from mechanical damage. In addition, the ionogel was applied as electrodes for a dielectric elastomer actuator, the ionogel can be welded onto an elastomer containing the same exchangeable beta-hydroxy ester linkages, for the fabrication of multilayer devices. which generated 12 \% areal strain under a 42.5 MV/m electrical field. Second, a self-healable ionic cable was fabricated from this multilayer structure. It can transmit music signals and maintain the performance during stretching.},
	urldate = {2023-10-19},
	journal = {CHEMICAL ENGINEERING JOURNAL},
	author = {Bui, Khoa and Nguyen, Giao T. M. and Vancaeyzeele, Cedric and Vidal, Frederic and Hu, Xiao and Wan, Chaoying and Plesse, Cedric},
	month = oct,
	year = {2023},
}

The ionogels represents a class of materials consisting of ionic liquid confined in a polymer network. The mobile ions provide ionic conductivity while the polymer network enables flexibility and stretchability. They can exhibit healing, welding, reshaping, and recycling abilities when they are gifted with vitrimer properties, which make them promising candidates for sustainable soft electronics. Herein, vitrimer ionogel based on transesterification was synthesized via the epoxy ring-opening reaction with carboxylic acids of functionalized poly (ethylene glycol) (PEG) and triglycidyl ether crosslinkers in the presence of the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIm TFSI). The ionogel with 50 wt% EMIm TFSI exhibits good maximum strain (300 %), low elastic modulus (60 kPa) and high conductivity (2.6 x 10-4 S cm- 1), owing to the plasticizing effect and the introduction of mobile ions. Also, the presence of EMIm TFSI increases the chain mobility, overcoming the dilution effect and consequently facilitating the transesterification reaction of exchangeable beta-hydroxy ester linkages. Thus, the ionogel shows fast network rearrangement and full recovery of both tensile strength and conductivity properties. The ionogels were applied as strain sensor, soft electrode, and ionic cable, respectively. When used as a piezoresistive strain sensor, the ionogel exhibits high sensitivity (Gauge factor = 2.8), low hysteresis (3 %), low response time delay of 0.5 s and fully recovered its performance after healing from mechanical damage. In addition, the ionogel was applied as electrodes for a dielectric elastomer actuator, the ionogel can be welded onto an elastomer containing the same exchangeable beta-hydroxy ester linkages, for the fabrication of multilayer devices. which generated 12 % areal strain under a 42.5 MV/m electrical field. Second, a self-healable ionic cable was fabricated from this multilayer structure. It can transmit music signals and maintain the performance during stretching.

@article{kariuki_investigating_2023,
	title = {Investigating the {Impact} of {Hydrophobic} {Polymer} {Segments} on the {Self}-{Assembly} {Behavior} of {Supramolecular} {Cyclic} {Peptide} {Systems} via {Asymmetric}-{Flow} {Field} {Flow} {Fractionation}},
	volume = {56},
	issn = {0024-9297},
	doi = {10.1021/acs.macromol.3c00442},
	abstract = {The present study examines the behavior of cyclic peptide polymer conjugates that have been designed to combine their self-assembling ability via H-bonding with the properties of amphiphilic diblock copolymers. Using a combination of asymmetric flow-field flow fractionation (AF(4)) and small-angle neutron scattering (SANS), we have uncovered unique insight based on the population of structures established at a 24 h equilibrium profile. Our results determine that by introducing a small quantity of hydrophobicity into the conjugated polymer corona, the resulting nanotube structures exhibit low unimer dissociation which signifies enhanced stability. Furthermore, as the hydrophobicity of the polymer corona is increased, the elongation of the nanotubes is observed due to an increase in the association of unimers. This encompasses not only the H-bonding of unimers into nanotubes but also the self-assembly of single nanotubes into segmented-nanotube structures with high aspect ratios. However, this influence relies on a subtle balance between the hydrophobicity and hydrophilicity of the polymer corona. This balance is proposed to determine the solvent entropic penalty of hydrating the system, whereby the cost scales with the hydrophobic quantity. Consequently, it has been suggested that at a critical hydrophobic quantity, the solvation penalty becomes high enough such that the self-assembly of the system deviates from ordered hydrogen bonding. The association behavior is instead dominated by the hydrophobic effect which results in the undesirable formation of disordered aggregates.},
	number = {17},
	urldate = {2024-03-30},
	journal = {MACROMOLECULES},
	author = {Kariuki, Maria and Rho, Julia Y. and Hall, Stephen C. L. and Perrier, Sebastien},
	month = aug,
	year = {2023},
	pages = {6618--6632},
}

The present study examines the behavior of cyclic peptide polymer conjugates that have been designed to combine their self-assembling ability via H-bonding with the properties of amphiphilic diblock copolymers. Using a combination of asymmetric flow-field flow fractionation (AF(4)) and small-angle neutron scattering (SANS), we have uncovered unique insight based on the population of structures established at a 24 h equilibrium profile. Our results determine that by introducing a small quantity of hydrophobicity into the conjugated polymer corona, the resulting nanotube structures exhibit low unimer dissociation which signifies enhanced stability. Furthermore, as the hydrophobicity of the polymer corona is increased, the elongation of the nanotubes is observed due to an increase in the association of unimers. This encompasses not only the H-bonding of unimers into nanotubes but also the self-assembly of single nanotubes into segmented-nanotube structures with high aspect ratios. However, this influence relies on a subtle balance between the hydrophobicity and hydrophilicity of the polymer corona. This balance is proposed to determine the solvent entropic penalty of hydrating the system, whereby the cost scales with the hydrophobic quantity. Consequently, it has been suggested that at a critical hydrophobic quantity, the solvation penalty becomes high enough such that the self-assembly of the system deviates from ordered hydrogen bonding. The association behavior is instead dominated by the hydrophobic effect which results in the undesirable formation of disordered aggregates.

@article{mohammed_localised_2023,
	title = {Localised polymerisation of acrylamide using single-barrel scanning electrochemical cell microscopy},
	volume = {59},
	issn = {1359-7345},
	doi = {10.1039/d3cc03582d},
	abstract = {Single-barrel scanning electrochemical cell microscopy has been adapted for polymerisation of acrylamide in droplet cells formed at gold electrode surfaces. Localised electrochemical atom transfer radical polymerisation enables controlled synthesis and deposition of polyacrylamide or synthesis of polyacrylamide brushes from initiator-functionalised electrode surfaces.Single-barrel scanning electrochemical cell microscopy has been used for the first time to achieve localized polymerization of acrylamide at a surface with fine control over the reactions and the resulting polymer features formed.},
	number = {73},
	urldate = {2023-11-05},
	journal = {CHEMICAL COMMUNICATIONS},
	author = {Mohammed, Mahir and Jones, Bryn A. and Liarou, Evelina and Wilson, Paul},
	month = sep,
	year = {2023},
	pages = {10992--10995},
}

Single-barrel scanning electrochemical cell microscopy has been adapted for polymerisation of acrylamide in droplet cells formed at gold electrode surfaces. Localised electrochemical atom transfer radical polymerisation enables controlled synthesis and deposition of polyacrylamide or synthesis of polyacrylamide brushes from initiator-functionalised electrode surfaces.Single-barrel scanning electrochemical cell microscopy has been used for the first time to achieve localized polymerization of acrylamide at a surface with fine control over the reactions and the resulting polymer features formed.

@article{bayliss_thermoresponsive_2023,
	title = {Thermoresponsive behaviour of poly({N},{N}-diethylacrylamide) in aqueous two-phase systems},
	volume = {14},
	issn = {1759-9954},
	doi = {10.1039/d3py00734k},
	abstract = {Aqueous two-phase systems (ATPS) have been in the focus of polymer chemistry in recent years, mainly due to their biocompatibility and various applications in biomaterials and biology. In the present contribution, the ATPS formed from poly(N,N-diethylacrylamide) (PDEA) and commercially available dextran as well as poly(ethylene glycol) are investigated. Furthermore, the effect of an ATPS on the thermoresponsive behaviour of PDEA is studied. A significant shift in cloud point temperature of PDEA in the ATPS compared to pure aqueous PDEA solutions is observed. This effect on thermoresponsive behavior will lead to new pathways for water-based polymer systems for example in multicompartment hydrogels or biotechnology.},
	number = {35},
	urldate = {2023-08-27},
	journal = {POLYMER CHEMISTRY},
	author = {Bayliss, Niamh and Yilmaz, Gokhan and Plucinski, Alexander and Becer, C. Remzi and Schmidt, Bernhard V. K. J.},
	month = sep,
	year = {2023},
	pages = {4101--4108},
}

Aqueous two-phase systems (ATPS) have been in the focus of polymer chemistry in recent years, mainly due to their biocompatibility and various applications in biomaterials and biology. In the present contribution, the ATPS formed from poly(N,N-diethylacrylamide) (PDEA) and commercially available dextran as well as poly(ethylene glycol) are investigated. Furthermore, the effect of an ATPS on the thermoresponsive behaviour of PDEA is studied. A significant shift in cloud point temperature of PDEA in the ATPS compared to pure aqueous PDEA solutions is observed. This effect on thermoresponsive behavior will lead to new pathways for water-based polymer systems for example in multicompartment hydrogels or biotechnology.

@article{wan_reversible_2023,
	title = {Reversible bond formation via sulfur free reversible addition fragmentation in photo-{3D} printing},
	volume = {196},
	issn = {0014-3057},
	doi = {10.1016/j.eurpolymj.2023.112324},
	abstract = {An addition-fragmentation monomer (AFM) has been used as a crosslinker in photopolymerization-based 3D printer resins in order to try and reduce shrinkage due to polymerisation. This results in reversible network formation via photo crosslinking with reversible covalent bond formation to effect mechanical performance. The 3D printing conditions were optimized with regards to print quality, print speed, etc. The AFM was synthesized via catalytic chain transfer polymerization (CCTP) and characterized using NMR and size exclusion chromatography (SEC). The incorporation of the AFM as a crosslinker allows for rapid reversible covalent bond formation during network formation in 3D photopolymerization printing resulting in a reduction in both polymerisation shrinkage and stress higher molecular weight crosslinkers lead to less shrinkage and reversible bond formation to less stress build up. Curing was monitored via photo-rheology and Fourier Transform Infrared Spectroscopy (FT-IR). At lower contents of AFM, the mechanical properties (strength and Young's modulus) are improved without compromising material properties, printing conditions and curing time. At higher AFM content, the kinetic analysis of the photopolymerization reaction shows a reduced final conversion of the vinylic bonds along with a delay of the gel point. The thermal and mechanical properties were evaluated with incorporation of different concentrations of AFM added to the resin formulations.},
	urldate = {2023-08-25},
	journal = {EUROPEAN POLYMER JOURNAL},
	author = {Wan, Zhongyuan and Hin, Lee Wai and Shegiwal, Ataulla and Haddleton, David},
	month = sep,
	year = {2023},
}

An addition-fragmentation monomer (AFM) has been used as a crosslinker in photopolymerization-based 3D printer resins in order to try and reduce shrinkage due to polymerisation. This results in reversible network formation via photo crosslinking with reversible covalent bond formation to effect mechanical performance. The 3D printing conditions were optimized with regards to print quality, print speed, etc. The AFM was synthesized via catalytic chain transfer polymerization (CCTP) and characterized using NMR and size exclusion chromatography (SEC). The incorporation of the AFM as a crosslinker allows for rapid reversible covalent bond formation during network formation in 3D photopolymerization printing resulting in a reduction in both polymerisation shrinkage and stress higher molecular weight crosslinkers lead to less shrinkage and reversible bond formation to less stress build up. Curing was monitored via photo-rheology and Fourier Transform Infrared Spectroscopy (FT-IR). At lower contents of AFM, the mechanical properties (strength and Young's modulus) are improved without compromising material properties, printing conditions and curing time. At higher AFM content, the kinetic analysis of the photopolymerization reaction shows a reduced final conversion of the vinylic bonds along with a delay of the gel point. The thermal and mechanical properties were evaluated with incorporation of different concentrations of AFM added to the resin formulations.

@article{liu_polyether-based_2023,
	title = {Polyether-based ionic liquids from simple mixing of terminal diamines with organic acids to dicationic diammonium carboxylates},
	volume = {387},
	issn = {0167-7322},
	doi = {10.1016/j.molliq.2023.122524},
	abstract = {A new family of dicationic ionic liquids (DIL) have been synthesised by the mixing of either 4,7,10-trioxa-1,13-tridecanediamine or a low molecular weight JeffamineTM with organic acids such as formic acid, acetic acid, propionic acid, butyric acid, maleic acid, valeric, hexanoic acid, heptanoic acid, benzoic acid and octanoic acid. The structure of the DILs was determined by 1H and 13C NMR and LC-MS. All ILs were soluble in protic polar solvents, especially DMSO, and mostly insoluble in aprotic or non-polar solvents. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were used to assess the thermal properties of the DILs. Temperature-dependant viscosity and ionic conductivity values were measured at temperatures ranging from 25 to 45 degrees C. The electrochemical stability of the library of ILs was determined using cyclic voltammetry (CV) with a working electrochemical window of 1.2 V (-0.6 V to 0.6 V).},
	urldate = {2023-08-25},
	journal = {JOURNAL OF MOLECULAR LIQUIDS},
	author = {Liu, Huizhe and Maugein, Vincent A. and Patias, Georgios and Zhao, Boyu and Efstathiou, Spyridon and Jones, Bryn A. and Town, James and Lester, Daniel W. and Houck, Hannes and Haddleton, David M.},
	month = oct,
	year = {2023},
}

A new family of dicationic ionic liquids (DIL) have been synthesised by the mixing of either 4,7,10-trioxa-1,13-tridecanediamine or a low molecular weight JeffamineTM with organic acids such as formic acid, acetic acid, propionic acid, butyric acid, maleic acid, valeric, hexanoic acid, heptanoic acid, benzoic acid and octanoic acid. The structure of the DILs was determined by 1H and 13C NMR and LC-MS. All ILs were soluble in protic polar solvents, especially DMSO, and mostly insoluble in aprotic or non-polar solvents. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were used to assess the thermal properties of the DILs. Temperature-dependant viscosity and ionic conductivity values were measured at temperatures ranging from 25 to 45 degrees C. The electrochemical stability of the library of ILs was determined using cyclic voltammetry (CV) with a working electrochemical window of 1.2 V (-0.6 V to 0.6 V).

@article{burgevin_cationic_2023,
	title = {Cationic star copolymers obtained by the arm first approach for gene transfection},
	volume = {14},
	issn = {1759-9954},
	doi = {10.1039/d3py00352c},
	abstract = {Cationic polymers can be used as vectors to transport and efficiently protect nucleic acids. In this work we describe the synthesis of dense star-like polymers of 2-dimethylaminoethyl acrylate (DMAEA) and 2-dimethylaminoethyl methacrylate (DMAEMA) and the hydrolysis of the DMAEA units side chains for the complexation and release of nucleic acids. The successful chain extension of p(DMAEA(80)-stat-DMAEMA(20)) with acrylamide monomers allowed the preparation of stars by the arm-first approach. Soluble stars with a high number of well-defined arms (N-arm \& SIM;55-100) were obtained with the introduction of non-cationic N-acrylmorpholine (NAM) prior to the crosslinking step. The influence of the architecture on the hydrolysis of the DMAEA units side chains was studied, with only small differences observed compared to the corresponding arm. All stars were able to complex a large (10 000 basepairs) plasmid DNA encoding for green fluorescent protein (GFP), and transfect HEK293T cells, with the larger, more charged star structure leading to higher transfection efficiency. Although the transfection efficiency is lower than that of the gold standard polyethylenimine (PEI), the stars much lower toxicity, at concentrations as high as 1 mg mL(-1), make them viable transfection agents.},
	number = {32},
	urldate = {2023-08-10},
	journal = {POLYMER CHEMISTRY},
	author = {Burgevin, Fannie and Hapeshi, Alexia and Song, Ji-Inn and Omedes-Pujol, Marta and Christie, Annette and Lindsay, Christopher and Perrier, Sebastien},
	month = aug,
	year = {2023},
	pages = {3707--3717},
}

Cationic polymers can be used as vectors to transport and efficiently protect nucleic acids. In this work we describe the synthesis of dense star-like polymers of 2-dimethylaminoethyl acrylate (DMAEA) and 2-dimethylaminoethyl methacrylate (DMAEMA) and the hydrolysis of the DMAEA units side chains for the complexation and release of nucleic acids. The successful chain extension of p(DMAEA(80)-stat-DMAEMA(20)) with acrylamide monomers allowed the preparation of stars by the arm-first approach. Soluble stars with a high number of well-defined arms (N-arm & SIM;55-100) were obtained with the introduction of non-cationic N-acrylmorpholine (NAM) prior to the crosslinking step. The influence of the architecture on the hydrolysis of the DMAEA units side chains was studied, with only small differences observed compared to the corresponding arm. All stars were able to complex a large (10 000 basepairs) plasmid DNA encoding for green fluorescent protein (GFP), and transfect HEK293T cells, with the larger, more charged star structure leading to higher transfection efficiency. Although the transfection efficiency is lower than that of the gold standard polyethylenimine (PEI), the stars much lower toxicity, at concentrations as high as 1 mg mL(-1), make them viable transfection agents.

@article{lertwimol_facile_2023,
	title = {A facile strategy for promoting cell adhesion and function on three-dimensional printed hydrogels using photocurable epsilon-poly-{L}-lysine},
	volume = {196},
	issn = {0014-3057},
	doi = {10.1016/j.eurpolymj.2023.112245},
	abstract = {This study introduces a new persuasive strategy for promoting cell adhesion and function on three-dimensional (3D) printed hydrogels by incorporating photocurable epsilon-poly-L-lysine (EPL) as the cell adhesive molecule. Two different polymers, dextran (Dex) and EPL, were first modified using methacrylic anhydride and glycidyl methacrylate, respectively, to obtain the methacrylate-functionalized polymers: Dex-MA and EPL-MA. Subsequently, these modified polymers were formulated with poly(ethylene glycol dimethacrylate) (PEGDMA) before fabricating the 3D-printed hydrogels through digital light processing (DLP). The effects of the PEGDMA, Dex-MA, and EPL-MA ratios in the formulation on the physical properties of 3D-printed hydrogel and their biological responses were assessed. The 3D-printed specimens possessed compressive moduli in the range of 280-520 kPa. SEM/EDS analysis confirmed the presence of nitrogen in the hydrogels. The ninhydrin assay revealed that the EPL-MA content fell in the range of 0-0.15 mg/mg. All prepared hydrogels exhibited non-cytotoxic behavior toward NIH/3T3 fibroblasts. The benefit of incorporating EPL-MA and, interestingly, the stiffness of 3D-printed hydrogel on cell performance has been confirmed by various biological evaluations, including viability, adhesion, growth, and function of NIH/3T3 fibroblasts. Taken together, we have developed a rather promising strategy using photocurable epsilon-poly-L-lysine for promoting cell adhesion and functionalisation with potential for skin tissue engineering and other regenerative medicine applications.},
	urldate = {2023-09-07},
	journal = {EUROPEAN POLYMER JOURNAL},
	author = {Lertwimol, Tareerat and Sungkhaphan, Piyarat and Uppanan, Paweena and Zhang, Qiang and Haddleton, David M. and Risangud, Nuttapol},
	month = sep,
	year = {2023},
}

This study introduces a new persuasive strategy for promoting cell adhesion and function on three-dimensional (3D) printed hydrogels by incorporating photocurable epsilon-poly-L-lysine (EPL) as the cell adhesive molecule. Two different polymers, dextran (Dex) and EPL, were first modified using methacrylic anhydride and glycidyl methacrylate, respectively, to obtain the methacrylate-functionalized polymers: Dex-MA and EPL-MA. Subsequently, these modified polymers were formulated with poly(ethylene glycol dimethacrylate) (PEGDMA) before fabricating the 3D-printed hydrogels through digital light processing (DLP). The effects of the PEGDMA, Dex-MA, and EPL-MA ratios in the formulation on the physical properties of 3D-printed hydrogel and their biological responses were assessed. The 3D-printed specimens possessed compressive moduli in the range of 280-520 kPa. SEM/EDS analysis confirmed the presence of nitrogen in the hydrogels. The ninhydrin assay revealed that the EPL-MA content fell in the range of 0-0.15 mg/mg. All prepared hydrogels exhibited non-cytotoxic behavior toward NIH/3T3 fibroblasts. The benefit of incorporating EPL-MA and, interestingly, the stiffness of 3D-printed hydrogel on cell performance has been confirmed by various biological evaluations, including viability, adhesion, growth, and function of NIH/3T3 fibroblasts. Taken together, we have developed a rather promising strategy using photocurable epsilon-poly-L-lysine for promoting cell adhesion and functionalisation with potential for skin tissue engineering and other regenerative medicine applications.

@article{poluektov_two-scale_2023,
	title = {A two-scale framework for coupled mechanics-diffusion-reaction processes},
	volume = {279},
	issn = {0020-7683},
	doi = {10.1016/j.ijsolstr.2023.112386},
	abstract = {There is a wide range of industrially-relevant problems where mechanical stresses directly affect kinetics of chemical reactions. For example, this includes formation of oxide layers on parts of micro-electro-mechanical systems (MEMS) and lithiation of Si in Li-ion batteries. Detailed understanding of these processes requires thermodynamically-consistent theories describing the coupled thermo-chemo-mechanical behaviour of those systems. Furthermore, as the majority of materials used in those systems have complex microstructures, multiscale modelling techniques are required for efficient simulation of their behaviour. Hence, the purpose of the present paper is two-fold: (1) to derive a thermodynamically-consistent thermo-chemo-mechanical theory; and (2) to propose a two-scale modelling approach based on the concept of computational homogenisation for the considered theory. The theory and the two-scale computational approach are implemented and tested using a number of computational examples, including the case of the reaction locking due to mechanical stresses.},
	urldate = {2023-08-10},
	journal = {INTERNATIONAL JOURNAL OF SOLIDS AND STRUCTURES},
	author = {Poluektov, Michael and Figiel, Lukasz},
	month = sep,
	year = {2023},
}

There is a wide range of industrially-relevant problems where mechanical stresses directly affect kinetics of chemical reactions. For example, this includes formation of oxide layers on parts of micro-electro-mechanical systems (MEMS) and lithiation of Si in Li-ion batteries. Detailed understanding of these processes requires thermodynamically-consistent theories describing the coupled thermo-chemo-mechanical behaviour of those systems. Furthermore, as the majority of materials used in those systems have complex microstructures, multiscale modelling techniques are required for efficient simulation of their behaviour. Hence, the purpose of the present paper is two-fold: (1) to derive a thermodynamically-consistent thermo-chemo-mechanical theory; and (2) to propose a two-scale modelling approach based on the concept of computational homogenisation for the considered theory. The theory and the two-scale computational approach are implemented and tested using a number of computational examples, including the case of the reaction locking due to mechanical stresses.

@article{wang_electrochemical_2023,
	title = {An electrochemical {Hofmann} rearrangement on acrylamide copolymers},
	volume = {14},
	issn = {1759-9954},
	doi = {10.1039/d3py00594a},
	abstract = {The primary amide side-chain of acrylamide copolymers has been utilised as an isocyanate surrogate. The isocyanate is formed under mild conditions via an electrochemical Hofmann rearrangement resulting in the formation of O-alkyl carbamate side-chains in alcohol solvents. This represents a new strategy for the modification of amide-functionalised (co)polymers.},
	number = {26},
	urldate = {2023-07-10},
	journal = {POLYMER CHEMISTRY},
	author = {Wang, Muzhao and Wilson, Paul},
	month = jul,
	year = {2023},
	pages = {3057--3062},
}

The primary amide side-chain of acrylamide copolymers has been utilised as an isocyanate surrogate. The isocyanate is formed under mild conditions via an electrochemical Hofmann rearrangement resulting in the formation of O-alkyl carbamate side-chains in alcohol solvents. This represents a new strategy for the modification of amide-functionalised (co)polymers.

@article{laroque_synthetic_2023,
	title = {Synthetic {Star} {Nanoengineered} {Antimicrobial} {Polymers} as {Antibiofilm} {Agents}: {Bacterial} {Membrane} {Disruption} and {Cell} {Aggregation}},
	volume = {24},
	issn = {1525-7797},
	doi = {10.1021/acs.biomac.3c00150},
	abstract = {Antimicrobial resistance has become a worldwide issue,with multiresistantbacterial strains emerging at an alarming rate. Multivalent antimicrobialpolymer architectures such as bottle brush or star polymers have showngreat potential, as they could lead to enhanced binding and interactionwith the bacterial cell membrane. In this study, a library of amphiphilicstar copolymers and their linear copolymer equivalents, based on acrylamidemonomers, were synthesized via RAFT polymerization. Their monomerdistribution and molecular weight were varied. Subsequently, theirantimicrobial activity toward a Gram-negative bacterium (Pseudomonas aeruginosa PA14) and a Gram-positivebacterium (Staphylococcus aureus USA300)and their hemocompatibility were investigated. The statistical starcopolymer, S-SP25, showed an improved antimicrobial activity comparedto its linear equivalent againstP. aeruginosaPA14. The star architecture enhanced its antimicrobial activity,causing bacterial cell aggregation, as revealed via electron microscopy.However, it also induced increased red blood cell aggregation comparedto its linear equivalents. Changing/shifting the position of the cationicblock to the core of the structure prevents the cell aggregation effectwhile maintaining a potent antimicrobial activity for the smalleststar copolymer. Finally, this compound showed antibiofilm propertiesagainst a robust in vitro biofilm model.},
	number = {7},
	urldate = {2023-06-24},
	journal = {BIOMACROMOLECULES},
	author = {Laroque, Sophie and Garcia Maset, Ramoin and Hapeshi, Alexia and Burgevin, Fannie and Locock, Katherine E. S. and Perrier, Seibastien},
	month = jun,
	year = {2023},
	pages = {3073--3085},
}

Antimicrobial resistance has become a worldwide issue,with multiresistantbacterial strains emerging at an alarming rate. Multivalent antimicrobialpolymer architectures such as bottle brush or star polymers have showngreat potential, as they could lead to enhanced binding and interactionwith the bacterial cell membrane. In this study, a library of amphiphilicstar copolymers and their linear copolymer equivalents, based on acrylamidemonomers, were synthesized via RAFT polymerization. Their monomerdistribution and molecular weight were varied. Subsequently, theirantimicrobial activity toward a Gram-negative bacterium (Pseudomonas aeruginosa PA14) and a Gram-positivebacterium (Staphylococcus aureus USA300)and their hemocompatibility were investigated. The statistical starcopolymer, S-SP25, showed an improved antimicrobial activity comparedto its linear equivalent againstP. aeruginosaPA14. The star architecture enhanced its antimicrobial activity,causing bacterial cell aggregation, as revealed via electron microscopy.However, it also induced increased red blood cell aggregation comparedto its linear equivalents. Changing/shifting the position of the cationicblock to the core of the structure prevents the cell aggregation effectwhile maintaining a potent antimicrobial activity for the smalleststar copolymer. Finally, this compound showed antibiofilm propertiesagainst a robust in vitro biofilm model.

@article{varanaraja_poly2-alkyl-2-oxazoline-based_2023,
	title = {Poly(2-alkyl-2-oxazoline)-{Based} {Copolymer} {Library} with a {Thermoresponsive} {Behavior} in {Dodecane}},
	volume = {5},
	issn = {2637-6105},
	doi = {10.1021/acsapm.3c00625},
	abstract = {Poly(2-oxazoline)s are an emerging class of polymersdue to theirhigh versatility and hence have proven to be beneficial in numerousapplications. The extensive study and interest in this polymer classis due to their great synthetic flexibility and good biocompatibility,resulting in the synthesis of extremely functional material, particularlyadvantageous in biomedical applications. Although the thermoresponsivebehavior of POx has been extensively studied in aqueous media, thereis only limited literature on polymers with temperature sensitivityand solubility in nonaqueous media. Herein, a systematic library of21 tunable copolymers based on unsaturated 2-fatty acid-2-oxazoline,2-phenyl-2-oxazoline, and 2-ethyl-2-oxazoline have been synthesized,and their thermal properties and solution behavior in aqueous andnonaqueous media have been investigated via DSC, TGA, and UV-vismeasurements, respectively. Finally, their ability as a dispersantfor carbonized materials in nonaqueous medium is evaluated using carbonblack.},
	number = {7},
	urldate = {2023-06-24},
	journal = {ACS APPLIED POLYMER MATERIALS},
	author = {Varanaraja, Zivani and Hollingsworth, Nathan and Green, Ross and Becer, C. Remzi},
	month = jun,
	year = {2023},
	note = {Infineum UK Ltd},
	pages = {5158--5168},
}

Poly(2-oxazoline)s are an emerging class of polymersdue to theirhigh versatility and hence have proven to be beneficial in numerousapplications. The extensive study and interest in this polymer classis due to their great synthetic flexibility and good biocompatibility,resulting in the synthesis of extremely functional material, particularlyadvantageous in biomedical applications. Although the thermoresponsivebehavior of POx has been extensively studied in aqueous media, thereis only limited literature on polymers with temperature sensitivityand solubility in nonaqueous media. Herein, a systematic library of21 tunable copolymers based on unsaturated 2-fatty acid-2-oxazoline,2-phenyl-2-oxazoline, and 2-ethyl-2-oxazoline have been synthesized,and their thermal properties and solution behavior in aqueous andnonaqueous media have been investigated via DSC, TGA, and UV-vismeasurements, respectively. Finally, their ability as a dispersantfor carbonized materials in nonaqueous medium is evaluated using carbonblack.

@article{vorauer_impact_2023,
	title = {Impact of solid-electrolyte interphase reformation on capacity loss in silicon-based lithium-ion batteries},
	volume = {4},
	issn = {2662-4443},
	doi = {10.1038/s43246-023-00368-1},
	abstract = {The solid electrolyte interface reformation process and material evolution in silicon composite anodes is not well understood. Here, the authors develop a correlated workflow to study the structural and chemical progression of silicon and solid electrolyte interface reformation upon cycling.High-density silicon composite anodes show large volume changes upon charging/discharging triggering the reformation of the solid electrolyte interface (SEI), an interface initially formed at the silicon surface. The question remains how the reformation process and accompanied material evolution, in particular for industrial up-scalable cells, impacts cell performance. Here, we develop a correlated workflow incorporating X-ray microscopy, field-emission scanning electron microscopy tomography, elemental imaging and deep learning-based microstructure quantification suitable to witness the structural and chemical progression of the silicon and SEI reformation upon cycling. The nanometer-sized SEI layer evolves into a micron-sized silicon electrolyte composite structure at prolonged cycles. Experimental-informed electrochemical modelling endorses an underutilisation of the active material due to the silicon electrolyte composite growth affecting the capacity. A chemo-mechanical model is used to analyse the stability of the SEI/silicon reaction front and to investigate the effects of material properties on the stability that can affect the capacity loss.},
	number = {1},
	urldate = {2023-06-18},
	journal = {COMMUNICATIONS MATERIALS},
	author = {Vorauer, T. and Schoeggl, J. and Sanadhya, S. G. and Poluektov, M. and Widanage, W. D. and Figiel, L. and Schaedler, S. and Tordoff, B. and Fuchsbichler, B. and Koller, S. and Brunner, R.},
	month = jun,
	year = {2023},
	note = {Varta Micro Innovat GmbH},
}

The solid electrolyte interface reformation process and material evolution in silicon composite anodes is not well understood. Here, the authors develop a correlated workflow to study the structural and chemical progression of silicon and solid electrolyte interface reformation upon cycling.High-density silicon composite anodes show large volume changes upon charging/discharging triggering the reformation of the solid electrolyte interface (SEI), an interface initially formed at the silicon surface. The question remains how the reformation process and accompanied material evolution, in particular for industrial up-scalable cells, impacts cell performance. Here, we develop a correlated workflow incorporating X-ray microscopy, field-emission scanning electron microscopy tomography, elemental imaging and deep learning-based microstructure quantification suitable to witness the structural and chemical progression of the silicon and SEI reformation upon cycling. The nanometer-sized SEI layer evolves into a micron-sized silicon electrolyte composite structure at prolonged cycles. Experimental-informed electrochemical modelling endorses an underutilisation of the active material due to the silicon electrolyte composite growth affecting the capacity. A chemo-mechanical model is used to analyse the stability of the SEI/silicon reaction front and to investigate the effects of material properties on the stability that can affect the capacity loss.

@article{song_biodiesel_2023,
	title = {Biodiesel {Promotes} {Iron}-{Catalyzed} {Oxidation} of {Engine} {Lubricating} {Oil}},
	volume = {62},
	issn = {0888-5885},
	doi = {10.1021/acs.iecr.3c00916},
	abstract = {The growing trend of increasing biodiesel concentrationsin dieselfuel blends has led to concerns about its effect on the oxidationof formulated oils within internal combustion engines. We observethat biodiesel is not only susceptible to rapid oxidation at elevatedtemperatures but is also responsible for acceleration of the oxidationprocess of the lubricant base oil when in the presence of solubleiron; this is supported by a range of control and model experiments.A mixture of oxidized biodiesel and Fe(III) leads to the formationof catalytic iron carboxylate networks that remain solubilized, asobserved by UV-Vis and infrared absorption studies. These observationsare important for the fundamental understanding of the chemistry withinindustry standard laboratory bench tests for lubricant oil formulationsand can aid the design of new lubricants with improved biodiesel compatibility.Such lubricants have the potential for a reduced carbon footprintvia waste reduction.},
	number = {23},
	urldate = {2023-06-27},
	journal = {INDUSTRIAL \& ENGINEERING CHEMISTRY RESEARCH},
	author = {Song, Hualong and Casey, Abby and Tory, Joanne and Coultas, David and Lester, Daniel and Scott, Peter and Rogers, Nicola J.},
	month = jun,
	year = {2023},
	note = {Infineum UK Ltd},
	pages = {9054--9061},
}

The growing trend of increasing biodiesel concentrationsin dieselfuel blends has led to concerns about its effect on the oxidationof formulated oils within internal combustion engines. We observethat biodiesel is not only susceptible to rapid oxidation at elevatedtemperatures but is also responsible for acceleration of the oxidationprocess of the lubricant base oil when in the presence of solubleiron; this is supported by a range of control and model experiments.A mixture of oxidized biodiesel and Fe(III) leads to the formationof catalytic iron carboxylate networks that remain solubilized, asobserved by UV-Vis and infrared absorption studies. These observationsare important for the fundamental understanding of the chemistry withinindustry standard laboratory bench tests for lubricant oil formulationsand can aid the design of new lubricants with improved biodiesel compatibility.Such lubricants have the potential for a reduced carbon footprintvia waste reduction.

@article{monaco_degradable_2023,
	title = {Degradable glycopolymers for {saRNA} transfection},
	volume = {14},
	issn = {1759-9954},
	doi = {10.1039/d3py00260h},
	abstract = {Gene delivery is a powerful technique that is often exploited in the treatment of several diseases. Currently, most gene vectors are expensive virus-based systems, which can trigger immune responses. As a cheaper and safer alternative to these systems, biodegradable polymers have been widely used to develop gene delivery systems due to their different desirable characteristics. In particular, poly(amido amine)s possess critical desirable characteristics, such as high cell transfection activity, that make them suitable and efficient for gene delivery. In this study, reducible poly(amido amine)s with different side chain lengths and glycopolymers have been developed to create polyplexes with self-amplifying RNA (saRNA). The cell transfection assay showed that sugar decorated poly(amido amine)s revealed better saRNA transfection activity than other non-decorated poly(amido amine)s. Nevertheless, no differences were obtained between the poly(amido amine)s with different side chain lengths. Overall, biodegradable poly(amido amine)s with different alcohols and sugars have been synthesized with high molecular weights and low molecular weight distributions to develop an optimal saRNA delivery system.},
	number = {22},
	urldate = {2023-06-10},
	journal = {POLYMER CHEMISTRY},
	author = {Monaco, Alessandra and Barbieri, Beatriz Dias and Yilmaz, Gokhan and Shattock, Robin J. and Becer, C. Remzi},
	month = jun,
	year = {2023},
	pages = {2750--2761},
}

Gene delivery is a powerful technique that is often exploited in the treatment of several diseases. Currently, most gene vectors are expensive virus-based systems, which can trigger immune responses. As a cheaper and safer alternative to these systems, biodegradable polymers have been widely used to develop gene delivery systems due to their different desirable characteristics. In particular, poly(amido amine)s possess critical desirable characteristics, such as high cell transfection activity, that make them suitable and efficient for gene delivery. In this study, reducible poly(amido amine)s with different side chain lengths and glycopolymers have been developed to create polyplexes with self-amplifying RNA (saRNA). The cell transfection assay showed that sugar decorated poly(amido amine)s revealed better saRNA transfection activity than other non-decorated poly(amido amine)s. Nevertheless, no differences were obtained between the poly(amido amine)s with different side chain lengths. Overall, biodegradable poly(amido amine)s with different alcohols and sugars have been synthesized with high molecular weights and low molecular weight distributions to develop an optimal saRNA delivery system.

@article{al-shok_post-polymerisation_2023,
	title = {Post-polymerisation modification of poly(3-hydroxybutyrate) ({PHB}) using thiol-ene and phosphine addition},
	volume = {14},
	issn = {1759-9954},
	doi = {10.1039/d3py00272a},
	abstract = {As we face the issues associated with fossil resource-based polymers and their environmental impact after their useful life, polyesters become more important as "greener" alternatives due to their potential hydrolytic and enzymatic degradability in various environments. Moreover, post-modifying their structure can additionally open up access to a variety of new materials. During this work the potential to post-modifying synthetic PHB made via the organocatalysed ring-opening polymerisation of beta-butyrolactone (beta-BL) is shown. Modification by thiol-ene 'click' chemistry was succesfully conducted under UV-initiation. Surprisingly, attempting the modification under thermal conditions using dimethylphenylphosphine (DMPP) as catalyst, resulted in the attachment of the phosphine, as shown via NMR spectroscopy. Control experiments using crotonic acid, methyl crotonate and n-butyric acid indicated that the presence of a carboxylic acid group is necessary in order for the phosphine addition to occur. Further, the formation of particles shown via dynamic light scattering (DLS), zeta-potential (ZP) and transmission electron microscopy (TEM) measurements suggest an amphiphilic character of the phosphine-functionalised polymers. Finally, stability studies in the presence of salt and different pH environments revealed a high responsiveness and dependency between pH and particle size as well as surface charge.},
	number = {22},
	urldate = {2023-05-24},
	journal = {POLYMER CHEMISTRY},
	author = {Al-Shok, Lucas and Town, James S. S. and Coursari, Despina and Wilson, Paul and Haddleton, David M. M.},
	month = jun,
	year = {2023},
	pages = {2734--2741},
}

As we face the issues associated with fossil resource-based polymers and their environmental impact after their useful life, polyesters become more important as "greener" alternatives due to their potential hydrolytic and enzymatic degradability in various environments. Moreover, post-modifying their structure can additionally open up access to a variety of new materials. During this work the potential to post-modifying synthetic PHB made via the organocatalysed ring-opening polymerisation of beta-butyrolactone (beta-BL) is shown. Modification by thiol-ene 'click' chemistry was succesfully conducted under UV-initiation. Surprisingly, attempting the modification under thermal conditions using dimethylphenylphosphine (DMPP) as catalyst, resulted in the attachment of the phosphine, as shown via NMR spectroscopy. Control experiments using crotonic acid, methyl crotonate and n-butyric acid indicated that the presence of a carboxylic acid group is necessary in order for the phosphine addition to occur. Further, the formation of particles shown via dynamic light scattering (DLS), zeta-potential (ZP) and transmission electron microscopy (TEM) measurements suggest an amphiphilic character of the phosphine-functionalised polymers. Finally, stability studies in the presence of salt and different pH environments revealed a high responsiveness and dependency between pH and particle size as well as surface charge.

@article{becer_obituary_2023,
	title = {Obituary - {Prof}. {Dr}. {Yusuf} {Yagci} (1952-2023)},
	volume = {44},
	issn = {1022-1336},
	doi = {10.1002/marc.202300173},
	number = {12},
	urldate = {2023-05-12},
	journal = {MACROMOLECULAR RAPID COMMUNICATIONS},
	author = {Becer, C. Remzi},
	month = jun,
	year = {2023},
}

@article{becer_obituary_2023-1,
	title = {Obituary - {Prof}. {Dr}. {Yusuf} {Yagci} (1952-2023)},
	volume = {224},
	issn = {1022-1352},
	doi = {10.1002/macp.202300088},
	number = {12},
	urldate = {2023-05-11},
	journal = {MACROMOLECULAR CHEMISTRY AND PHYSICS},
	author = {Becer, C. Remzi},
	month = jun,
	year = {2023},
}

@article{clothier_multiblock_2023,
	title = {Multiblock copolymer synthesis via {RAFT} emulsion polymerization},
	volume = {52},
	issn = {0306-0012},
	doi = {10.1039/d2cs00115b},
	abstract = {A multiblock copolymer is a polymer of a specific structure that consists of multiple covalently linked segments, each comprising a different monomer type. The control of the monomer sequence has often been described as the "holy grail" of synthetic polymer chemistry, with the ultimate goal being synthetic access to polymers of a "perfect" structure, where each monomeric building block is placed at a desired position along the polymer chain. Given that polymer properties are intimately linked to the microstructure and monomer distribution along the constituent chains, it goes without saying that there exist seemingly endless opportunities in terms of fine-tuning the properties of such materials by careful consideration of the length of each block, the number and order of blocks, and the inclusion of monomers with specific functional groups. The area of multiblock copolymer synthesis remains relatively unexplored, in particular with regard to structure-property relationships, and there are currently significant opportunities for the design and synthesis of advanced materials. The present review focuses on the synthesis of multiblock copolymers via reversible addition-fragmentation chain transfer (RAFT) polymerization implemented as aqueous emulsion polymerization. RAFT emulsion polymerization offers intriguing opportunities not only for the advanced synthesis of multiblock copolymers, but also provides access to polymeric nanoparticles of specific morphologies. Precise multiblock copolymer synthesis coupled with self-assembly offers material morphology control on length scales ranging from a few nanometers to a micrometer. It is imperative that polymer chemists interact with physicists and material scientists to maximize the impact of these materials of the future.},
	number = {10},
	urldate = {2023-05-21},
	journal = {CHEMICAL SOCIETY REVIEWS},
	author = {Clothier, Glenn K. K. and Guimaraes, Thiago R. and Thompson, Steven W. and Rho, Julia Y. and Perrier, Sebastien and Moad, Graeme and Zetterlund, Per B.},
	month = may,
	year = {2023},
	pages = {3438--3469},
}

A multiblock copolymer is a polymer of a specific structure that consists of multiple covalently linked segments, each comprising a different monomer type. The control of the monomer sequence has often been described as the "holy grail" of synthetic polymer chemistry, with the ultimate goal being synthetic access to polymers of a "perfect" structure, where each monomeric building block is placed at a desired position along the polymer chain. Given that polymer properties are intimately linked to the microstructure and monomer distribution along the constituent chains, it goes without saying that there exist seemingly endless opportunities in terms of fine-tuning the properties of such materials by careful consideration of the length of each block, the number and order of blocks, and the inclusion of monomers with specific functional groups. The area of multiblock copolymer synthesis remains relatively unexplored, in particular with regard to structure-property relationships, and there are currently significant opportunities for the design and synthesis of advanced materials. The present review focuses on the synthesis of multiblock copolymers via reversible addition-fragmentation chain transfer (RAFT) polymerization implemented as aqueous emulsion polymerization. RAFT emulsion polymerization offers intriguing opportunities not only for the advanced synthesis of multiblock copolymers, but also provides access to polymeric nanoparticles of specific morphologies. Precise multiblock copolymer synthesis coupled with self-assembly offers material morphology control on length scales ranging from a few nanometers to a micrometer. It is imperative that polymer chemists interact with physicists and material scientists to maximize the impact of these materials of the future.

@article{zhao_active_2023,
	title = {Active {Learning} as a {Tool} for {Optimizing} "{Plug}-n-{Play}" {Electrochemical} {Atom} {Transfer} {Radical} {Polymerization}},
	volume = {224},
	issn = {1022-1352},
	doi = {10.1002/macp.202300039},
	abstract = {A recently reported "plug-n-play" approach to simplified electrochemical atom transfer radical polymerization (seATRP) is investigated using machine learning. It is shown that Bayesian optimization via an active learning (AL) algorithm accelerates optimization of the polymerization of oligo(ethylene glycol methyl ether acrylate)(480) (OEGA(480)) in water. Molecular weight distribution (M-w/M-n; dispersity; D-m) is the output selected for optimization targeting poly(oligo[ethylene glycol methyl ether acrylate]) (POEGA(480)) with low dispersity (D-m {\textless} 1.30). Input variables included applied potential (E-app), [M] and [M]/[I], which led to a potential space of 275 possible reaction conditions. From a training data set of seven reactions, selected to yield uncontrolled POEGA(480) with higher dispersities (D-m {\textgreater} 1.5), ten iteration loops are performed. During each iteration the algorithm suggests the next reaction conditions. The reactions are then performed and the conversion, number average molecular weight (M-n) and D-m values are recorded and the D-m values fed back into the algorithm. Overall, 80\% of the experiments yield POEGA with D-m {\textless} 1.30. Conversely, only 30\% of experiments performed using reaction conditions selected at random from the possible reaction space yield POEGA with D-m {\textless} 1.30. This study suggests that adopting AL methods can improve the efficiency of optimizing a given seATRP reaction.},
	number = {12},
	urldate = {2023-05-07},
	journal = {MACROMOLECULAR CHEMISTRY AND PHYSICS},
	author = {Zhao, Boyu and Cheng, Jiahao and Gao, Junlong and Haddleton, David. M. and Wilson, Paul},
	month = jun,
	year = {2023},
}

A recently reported "plug-n-play" approach to simplified electrochemical atom transfer radical polymerization (seATRP) is investigated using machine learning. It is shown that Bayesian optimization via an active learning (AL) algorithm accelerates optimization of the polymerization of oligo(ethylene glycol methyl ether acrylate)(480) (OEGA(480)) in water. Molecular weight distribution (M-w/M-n; dispersity; D-m) is the output selected for optimization targeting poly(oligo[ethylene glycol methyl ether acrylate]) (POEGA(480)) with low dispersity (D-m \textless 1.30). Input variables included applied potential (E-app), [M] and [M]/[I], which led to a potential space of 275 possible reaction conditions. From a training data set of seven reactions, selected to yield uncontrolled POEGA(480) with higher dispersities (D-m \textgreater 1.5), ten iteration loops are performed. During each iteration the algorithm suggests the next reaction conditions. The reactions are then performed and the conversion, number average molecular weight (M-n) and D-m values are recorded and the D-m values fed back into the algorithm. Overall, 80% of the experiments yield POEGA with D-m \textless 1.30. Conversely, only 30% of experiments performed using reaction conditions selected at random from the possible reaction space yield POEGA with D-m \textless 1.30. This study suggests that adopting AL methods can improve the efficiency of optimizing a given seATRP reaction.

@article{coverdale_triplex_2023,
	title = {Triplex metallohelices have enantiomer-dependent mechanisms of action in colon cancer cells},
	volume = {52},
	issn = {1477-9226},
	doi = {10.1039/d3dt00948c},
	abstract = {Self-assembled enantiomers of an asymmetric di-iron metallohelix differ in their antiproliferative activities against HCT116 colon cancer cells such that the compound with ?-helicity at the metals becomes more potent than the Delta compound with increasing exposure time. From concentration- and temperature-dependent Fe-57 isotopic labelling studies of cellular accumulation we postulate that while the more potent ? enantiomer undergoes carrier-mediated efflux, for Delta the process is principally equilibrative. Cell fractionation studies demonstrate that both enantiomers localise in a similar fashion; compound is observed mostly within the cytoskeleton and/or genomic DNA, with significant amounts also found in the nucleus and membrane, but with negligible concentration in the cytosol. Cell cycle analyses using flow cytometry reveal that the Delta enantiomer induces mild arrest in the G(1) phase, while ? causes a very large dose-dependent increase in the G(2)/M population at a concentration significantly below the relevant IC50. Correspondingly, G(2)-M checkpoint failure as a result of ?-metallohelix binding to DNA is shown to be feasible by linear dichroism studies, which indicate, in contrast to the Delta compound, a quite specific mode of binding, probably in the major groove. Further, spindle assembly checkpoint (SAC) failure, which could also be responsible for the observed G(2)/M arrest, is established as a feasible mechanism for the ? helix via drug combination (synergy) studies and the discovery of tubulin and actin inhibition. Here, while the ? compound stabilizes F-actin and induces a distinct change in tubulin architecture of HCT116 cells, Delta promotes depolymerization and more subtle changes in microtubule and actin networks.},
	number = {20},
	urldate = {2023-05-09},
	journal = {DALTON TRANSACTIONS},
	author = {Coverdale, J. P. C. and Kostrhunova, H. and Markova, L. and Song, H. and Postings, M. and Bridgewater, H. E. and Brabec, V. and Rogers, N. J. and Scott, P.},
	month = may,
	year = {2023},
	pages = {6656--6667},
}

Self-assembled enantiomers of an asymmetric di-iron metallohelix differ in their antiproliferative activities against HCT116 colon cancer cells such that the compound with ?-helicity at the metals becomes more potent than the Delta compound with increasing exposure time. From concentration- and temperature-dependent Fe-57 isotopic labelling studies of cellular accumulation we postulate that while the more potent ? enantiomer undergoes carrier-mediated efflux, for Delta the process is principally equilibrative. Cell fractionation studies demonstrate that both enantiomers localise in a similar fashion; compound is observed mostly within the cytoskeleton and/or genomic DNA, with significant amounts also found in the nucleus and membrane, but with negligible concentration in the cytosol. Cell cycle analyses using flow cytometry reveal that the Delta enantiomer induces mild arrest in the G(1) phase, while ? causes a very large dose-dependent increase in the G(2)/M population at a concentration significantly below the relevant IC50. Correspondingly, G(2)-M checkpoint failure as a result of ?-metallohelix binding to DNA is shown to be feasible by linear dichroism studies, which indicate, in contrast to the Delta compound, a quite specific mode of binding, probably in the major groove. Further, spindle assembly checkpoint (SAC) failure, which could also be responsible for the observed G(2)/M arrest, is established as a feasible mechanism for the ? helix via drug combination (synergy) studies and the discovery of tubulin and actin inhibition. Here, while the ? compound stabilizes F-actin and induces a distinct change in tubulin architecture of HCT116 cells, Delta promotes depolymerization and more subtle changes in microtubule and actin networks.

@article{liu_enantioselective_2023,
	title = {Enantioselective {Degrader} for {Elimination} of {Extracellular} {Aggregation}-{Prone} {Proteins} {hIAPP} {Associated} with {Type} 2 {Diabetes}},
	volume = {17},
	issn = {1936-0851},
	doi = {10.1021/acsnano.2c11476},
	abstract = {Targeted protein degradation has demonstrated the power to modulate protein homeostasis. For overcoming the limitation to intracellular protein degradation, lysosome targeting chimeras have been recently developed and successfully utilized to degrade a range of disease-relevant extracellular and membrane proteins. Inspired by this strategy, here we describe our proof-of-concept studies using metallohelix-based degraders to deliver the extracellular human islet amyloid polypeptide (hIAPP) into the lysosomes for degradation. Our designed metallohelix can bind and inhibit hIAPP aggregation, and the conjugated tri-GalNAc motif can target macrophage galactose-type lectin 1 (MGL1), yielding chimeric molecules that can both inhibit hIAPP aggregation and direct the bound hIAPP for lysosomal degradation in macrophages. Further studies demonstrate that the enhanced hIAPP clearance has been through the endolysosomal system and depends on MGL1-mediated endocytosis. Intriguingly, ? enantiomers show even better efficiency in preventing hIAPP aggregation and promoting internalization and degradation of hIAPP than Delta enantiomers. Moreover, metallohelix-based degraders also faciltate the clearance of hIAPP through asialoglycoprotein receptor in liver cells. Overall, our studies demonstrate that chiral metallohelix can be employed for targeted degradation of extracellular misfolded proteins and possess enantioselectivity.},
	number = {9},
	urldate = {2023-04-30},
	journal = {ACS NANO},
	author = {Liu, Zhenqi and Yu, Dongqin and Song, Hualong and Postings, Miles Lewis and Scott, Peter and Wang, Zhao and Ren, Jinsong and Qu, Xiaogang},
	month = may,
	year = {2023},
	pages = {8141--8152},
}

Targeted protein degradation has demonstrated the power to modulate protein homeostasis. For overcoming the limitation to intracellular protein degradation, lysosome targeting chimeras have been recently developed and successfully utilized to degrade a range of disease-relevant extracellular and membrane proteins. Inspired by this strategy, here we describe our proof-of-concept studies using metallohelix-based degraders to deliver the extracellular human islet amyloid polypeptide (hIAPP) into the lysosomes for degradation. Our designed metallohelix can bind and inhibit hIAPP aggregation, and the conjugated tri-GalNAc motif can target macrophage galactose-type lectin 1 (MGL1), yielding chimeric molecules that can both inhibit hIAPP aggregation and direct the bound hIAPP for lysosomal degradation in macrophages. Further studies demonstrate that the enhanced hIAPP clearance has been through the endolysosomal system and depends on MGL1-mediated endocytosis. Intriguingly, ? enantiomers show even better efficiency in preventing hIAPP aggregation and promoting internalization and degradation of hIAPP than Delta enantiomers. Moreover, metallohelix-based degraders also faciltate the clearance of hIAPP through asialoglycoprotein receptor in liver cells. Overall, our studies demonstrate that chiral metallohelix can be employed for targeted degradation of extracellular misfolded proteins and possess enantioselectivity.

@article{golba_visible_2023,
	title = {Visible {Light} {Conjugation} with {Triazolinediones} as a {Route} to {Degradable} {Poly}(ethylene glycol)-{Lipids} for {mRNA} {Lipid} {Nanoparticle} {Formulation}},
	volume = {62},
	issn = {1433-7851},
	doi = {10.1002/anie.202301102},
	abstract = {Polyethylene glycol (PEG) is considered as the gold standard for colloidal stabilization of nanomedicines, yet PEG is non-degradable and lacks functionality on the backbone. Herein, we introduce concomitantly PEG backbone functionality and degradability via a one-step modification with 1,2,4-triazoline-3,5-diones (TAD) under green light. The TAD-PEG conjugates are degradable in aqueous medium under physiological conditions, with the rate of hydrolysis depending on pH and temperature. Subsequently, a PEG-lipid is modified with TAD-derivatives and successfully used for messenger RNA (mRNA) lipid nanoparticle (LNP) delivery, thereby improving mRNA transfection efficiency on multiple cell cultures in vitro. In vivo, in mice, mRNA LNP formulation exhibited a similar tissue distribution as common LNPs, with a slight decrease in transfection efficiency. Our findings pave the road towards the design of degradable, backbone-functionalized PEG for applications in nanomedicine and beyond.},
	number = {23},
	urldate = {2023-04-28},
	journal = {ANGEWANDTE CHEMIE-INTERNATIONAL EDITION},
	author = {Golba, Bianka and Soete, Matthieu and Zhong, Zifu and Sanders, Niek and Du Prez, Filip E. and Houck, Hannes A. and De Geest, Bruno G.},
	month = jun,
	year = {2023},
}

Polyethylene glycol (PEG) is considered as the gold standard for colloidal stabilization of nanomedicines, yet PEG is non-degradable and lacks functionality on the backbone. Herein, we introduce concomitantly PEG backbone functionality and degradability via a one-step modification with 1,2,4-triazoline-3,5-diones (TAD) under green light. The TAD-PEG conjugates are degradable in aqueous medium under physiological conditions, with the rate of hydrolysis depending on pH and temperature. Subsequently, a PEG-lipid is modified with TAD-derivatives and successfully used for messenger RNA (mRNA) lipid nanoparticle (LNP) delivery, thereby improving mRNA transfection efficiency on multiple cell cultures in vitro. In vivo, in mice, mRNA LNP formulation exhibited a similar tissue distribution as common LNPs, with a slight decrease in transfection efficiency. Our findings pave the road towards the design of degradable, backbone-functionalized PEG for applications in nanomedicine and beyond.

@article{mackley_sample_2023,
	title = {Sample {Preparation} of {Atherosclerotic} {Plaque} for {SAXS}/{WAXS} {Experimentation}},
	volume = {8},
	issn = {2470-1343},
	doi = {10.1021/acsomega.3c00060},
	abstract = {Atherosclerosis is often described as a single disease entity; however, the morphology of each plaque is unique to the individual. The field currently lacks a technique that can discriminate stable from unstable plaques, to identify those at risk of a thromboembolic event. Small-and wide-angle X-ray scattering (SAXS/ WAXS) holds the potential to be able to identify key materials present in a plaque, such as cholesterol species, collagen, low-density lipoproteins (LDLs), and hydroxyapatite. Protocols have been established for the preparation of excised human atherosclerotic tissue that are investigated herein. This includes the fixing, sectioning, and substrate selection of the sample. Through several sample preparation methods, vast improvements have been made to sample-to-noise ratio and background subtraction.},
	number = {15},
	urldate = {2023-05-07},
	journal = {ACS OMEGA},
	author = {Mackley, Rebecca R. and Huband, Steven and Schiller, Tara L.},
	month = apr,
	year = {2023},
	pages = {13833--13839},
}

Atherosclerosis is often described as a single disease entity; however, the morphology of each plaque is unique to the individual. The field currently lacks a technique that can discriminate stable from unstable plaques, to identify those at risk of a thromboembolic event. Small-and wide-angle X-ray scattering (SAXS/ WAXS) holds the potential to be able to identify key materials present in a plaque, such as cholesterol species, collagen, low-density lipoproteins (LDLs), and hydroxyapatite. Protocols have been established for the preparation of excised human atherosclerotic tissue that are investigated herein. This includes the fixing, sectioning, and substrate selection of the sample. Through several sample preparation methods, vast improvements have been made to sample-to-noise ratio and background subtraction.

@article{zhao_recent_2023,
	title = {Recent progress and applications enabled via electrochemically triggered and controlled chain-growth polymerizations},
	volume = {14},
	issn = {1759-9954},
	doi = {10.1039/d3py00062a},
	abstract = {The use of external stimuli to trigger and/or control polymer synthesis has become a prominent research theme over the last 20 years. With the need for more sustainable methods of polymer synthesis and production, interest in this area has intensified in the last decade. External stimuli include, but are not limited to; heat, light, ultrasound and electricity. Relative to their chemically mediated counterparts, these methods of stimulus are non-invasive, atom economic and offer excellent spatial and temporal control over reaction progress. In particular, the use of an electric field to deliver electrons as reagents in electrosynthesis is considered to be an emerging green and sustainable solution in organic and polymer synthesis. Through modulating the applied potential/current precise control over the kinetics and thermodynamics of electron-transfer reactions can be achieved, which can enhance the efficiency and selectivity of targeted chemical transformations. In this review, we have captured the recent progress made in electrochemically triggered and controlled polymer synthesis techniques, focusing on chain-growth polymerizations including radical, ionic and ring-opening polymerizations and applications enabled by the use of an electric field to perform such reactions.},
	number = {17},
	urldate = {2023-04-28},
	journal = {POLYMER CHEMISTRY},
	author = {Zhao, Boyu and Wilson, Paul},
	month = may,
	year = {2023},
	pages = {2000--2021},
}

The use of external stimuli to trigger and/or control polymer synthesis has become a prominent research theme over the last 20 years. With the need for more sustainable methods of polymer synthesis and production, interest in this area has intensified in the last decade. External stimuli include, but are not limited to; heat, light, ultrasound and electricity. Relative to their chemically mediated counterparts, these methods of stimulus are non-invasive, atom economic and offer excellent spatial and temporal control over reaction progress. In particular, the use of an electric field to deliver electrons as reagents in electrosynthesis is considered to be an emerging green and sustainable solution in organic and polymer synthesis. Through modulating the applied potential/current precise control over the kinetics and thermodynamics of electron-transfer reactions can be achieved, which can enhance the efficiency and selectivity of targeted chemical transformations. In this review, we have captured the recent progress made in electrochemically triggered and controlled polymer synthesis techniques, focusing on chain-growth polymerizations including radical, ionic and ring-opening polymerizations and applications enabled by the use of an electric field to perform such reactions.

@article{rajakanthan_effect_2023,
	title = {The effect of side chain spacer length on the thermoresponsive behaviour of poly(methylamide acrylate)s},
	volume = {14},
	issn = {1759-9954},
	doi = {10.1039/d3py00154g},
	abstract = {We report the synthesis of three methylamide acrylate monomers with varying spacer length between the polymerizable acrylate and pendant amide functionalities; methylamide ethyl acrylate (MAmEA), methylamide propyl acrylate (MAmPA) and methylamide butyl acrylate (MAmBA). Each monomer was subsequently polymerised via redox-initiated reversible addittion-fragmentation chain transfer (RRAFT) to yield well-defined homopolymers with differing physicochemical properties. All homopolymers were found to be amorphous, and thermally degrade via a two-step decomposition process. Whilst P(MAmEA) and P(MAmPA) were found to be soluble in aqueous solution between 30-80 degrees C, P(MAmBA) showed a lower critical solution temperature (LCST) behaviour. Detailed aqueous solubilty studies performed on P(MAmBA) revealed that the cloud point temperature (T-cp) could be tuned based on the degree of polymerisation (DPn), concentration and nature of the aqueous media, highlighting its potential use as a water-soluble, thermoresponsive polymer in a range of applications.},
	number = {17},
	urldate = {2023-04-15},
	journal = {POLYMER CHEMISTRY},
	author = {Rajakanthan, Alexander and Wilson, Paul and Kempe, Kristian},
	month = may,
	year = {2023},
	pages = {2054--2062},
}

We report the synthesis of three methylamide acrylate monomers with varying spacer length between the polymerizable acrylate and pendant amide functionalities; methylamide ethyl acrylate (MAmEA), methylamide propyl acrylate (MAmPA) and methylamide butyl acrylate (MAmBA). Each monomer was subsequently polymerised via redox-initiated reversible addittion-fragmentation chain transfer (RRAFT) to yield well-defined homopolymers with differing physicochemical properties. All homopolymers were found to be amorphous, and thermally degrade via a two-step decomposition process. Whilst P(MAmEA) and P(MAmPA) were found to be soluble in aqueous solution between 30-80 degrees C, P(MAmBA) showed a lower critical solution temperature (LCST) behaviour. Detailed aqueous solubilty studies performed on P(MAmBA) revealed that the cloud point temperature (T-cp) could be tuned based on the degree of polymerisation (DPn), concentration and nature of the aqueous media, highlighting its potential use as a water-soluble, thermoresponsive polymer in a range of applications.

@article{gauci_two_2023,
	title = {Two {Functions} from a {Single} {Photoresist}: {Tuning} {Microstructure} {Degradability} from {Light}-{Stabilized} {Dynamic} {Materials}},
	volume = {35},
	issn = {0935-9648},
	doi = {10.1002/adma.202300151},
	abstract = {A photoresist-based on a light-stabilized dynamic material driven by an out-of-equilibrium photo-Diels-Alder reaction of triazolinediones with naphthalenes-whose ability to intrinsically degrade postprinting can be tuned by a simple adjustment of laser intensity during 3D laser lithography is introduced. The resist's ability to form stable networks under green light irradiation that degrade in the dark is transformed into a tunable degradable 3D printing material platform. In-depth characterization of the printed microstructures via atomic force microscopy before and during degradation reveals the high dependency of the final structures' properties on the writing parameters. Upon identifying the ideal writing parameters and their effect on the network structure, it is possible to selectively toggle between stable and fully degradable structures. This simplifies the direct laser writing manufacturing process of multifunctional materials significantly, which typically requires the use of separate resists and consecutive writing efforts to achieve degradable and nondegradable material sections.},
	number = {22},
	urldate = {2023-04-12},
	journal = {ADVANCED MATERIALS},
	author = {Gauci, Steven C. and Ehrmann, Katharina and Gernhardt, Marvin and Tuten, Bryan and Blasco, Eva and Frisch, Hendrik and Jayalatharachchi, Vishakya and Blinco, James P. and Houck, Hannes A. and Barner-Kowollik, Christopher},
	month = jun,
	year = {2023},
}

A photoresist-based on a light-stabilized dynamic material driven by an out-of-equilibrium photo-Diels-Alder reaction of triazolinediones with naphthalenes-whose ability to intrinsically degrade postprinting can be tuned by a simple adjustment of laser intensity during 3D laser lithography is introduced. The resist's ability to form stable networks under green light irradiation that degrade in the dark is transformed into a tunable degradable 3D printing material platform. In-depth characterization of the printed microstructures via atomic force microscopy before and during degradation reveals the high dependency of the final structures' properties on the writing parameters. Upon identifying the ideal writing parameters and their effect on the network structure, it is possible to selectively toggle between stable and fully degradable structures. This simplifies the direct laser writing manufacturing process of multifunctional materials significantly, which typically requires the use of separate resists and consecutive writing efforts to achieve degradable and nondegradable material sections.

@article{magee_silane_2023,
	title = {Silane functionalization of {WS2} nanotubes for interaction with poly(lactic acid)},
	volume = {15},
	issn = {2040-3364},
	doi = {10.1039/d3nr00583f},
	abstract = {Functionalisation of nanofillers is required for the promotion of strong interfacial interactions with polymers and is essential as a route for the preparation of (nano)composites with superior mechanical properties. Tungsten disulphide nanotubes (WS2 NTs) were functionalized using (3-aminopropyl) triethoxysilane (APTES) for preparation of composites with poly(lactic acid) (PLA). The WS2 NTs : APTES ratios used were 1 : 1, 1 : 2 and 1 : 4 WS2 NTs : APTES. The APTES formed siloxane networks bound to the NTs via surface oxygen and carbon moieties adsorbed on the WS2 NTs surface, detected by X-ray photoelectron spectroscopy (XPS) studies and chemical mapping using energy dispersive X-ray spectroscopy in the scanning transmission electron microscope (STEM-EDS). The successful silane modification of the WS2 NTs was clearly evident with both significant peak shifting by as much as 60 cm(-1) for Si-O-Si vibrations (FTIR) and peak broadening of the A(1g) band in the Raman spectra of the WS2 NTs. The evolution of new bands was also observed and are associated with Si-CH2-CH2 and, symmetric and assymetric -NH3+ deformation modes (FTIR). Further evidence for functionalization was obtained from zeta potential measurements as there was a change in surface charge from negative for pure WS2 NTs to positive for APTES modified WS2 NTs. Additionally, the thermal stability of APTES was shifted to much higher temperatures as it was bound to the WS2 NTs. The APTES modified WS2 NTs were organophilic and readily dispersed in PLA, while presence of the pendant amine and hydroxyl groups resulted in strong interfacial interactions with the polymer matrix. The inclusion of as little as 0.5 wt\% WS2 NTs modified with 2.0 wt\% APTES resulted in an increase of 600\% in both the elongation at break (a measure of ductility) and the tensile toughness relative to neat PLA, without impacting the stiffness or strength of the polymer.},
	number = {16},
	urldate = {2023-05-02},
	journal = {NANOSCALE},
	author = {Magee, Eimear and Tang, Fengzai and Walker, Marc and Zak, Alla and Tenne, Reshef and McNally, Tony},
	month = apr,
	year = {2023},
	note = {Holon Inst Technol HIT},
	pages = {7577--7590},
}

Functionalisation of nanofillers is required for the promotion of strong interfacial interactions with polymers and is essential as a route for the preparation of (nano)composites with superior mechanical properties. Tungsten disulphide nanotubes (WS2 NTs) were functionalized using (3-aminopropyl) triethoxysilane (APTES) for preparation of composites with poly(lactic acid) (PLA). The WS2 NTs : APTES ratios used were 1 : 1, 1 : 2 and 1 : 4 WS2 NTs : APTES. The APTES formed siloxane networks bound to the NTs via surface oxygen and carbon moieties adsorbed on the WS2 NTs surface, detected by X-ray photoelectron spectroscopy (XPS) studies and chemical mapping using energy dispersive X-ray spectroscopy in the scanning transmission electron microscope (STEM-EDS). The successful silane modification of the WS2 NTs was clearly evident with both significant peak shifting by as much as 60 cm(-1) for Si-O-Si vibrations (FTIR) and peak broadening of the A(1g) band in the Raman spectra of the WS2 NTs. The evolution of new bands was also observed and are associated with Si-CH2-CH2 and, symmetric and assymetric -NH3+ deformation modes (FTIR). Further evidence for functionalization was obtained from zeta potential measurements as there was a change in surface charge from negative for pure WS2 NTs to positive for APTES modified WS2 NTs. Additionally, the thermal stability of APTES was shifted to much higher temperatures as it was bound to the WS2 NTs. The APTES modified WS2 NTs were organophilic and readily dispersed in PLA, while presence of the pendant amine and hydroxyl groups resulted in strong interfacial interactions with the polymer matrix. The inclusion of as little as 0.5 wt% WS2 NTs modified with 2.0 wt% APTES resulted in an increase of 600% in both the elongation at break (a measure of ductility) and the tensile toughness relative to neat PLA, without impacting the stiffness or strength of the polymer.

@article{becker_step-growth_2023,
	title = {Step-{Growth} {Glycopolymers} with a {Defined} {Tacticity} for {Selective} {Carbohydrate}-{Lectin} {Recognition}},
	volume = {24},
	issn = {1525-7797},
	doi = {10.1021/acs.biomac.3c00133},
	abstract = {Glycopolymers are potent candidates for biomedical applications by exploiting multivalent carbohydrate-lectin interactions. Owing to their specific recognition capabilities, glycosylated polymers can be utilized for targeted drug delivery to certain cell types bearing the corresponding lectin receptors. A fundamental challenge in glycopolymer research, however, is the specificity of recognition to receptors binding to the same sugar unit (e.g., mannose). Variation of polymer backbone chirality has emerged as an effective method to distinguish between lectins on a molecular level. Herein, we present a facile route toward producing glycopolymers with a defined tacticity based on a step-growth polymerization technique using click chemistry. A set of polymers have been fabricated and further functionalized with mannose moieties to enable lectin binding to receptors relevant to the immune system (mannose-binding lectin, dendritic cell-specific intercellular adhesion molecule-3-grabbing non-integrin, and dendritic and thymic epithelial cell-205). Surface plasmon resonance spectrometry was employed to determine the kinetic parameters of the step-growth glycopolymers. The results highlight the importance of structural complexity in advancing glycopolymer synthesis, yet multivalency remains a main driving force in lectin recognition.},
	number = {4},
	urldate = {2023-04-19},
	journal = {BIOMACROMOLECULES},
	author = {Becker, Jonas and Terracciano, Roberto and Yilmaz, Gokhan and Napier, Richard and Becer, C. Remzi},
	month = apr,
	year = {2023},
	pages = {1924--1933},
}

Glycopolymers are potent candidates for biomedical applications by exploiting multivalent carbohydrate-lectin interactions. Owing to their specific recognition capabilities, glycosylated polymers can be utilized for targeted drug delivery to certain cell types bearing the corresponding lectin receptors. A fundamental challenge in glycopolymer research, however, is the specificity of recognition to receptors binding to the same sugar unit (e.g., mannose). Variation of polymer backbone chirality has emerged as an effective method to distinguish between lectins on a molecular level. Herein, we present a facile route toward producing glycopolymers with a defined tacticity based on a step-growth polymerization technique using click chemistry. A set of polymers have been fabricated and further functionalized with mannose moieties to enable lectin binding to receptors relevant to the immune system (mannose-binding lectin, dendritic cell-specific intercellular adhesion molecule-3-grabbing non-integrin, and dendritic and thymic epithelial cell-205). Surface plasmon resonance spectrometry was employed to determine the kinetic parameters of the step-growth glycopolymers. The results highlight the importance of structural complexity in advancing glycopolymer synthesis, yet multivalency remains a main driving force in lectin recognition.

@article{ghielmetti_regioselective_2023,
	title = {Regioselective photocycloaddition for light-stabilised dynamic materials design},
	volume = {14},
	issn = {1759-9954},
	doi = {10.1039/d3py00027c},
	abstract = {The exact molecular network connectivity in dynamic polymer networks greatly impacts material properties and reprocessing conditions. While endo/exo stereoisomer effects of thermoreversible cycloaddition reactions (e.g. furan/maleimide) are well known to influence the overall decrosslinking kinetics of dynamic polymer networks, the impact of regioisomerism is often overlooked. Herein, we highlight the importance of interchanging regioisomer fractions in light-stabilised dynamic materials (LSDMs). Specifically, the photo-driven [4 + 2] cycloaddition of substituted naphthalenes with triazolinediones (TADs) is demonstrated to continuously equilibrate under green light, resulting in an enrichment in one of two regioisomers and effectively changing the overall cycloreversion kinetics. To bypass implications of this chemically inhomogeneous nature of the crosslinks when embedded in a macromolecular gel, a library of naphthalene reaction partners is screened to develop a completely regioselective TAD/naphthalene system. Additionally, naphthalene substitution allowed for a fine control over the cycloreversion kinetics with debonding half-life times ranging from 9 to 260 h at ambient temperature. In particular, 2,3-naphthalimides were found to yield both complete regioselectivity and fast dissociation kinetics, making it an interesting scaffold for the design of dynamic covalent materials. Consequently, 2,3-naphthalimide-based monomers were prepared and copolymerised with methyl methacrylate, methyl acrylate and N-isopropyl acrylamide. The copolymers were successfully photo-crosslinked with green light (lambda = 515-525 nm) using a bis-triazolinedione compound to obtain organogels that spontaneously collapsed in the dark, which offers new opportunities to further advance the development and applications of light-stabilised dynamic materials.},
	number = {13},
	urldate = {2023-03-24},
	journal = {POLYMER CHEMISTRY},
	author = {Ghielmetti, Alyssa J. J. and Barner-Kowollik, Christopher and Du Prez, Filip E. E. and Houck, Hannes A. A.},
	month = mar,
	year = {2023},
	pages = {1554--1566},
}

The exact molecular network connectivity in dynamic polymer networks greatly impacts material properties and reprocessing conditions. While endo/exo stereoisomer effects of thermoreversible cycloaddition reactions (e.g. furan/maleimide) are well known to influence the overall decrosslinking kinetics of dynamic polymer networks, the impact of regioisomerism is often overlooked. Herein, we highlight the importance of interchanging regioisomer fractions in light-stabilised dynamic materials (LSDMs). Specifically, the photo-driven [4 + 2] cycloaddition of substituted naphthalenes with triazolinediones (TADs) is demonstrated to continuously equilibrate under green light, resulting in an enrichment in one of two regioisomers and effectively changing the overall cycloreversion kinetics. To bypass implications of this chemically inhomogeneous nature of the crosslinks when embedded in a macromolecular gel, a library of naphthalene reaction partners is screened to develop a completely regioselective TAD/naphthalene system. Additionally, naphthalene substitution allowed for a fine control over the cycloreversion kinetics with debonding half-life times ranging from 9 to 260 h at ambient temperature. In particular, 2,3-naphthalimides were found to yield both complete regioselectivity and fast dissociation kinetics, making it an interesting scaffold for the design of dynamic covalent materials. Consequently, 2,3-naphthalimide-based monomers were prepared and copolymerised with methyl methacrylate, methyl acrylate and N-isopropyl acrylamide. The copolymers were successfully photo-crosslinked with green light (lambda = 515-525 nm) using a bis-triazolinedione compound to obtain organogels that spontaneously collapsed in the dark, which offers new opportunities to further advance the development and applications of light-stabilised dynamic materials.

@article{rajkumar_extensible_2023,
	title = {An extensible density-biasing approach for molecular simulations of multicomponent block copolymers},
	volume = {19},
	issn = {1744-683X},
	doi = {10.1039/d2sm01516a},
	abstract = {A node-density biased Monte Carlo methodology is proposed for the molecular structure generation of complex block copolymers. Within this methodology, the block copolymer is represented as bead-spring model. Using self-consistent field theory, a density field for all monomer species within the system is calculated. Block copolymers are generated by random walk configuration biased by the density fields. The proposed algorithm then modifies the generation process by taking the global structure of the polymer into account. It is then demonstrated that these global considerations can be built into the sampling procedure, specifically through functions that assign a permissible difference in density field value between relevant monomer species to each step of the random walk. In this way, the random walk may be naturally controlled to provide the most appropriate conformations. The overall viability of this approach has been demonstrated by using the resulting configurations in molecular dynamics simulations. This new methodology is demonstrated to be powerful enough to generate molecular configurations for a much wider variety of materials than the original approach. Two key examples of the new capabilities of the method are viable configurations for ABABA pentablock copolymers and ABC triblock terpolymers.},
	number = {8},
	urldate = {2023-02-25},
	journal = {SOFT MATTER},
	author = {Rajkumar, Aravinthen and Brommer, Peter and Figiel, Lukasz},
	month = feb,
	year = {2023},
	pages = {1569--1585},
}

A node-density biased Monte Carlo methodology is proposed for the molecular structure generation of complex block copolymers. Within this methodology, the block copolymer is represented as bead-spring model. Using self-consistent field theory, a density field for all monomer species within the system is calculated. Block copolymers are generated by random walk configuration biased by the density fields. The proposed algorithm then modifies the generation process by taking the global structure of the polymer into account. It is then demonstrated that these global considerations can be built into the sampling procedure, specifically through functions that assign a permissible difference in density field value between relevant monomer species to each step of the random walk. In this way, the random walk may be naturally controlled to provide the most appropriate conformations. The overall viability of this approach has been demonstrated by using the resulting configurations in molecular dynamics simulations. This new methodology is demonstrated to be powerful enough to generate molecular configurations for a much wider variety of materials than the original approach. Two key examples of the new capabilities of the method are viable configurations for ABABA pentablock copolymers and ABC triblock terpolymers.

@article{neves_discrimination_2023,
	title = {Discrimination between protein glycoforms using lectin-functionalised gold nanoparticles as signal enhancers},
	volume = {8},
	issn = {2055-6756},
	doi = {10.1039/d2nh00470d},
	abstract = {Glycoforms (and other post-translational modifications) of otherwise identical proteins can indicate pathogenesis/disease state and hence new tools to detect and sense a protein's glycosylation status are essential. Antibody-based assays against specific protein sequences do not typically discriminate between glycoforms. Here we demonstrate a 'sandwich' bio-assay approach, whereby antibodies immobilised onto biolayer interferometry sensors first select proteins, and then the specific glycoform is identified using gold nanoparticles functionalised with lectins which provide signal enhancement. The nanoparticles significantly enhance the signal relative to lectins alone, allowing glycoform specific detection as low as 0.04 mu g mL(-1) (1.4 nM) in buffer, and crucially there is no need for an enrichment step and all steps can be automated. Proof of concept is demonstrated using prostate specific antigen: a biomarker for prostate cancer, where glycoform analysis could distinguish between cancerous and non-cancerous status, rather than only detecting overall protein concentration.},
	number = {3},
	urldate = {2023-03-29},
	journal = {NANOSCALE HORIZONS},
	author = {Neves, Marta M. P. S. and Richards, Sarah-Jane and Baker, Alexander N. N. and Walker, Marc and Georgiou, Panagiotis G. G. and Gibson, Matthew I. I.},
	month = feb,
	year = {2023},
	pages = {377--382},
}

Glycoforms (and other post-translational modifications) of otherwise identical proteins can indicate pathogenesis/disease state and hence new tools to detect and sense a protein's glycosylation status are essential. Antibody-based assays against specific protein sequences do not typically discriminate between glycoforms. Here we demonstrate a 'sandwich' bio-assay approach, whereby antibodies immobilised onto biolayer interferometry sensors first select proteins, and then the specific glycoform is identified using gold nanoparticles functionalised with lectins which provide signal enhancement. The nanoparticles significantly enhance the signal relative to lectins alone, allowing glycoform specific detection as low as 0.04 mu g mL(-1) (1.4 nM) in buffer, and crucially there is no need for an enrichment step and all steps can be automated. Proof of concept is demonstrated using prostate specific antigen: a biomarker for prostate cancer, where glycoform analysis could distinguish between cancerous and non-cancerous status, rather than only detecting overall protein concentration.

@article{topcu_microphase_2023,
	title = {Microphase separation assisted reduction in the percolation threshold of {MWCNT}/block polymer composites},
	volume = {19},
	issn = {1744-683X},
	doi = {10.1039/d2sm01277d},
	abstract = {Block copolymers continue to attract a great deal of interest since they allow the formation of microphase-separated domains, useful for nanopatterning/templating. Herein, we present the drastic effect of microphase separation of a diblock copolymer on the electrical properties of polymer nanocomposites. Microphase-separated poly(styrene-b-2-ethylhexyl acrylate) (P(St-b-EHA)) block copolymers having different block lengths were synthesized and utilized as templates for multi-walled carbon nanotubes (MWCNTs). The percolation threshold of the films decreased from 0.46 to 0.19 vol\% with decreasing styrene phase fraction. More importantly, we observed a non-linear and unique reduction in percolation threshold with transforming the phase into lamellar structures.},
	number = {6},
	urldate = {2023-02-12},
	journal = {SOFT MATTER},
	author = {Topcu, Gokhan and Reinoso Arenas, David and McNally, Tony and Becer, C. Remzi},
	month = feb,
	year = {2023},
	pages = {1109--1114},
}

Block copolymers continue to attract a great deal of interest since they allow the formation of microphase-separated domains, useful for nanopatterning/templating. Herein, we present the drastic effect of microphase separation of a diblock copolymer on the electrical properties of polymer nanocomposites. Microphase-separated poly(styrene-b-2-ethylhexyl acrylate) (P(St-b-EHA)) block copolymers having different block lengths were synthesized and utilized as templates for multi-walled carbon nanotubes (MWCNTs). The percolation threshold of the films decreased from 0.46 to 0.19 vol% with decreasing styrene phase fraction. More importantly, we observed a non-linear and unique reduction in percolation threshold with transforming the phase into lamellar structures.

@article{gerassimidou_systematic_2023,
	title = {Systematic {Evidence} {Mapping} to {Assess} the {Sustainability} of {Bioplastics} {Derived} from {Food} {Waste}: {Do} {We} {Know} {Enough}?},
	volume = {15},
	issn = {2071-1050},
	doi = {10.3390/su15010611},
	abstract = {The production of bioplastics from food loss and waste (FLW), termed FLW-derived bioplastics, is considered an attractive alternative to first-generation bioplastics. To our knowledge, a clear understanding of the sustainability performance of FLW-derived bioplastics from environmental, economic, technical, and social aspects is still lacking. This systematic evidence mapping aims to fill this gap by undertaking a reality check on the life cycle sustainability performance of FLW-derived bioplastics from a multidimensional perspective underpinned by systems thinking approach to assess their potential to revolutionise the plastics economy. Results revealed that FLW-derived bioplastic production is highly complex and uncertain. The low technological readiness of FLW valorisation processes and the under-researched logistics of FLW management on a regional scale currently withhold advancement in this field. Nonetheless, progress is looming, and ensuring that FLW-derived bioplastics production enables the transition toward a sustainable bioeconomy is critical. Innovation in both the food and plastics value chains is urgently needed to address their challenges and mitigate pollution. Yet, any steps forward need to be holistically calculated to yield sustainability benefits and prevent unintended consequences.},
	number = {1},
	urldate = {2023-01-23},
	journal = {SUSTAINABILITY},
	author = {Gerassimidou, Spyridoula and Martin, Olwenn V. and Diaz, Gilenny Yamily Feliz and Wan, Chaoying and Komilis, Dimitrios and Iacovidou, Eleni},
	month = jan,
	year = {2023},
}

The production of bioplastics from food loss and waste (FLW), termed FLW-derived bioplastics, is considered an attractive alternative to first-generation bioplastics. To our knowledge, a clear understanding of the sustainability performance of FLW-derived bioplastics from environmental, economic, technical, and social aspects is still lacking. This systematic evidence mapping aims to fill this gap by undertaking a reality check on the life cycle sustainability performance of FLW-derived bioplastics from a multidimensional perspective underpinned by systems thinking approach to assess their potential to revolutionise the plastics economy. Results revealed that FLW-derived bioplastic production is highly complex and uncertain. The low technological readiness of FLW valorisation processes and the under-researched logistics of FLW management on a regional scale currently withhold advancement in this field. Nonetheless, progress is looming, and ensuring that FLW-derived bioplastics production enables the transition toward a sustainable bioeconomy is critical. Innovation in both the food and plastics value chains is urgently needed to address their challenges and mitigate pollution. Yet, any steps forward need to be holistically calculated to yield sustainability benefits and prevent unintended consequences.

@article{hayes_hybrid_2023,
	title = {Hybrid {Multiblock} {Copolymers} of 2-{Oxazoline} and {Acrylates} via {Cu}- {Catalyzed} {Azide}-{Alkyne} {Cycloaddition} {Step}-{Growth} {Mechanism}},
	volume = {56},
	issn = {0024-9297},
	doi = {10.1021/acs.macromol.2c01865},
	abstract = {Multiblock copolymers exhibit interesting self-assembly behaviors owing to their repetitive block structure. Incompatible chemical structures of each block enable unprecedented self-assembled structures and create a wide range of new applications including the ability to blend immiscible polymers. Although multiblock structures of the same monomer classes are well reported, the combination of different classes such as 2-oxazolines and acrylates in a hybrid multiblock structure has never been studied previously. Herein, we report a relatively simple synthetic approach including a detailed evaluation of reaction parameters. Thus, the effect of acrylate monomer type, block length, and solvent composition was investigated and found to influence the linear growth versus cyclization. Finally, selected hybrid multiblock copolymers designed in this study were self-assembled in aqueous media forming stomatocyte-like nanoparticles.},
	number = {1},
	urldate = {2023-01-15},
	journal = {MACROMOLECULES},
	author = {Hayes, Graham and Drain, Ben and Lefley, James and Becer, C. Remzi},
	month = jan,
	year = {2023},
	pages = {271--280},
}

Multiblock copolymers exhibit interesting self-assembly behaviors owing to their repetitive block structure. Incompatible chemical structures of each block enable unprecedented self-assembled structures and create a wide range of new applications including the ability to blend immiscible polymers. Although multiblock structures of the same monomer classes are well reported, the combination of different classes such as 2-oxazolines and acrylates in a hybrid multiblock structure has never been studied previously. Herein, we report a relatively simple synthetic approach including a detailed evaluation of reaction parameters. Thus, the effect of acrylate monomer type, block length, and solvent composition was investigated and found to influence the linear growth versus cyclization. Finally, selected hybrid multiblock copolymers designed in this study were self-assembled in aqueous media forming stomatocyte-like nanoparticles.

@article{zhang_end_2023,
	title = {End functionalization of polyisoprene and polymyrcene obtained by anionic polymerization via one-pot ring-opening mono-addition of epoxides},
	volume = {183},
	issn = {0014-3057},
	doi = {10.1016/j.eurpolymj.2022.111755},
	abstract = {End-functionalization of polyisoprene and polymyrcene were successfully synthesized using anionic polymerization in THF. A number of epoxides, propylene oxide (PO), butylene oxide (BO), allyl glycidyl ether (AGE), 1,2-epoxy-5-hexene (EH) and N,N-dibenzyl amino glycidol (DBAG), were utilised as terminating agents for the induction of hydroxyl functional group in the final products. Polymers were fully hydrogenated following epoxide termination. The functional polymers were characterized by 1H and 13C NMR showing high levels of regioselective termination, SEC showing good control over molecular weight to polymers with narrow molecular weight distributions, MALDI-ToF MS confirming very high levels of functionalisation and thermal analysis (TGA \& DSC).},
	urldate = {2023-01-17},
	journal = {EUROPEAN POLYMER JOURNAL},
	author = {Zhang, Jirui and Pointer, William and Patias, Georgios and Al-Shok, Lucas and Hand, Rachel A. and Smith, Timothy and Haddleton, David M.},
	month = jan,
	year = {2023},
}

End-functionalization of polyisoprene and polymyrcene were successfully synthesized using anionic polymerization in THF. A number of epoxides, propylene oxide (PO), butylene oxide (BO), allyl glycidyl ether (AGE), 1,2-epoxy-5-hexene (EH) and N,N-dibenzyl amino glycidol (DBAG), were utilised as terminating agents for the induction of hydroxyl functional group in the final products. Polymers were fully hydrogenated following epoxide termination. The functional polymers were characterized by 1H and 13C NMR showing high levels of regioselective termination, SEC showing good control over molecular weight to polymers with narrow molecular weight distributions, MALDI-ToF MS confirming very high levels of functionalisation and thermal analysis (TGA & DSC).

@article{thorn_smart_2023,
	title = {Smart and repeatable easy-repairing and self-sensing composites with enhanced mechanical performance for extended components life},
	volume = {165},
	issn = {1359-835X},
	doi = {10.1016/j.compositesa.2022.107337},
	abstract = {Structural composites with smart functionalities of self-healing and self-sensing are of particular interest in the fields of aerospace, automotive, and renewable energy. However, most of the current self-healing methodologies either require a relatively complex design of the healing network, or sacrifice the initial mechanical or thermal performance of the carbon fibre composite system after introducing the healing agents. Herein, an extremely simple methodology based on commonly used thermoplastic interleaves has been demonstrated to achieve repeatable easy-repairing and self-sensing functionalities, alongside enhanced mechanical performance in comparison with unmodified carbon fibre/epoxy system. Moreover, due to the high glass transition temperature of the thermoplastic, the repairable composites are shown to have an unchanged storage modulus up to 80 degrees C, solving the previous limitation of repairable epoxy matrix systems with thermoplastics. High retention of peak load (99\%) and a decent recovery of interlaminar fracture toughness (34\%) was achieved. Most importantly, the mechanical properties remained greater than the unmodified system after four consecutive cycles of damage and healing. Repeatable in-situ damage sensing was achieved based on the piezoresistive method. This "new" discovery based on an "old" approach, which is fully compatible with current composite manufacturing, may overcome existing conflicts between mechanical performance and healing functions, providing a new solution to extend components' service life towards a more sustainable development of the composite sector.},
	urldate = {2023-05-29},
	journal = {COMPOSITES PART A-APPLIED SCIENCE AND MANUFACTURING},
	author = {Thorn, Thomas D. S. and Liu, Yi and Yao, Xudan and Papageorgiou, Dimitrios G. and Robinson, Paul and Bilotti, Emiliano and Peijs, Ton and Zhang, Han},
	month = feb,
	year = {2023},
}

Structural composites with smart functionalities of self-healing and self-sensing are of particular interest in the fields of aerospace, automotive, and renewable energy. However, most of the current self-healing methodologies either require a relatively complex design of the healing network, or sacrifice the initial mechanical or thermal performance of the carbon fibre composite system after introducing the healing agents. Herein, an extremely simple methodology based on commonly used thermoplastic interleaves has been demonstrated to achieve repeatable easy-repairing and self-sensing functionalities, alongside enhanced mechanical performance in comparison with unmodified carbon fibre/epoxy system. Moreover, due to the high glass transition temperature of the thermoplastic, the repairable composites are shown to have an unchanged storage modulus up to 80 degrees C, solving the previous limitation of repairable epoxy matrix systems with thermoplastics. High retention of peak load (99%) and a decent recovery of interlaminar fracture toughness (34%) was achieved. Most importantly, the mechanical properties remained greater than the unmodified system after four consecutive cycles of damage and healing. Repeatable in-situ damage sensing was achieved based on the piezoresistive method. This "new" discovery based on an "old" approach, which is fully compatible with current composite manufacturing, may overcome existing conflicts between mechanical performance and healing functions, providing a new solution to extend components' service life towards a more sustainable development of the composite sector.

@article{du_vivo_2023,
	title = {In vivo visualization of enantioselective targeting of amyloid and improvement of cognitive function by clickable chiral metallohelices},
	volume = {14},
	issn = {2041-6520},
	doi = {10.1039/d2sc05897a},
	abstract = {The pathogenesis of Alzheimer's disease (AD) is closely related to several contributing factors, especially amyloid-beta (A beta) aggregation. Bioorthogonal reactions provide a general, facile, and robust route for the localization and derivatization of A beta-targeted agents. Herein, a pair of chiral alkyne-containing metallohelices (lambda A and \& UDelta;A) were demonstrated to enantioselectively target and modulate A beta aggregation, which has been monitored in triple-transgenic AD model mice and proved to improve cognitive function. Compared with its enantiomer \& UDelta;A, lambda A performed better in blocking A beta fibrillation, relieving A beta-triggered toxicity, and recovering memory deficits in vivo. Moreover, clickable lambda A could act as a functional module for subsequent visualization and versatile modification of amyloid via bioorthogonal reaction. As a proof-of-concept, thioflavin T, tacrine, and magnetic nanoparticles were conjugated with lambda A to realize A beta photo-oxygenation, acetylcholinesterase inhibition, and A beta clearance, respectively. This proof-of-principle work provided new insights into the biolabeling and bioconjugation of multifunctional metallosupramolecules through click reactions for AD therapy.},
	number = {3},
	urldate = {2022-12-22},
	journal = {CHEMICAL SCIENCE},
	author = {Du, Zhi and Liu, Chun and Liu, Zhenqi and Song, Hualong and Scott, Peter and Du, Xiubo and Ren, Jinsong and Qu, Xiaogang},
	month = jan,
	year = {2023},
	pages = {506--513},
}

The pathogenesis of Alzheimer's disease (AD) is closely related to several contributing factors, especially amyloid-beta (A beta) aggregation. Bioorthogonal reactions provide a general, facile, and robust route for the localization and derivatization of A beta-targeted agents. Herein, a pair of chiral alkyne-containing metallohelices (lambda A and & UDelta;A) were demonstrated to enantioselectively target and modulate A beta aggregation, which has been monitored in triple-transgenic AD model mice and proved to improve cognitive function. Compared with its enantiomer & UDelta;A, lambda A performed better in blocking A beta fibrillation, relieving A beta-triggered toxicity, and recovering memory deficits in vivo. Moreover, clickable lambda A could act as a functional module for subsequent visualization and versatile modification of amyloid via bioorthogonal reaction. As a proof-of-concept, thioflavin T, tacrine, and magnetic nanoparticles were conjugated with lambda A to realize A beta photo-oxygenation, acetylcholinesterase inhibition, and A beta clearance, respectively. This proof-of-principle work provided new insights into the biolabeling and bioconjugation of multifunctional metallosupramolecules through click reactions for AD therapy.

@article{hayes_polymers_2023,
	title = {Polymers without {Petrochemicals}: {Sustainable} {Routes} to {Conventional} {Monomers}},
	volume = {123},
	issn = {0009-2665},
	doi = {10.1021/acs.chemrev.2c00354},
	abstract = {Access to a wide range of plastic materials has been rationalized by the increased demand from growing populations and the development of high-throughput production systems. Plastic materials at low costs with reliable properties have been utilized in many everyday products. Multibillion-dollar companies are established around these plastic materials, and each polymer takes years to optimize, secure intellectual property, comply with the regulatory bodies such as the Registration, Evaluation, Authorisation and Restriction of Chemicals and the Environmental Protection Agency and develop consumer confidence. Therefore, developing a fully sustainable new plastic material with even a slightly different chemical structure is a costly and long process. Hence, the production of the common plastic materials with exactly the same chemical structures that does not require any new registration processes better reflects the reality of how to address the critical future of sustainable plastics. In this review, we have highlighted the very recent examples on the synthesis of common monomers using chemicals from sustainable feedstocks that can be used as a like-for-like substitute to prepare conventional petrochemical-free thermoplastics.},
	number = {5},
	urldate = {2022-11-04},
	journal = {CHEMICAL REVIEWS},
	author = {Hayes, Graham and Laurel, Matthew and MacKinnon, Dan and Zhao, Tieshuai and Houck, Hannes A. and Becer, C. Remzi},
	month = mar,
	year = {2023},
	pages = {2609--2734},
}

Access to a wide range of plastic materials has been rationalized by the increased demand from growing populations and the development of high-throughput production systems. Plastic materials at low costs with reliable properties have been utilized in many everyday products. Multibillion-dollar companies are established around these plastic materials, and each polymer takes years to optimize, secure intellectual property, comply with the regulatory bodies such as the Registration, Evaluation, Authorisation and Restriction of Chemicals and the Environmental Protection Agency and develop consumer confidence. Therefore, developing a fully sustainable new plastic material with even a slightly different chemical structure is a costly and long process. Hence, the production of the common plastic materials with exactly the same chemical structures that does not require any new registration processes better reflects the reality of how to address the critical future of sustainable plastics. In this review, we have highlighted the very recent examples on the synthesis of common monomers using chemicals from sustainable feedstocks that can be used as a like-for-like substitute to prepare conventional petrochemical-free thermoplastics.

@article{jolley_development_2022,
	title = {Development and {Application} of a {Poly}(acrylic acid)-{Grafted} {Styrene}-{Butadiene} {Rubber} as a {Binder} {System} for {Silicon}-{Graphite} {Anodes} in {Li}-{Ion} {Batteries}},
	issn = {2574-0962},
	doi = {10.1021/acsaem.2c03489},
	abstract = {Silicon anodes require polymer binder systems that are both mechanically robust and electrochemically stable, to accommodate the dramatic volume expansion experienced during cycling operation. Herein, we report the use of a poly(acrylic acid)-grafted styrene-butadiene rubber (PAA-g-SBR) with 80\% partially neutralized Na-PAA as the binder system for silicon graphite anodes. The PAA-g-SBR graft copolymer was synthesized by grafting tert-butyl acrylate onto SBR and treating the intermediate with H3PO4. The PAA-g-SBR/Na-PAA binder system was found to provide superior electrochemical performances to that of a Na-PAA/SBR system. The Na-PAA/PAA-g-SBR system had a stable capacity retention of 673 mAh g-1 for 130 cycles, while the capacity retention of the Na-PAA/SBR system was found to decline immediately. The Na-PAA/PAA-g-SBR system also displayed more preferable mechanical properties, with a lower Young's modulus value and a larger strain at failure compared to that of the Na-PAA/SBR system. Overall, these findings indicate a promising and robust polymer binder system for the application of silicon anodes in the next generation of lithium-ion batteries.},
	urldate = {2023-01-12},
	journal = {ACS APPLIED ENERGY MATERIALS},
	author = {Jolley, Michael J. and Pathan, Tanveerkhan S. and Wemyss, Alan. M. and Prokes, Ivan and Moharana, Sanghamitra and Wan, Chaoying and Loveridge, Melanie J.},
	month = dec,
	year = {2022},
}

Silicon anodes require polymer binder systems that are both mechanically robust and electrochemically stable, to accommodate the dramatic volume expansion experienced during cycling operation. Herein, we report the use of a poly(acrylic acid)-grafted styrene-butadiene rubber (PAA-g-SBR) with 80% partially neutralized Na-PAA as the binder system for silicon graphite anodes. The PAA-g-SBR graft copolymer was synthesized by grafting tert-butyl acrylate onto SBR and treating the intermediate with H3PO4. The PAA-g-SBR/Na-PAA binder system was found to provide superior electrochemical performances to that of a Na-PAA/SBR system. The Na-PAA/PAA-g-SBR system had a stable capacity retention of 673 mAh g-1 for 130 cycles, while the capacity retention of the Na-PAA/SBR system was found to decline immediately. The Na-PAA/PAA-g-SBR system also displayed more preferable mechanical properties, with a lower Young's modulus value and a larger strain at failure compared to that of the Na-PAA/SBR system. Overall, these findings indicate a promising and robust polymer binder system for the application of silicon anodes in the next generation of lithium-ion batteries.

@article{georgiou_polyvinyl_2022,
	title = {Poly(vinyl alcohol) {Molecular} {Bottlebrushes} {Nucleate} {Ice}},
	issn = {1525-7797},
	doi = {10.1021/acs.biomac.2c01097},
	abstract = {Ice binding proteins (IBP) have evolved to limit the growth of ice but also to promote ice formation by ice-nucleating proteins (INPs). IBPs, which modulate these seemingly distinct processes, often have high sequence similarities, and molecular size/assembly is hypothesized to be a crucial determinant. There are only a few synthetic materials that reproduce INP function, and rational design of ice nucleators has not been achieved due to outstanding questions about the mechanisms of ice binding. Poly(vinyl alcohol) (PVA) is a water-soluble synthetic polymer well known to effectively block ice recrystallization, by binding to ice. Here, we report the synthesis of a polymeric ice nucleator, which mimics the dense assembly of IBPs, using confined ice-binding polymers in a high-molar-mass molecular bottlebrush. Poly(vinyl alcohol)-based molecular bottlebrushes with different side-chain densities were synthesized via a combination of ring-opening metathesis polymerization (ROMP) and reversible addition-fragmentation chain-transfer (RAFT) polymerization, using "grafting-to" and "grafting-through" approaches. The facile preparation of the PVA bottlebrushes was performed via selective hydrolysis of the acetate of the poly(vinyl acetate) (PVAc) side chains of the PVAc bottlebrush precursors. Ice-binding polymer side-chain density was shown to be crucial for nucleation activity, with less dense brushes resulting in colder nucleation than denser brushes. This bio-inspired approach provides a synthetic framework for probing heterogeneous ice nucleation and a route toward defined synthetic nucleators for biotechnological applications.},
	urldate = {2022-12-17},
	journal = {BIOMACROMOLECULES},
	author = {Georgiou, Panagiotis G. and Kinney, Nina L. H. and Kontopoulou, Ioanna and Baker, Alexander N. and Hindmarsh, Steven A. and Bissoyi, Akalabya and Congdon, Thomas R. and Whale, Thomas F. and Gibson, Matthew I.},
	month = nov,
	year = {2022},
}

Ice binding proteins (IBP) have evolved to limit the growth of ice but also to promote ice formation by ice-nucleating proteins (INPs). IBPs, which modulate these seemingly distinct processes, often have high sequence similarities, and molecular size/assembly is hypothesized to be a crucial determinant. There are only a few synthetic materials that reproduce INP function, and rational design of ice nucleators has not been achieved due to outstanding questions about the mechanisms of ice binding. Poly(vinyl alcohol) (PVA) is a water-soluble synthetic polymer well known to effectively block ice recrystallization, by binding to ice. Here, we report the synthesis of a polymeric ice nucleator, which mimics the dense assembly of IBPs, using confined ice-binding polymers in a high-molar-mass molecular bottlebrush. Poly(vinyl alcohol)-based molecular bottlebrushes with different side-chain densities were synthesized via a combination of ring-opening metathesis polymerization (ROMP) and reversible addition-fragmentation chain-transfer (RAFT) polymerization, using "grafting-to" and "grafting-through" approaches. The facile preparation of the PVA bottlebrushes was performed via selective hydrolysis of the acetate of the poly(vinyl acetate) (PVAc) side chains of the PVAc bottlebrush precursors. Ice-binding polymer side-chain density was shown to be crucial for nucleation activity, with less dense brushes resulting in colder nucleation than denser brushes. This bio-inspired approach provides a synthetic framework for probing heterogeneous ice nucleation and a route toward defined synthetic nucleators for biotechnological applications.

@article{kim_poly2-oxazoline_2022,
	title = {Poly(2-oxazoline) with {Pendant} {Hydroxyl} {Groups} via a {Silyl} {Ether}-{Based} {Protecting} {Group}},
	issn = {0024-9297},
	doi = {10.1021/acs.macromol.2c02050},
	abstract = {The introduction of a functionality onto a poly(2-oxazoline) (POx) chain has been widely explored, yet reports of POx bearing hydroxyl side chains in a well-defined manner have not. Here, we report a simple yet elegant approach for the synthesis of POx with pendant hydroxyl groups through use of silyl protecting groups. First, a hydroxyl group containing 2-oxazoline monomer was synthesized from L-caprolactone, which on its own results in poorly defined polymers. Moreover, protecting the hydroxy group with silyl ether-based protecting group led to well-defined polymers with free hydroxyl groups on the side chains upon deprotection. Finally, copolymers with 2-ethyl-2-oxazoline resulted in polymers with tunable hydrophilicity, and copolymers with 2-n-propyl-2-oxazoline resulted in polymers with tunable thermoresponsive behavior in water.},
	urldate = {2022-12-14},
	journal = {MACROMOLECULES},
	author = {Kim, Jungyeon and Beyer, Valentin and Becer, C. Remzi},
	month = nov,
	year = {2022},
}

The introduction of a functionality onto a poly(2-oxazoline) (POx) chain has been widely explored, yet reports of POx bearing hydroxyl side chains in a well-defined manner have not. Here, we report a simple yet elegant approach for the synthesis of POx with pendant hydroxyl groups through use of silyl protecting groups. First, a hydroxyl group containing 2-oxazoline monomer was synthesized from L-caprolactone, which on its own results in poorly defined polymers. Moreover, protecting the hydroxy group with silyl ether-based protecting group led to well-defined polymers with free hydroxyl groups on the side chains upon deprotection. Finally, copolymers with 2-ethyl-2-oxazoline resulted in polymers with tunable hydrophilicity, and copolymers with 2-n-propyl-2-oxazoline resulted in polymers with tunable thermoresponsive behavior in water.

@article{micallef_polymer-tethered_2022,
	title = {Polymer-tethered glyconanoparticle colourimetric biosensors for lectin binding: structural and experimental parameters to ensure a robust output},
	volume = {12},
	issn = {2046-2069},
	doi = {10.1039/d2ra06265h},
	abstract = {Glycan-lectin interactions play essential roles in biology; as the site of attachment for pathogens, cell-cell communication, and as crucial players in the immune system. Identifying if a new glycan (natural or unnatural) binds a protein partner, or if a new protein (or mutant) binds a glycan remains a non-trivial problem, with few accessible or low-cost tools available. Micro-arrays allow for the interrogation of 100's of glycans but are not widely available in individual laboratories. Biophysical techniques such as isothermal titration calorimetry, surface plasmon resonance spectrometry, biolayer interferometry and nuclear magnetic resonance spectroscopy all provide detailed understanding of glycan binding but are relatively expensive. Glycosylated plasmonic nanoparticles based on gold cores with polymeric tethers have emerged as biosensors to detect glycan-protein binding, based on colourimetric (red to blue) outputs which can be easily interpreted by a simple UV-visible spectrometer or by eye. Despite the large number of reports there are no standard protocols for each system or recommended start points, to allow a new user to deploy this technology. Here we explore the key parameters of nanoparticle size, polymeric tether length and gold concentration to provide some guidelines for how polymer-tethered glycosylated gold nanoparticles can be used to probe a new glycan/protein interactions, with minimal optimisation barriers. This work aimed to remove the need to explore chemical and nanoparticle space and hence remove a barrier for other users when deploying this system. We show that the concentration of the gold core is crucial to balance strong responses versus false positives and recommend a gold core size and polymer tether length which balances sufficient colloidal stability and output. Whilst subtle differences between glycans/lectins will impact the outcomes, these parameters should enable a lab user to quickly evaluate binding using minimal quantities of the glycan and lectin, to select candidates for further study.},
	number = {51},
	urldate = {2022-11-29},
	journal = {RSC ADVANCES},
	author = {Micallef, Julian and Baker, Alexander N. and Richards, Sarah-Jane and Soutar, Douglas E. and Georgiou, Panagiotis G. and Walker, Marc and Gibson, Matthew I.},
	month = nov,
	year = {2022},
	pages = {33080--33090},
}

Glycan-lectin interactions play essential roles in biology; as the site of attachment for pathogens, cell-cell communication, and as crucial players in the immune system. Identifying if a new glycan (natural or unnatural) binds a protein partner, or if a new protein (or mutant) binds a glycan remains a non-trivial problem, with few accessible or low-cost tools available. Micro-arrays allow for the interrogation of 100's of glycans but are not widely available in individual laboratories. Biophysical techniques such as isothermal titration calorimetry, surface plasmon resonance spectrometry, biolayer interferometry and nuclear magnetic resonance spectroscopy all provide detailed understanding of glycan binding but are relatively expensive. Glycosylated plasmonic nanoparticles based on gold cores with polymeric tethers have emerged as biosensors to detect glycan-protein binding, based on colourimetric (red to blue) outputs which can be easily interpreted by a simple UV-visible spectrometer or by eye. Despite the large number of reports there are no standard protocols for each system or recommended start points, to allow a new user to deploy this technology. Here we explore the key parameters of nanoparticle size, polymeric tether length and gold concentration to provide some guidelines for how polymer-tethered glycosylated gold nanoparticles can be used to probe a new glycan/protein interactions, with minimal optimisation barriers. This work aimed to remove the need to explore chemical and nanoparticle space and hence remove a barrier for other users when deploying this system. We show that the concentration of the gold core is crucial to balance strong responses versus false positives and recommend a gold core size and polymer tether length which balances sufficient colloidal stability and output. Whilst subtle differences between glycans/lectins will impact the outcomes, these parameters should enable a lab user to quickly evaluate binding using minimal quantities of the glycan and lectin, to select candidates for further study.

@article{ma_aggregation-induced_2022,
	title = {Aggregation-{Induced} {Emission} {Poly}(meth)acrylates for {Photopatterning} via {Wavelength}-{Dependent} {Visible}-{Light}-{Regulated} {Controlled} {Radical} {Polymerization} in {Batch} and {Flow} {Conditions}},
	volume = {55},
	issn = {0024-9297},
	doi = {10.1021/acs.macromol.2c01413},
	abstract = {A robust wavelength-dependent visible-light-regulated reversible-deactivation radical polymerization protocol is first reported for the batch preparation of {\textgreater}20 aggregation-induced emission (AIE)active polyacrylates and polymethacrylates. The resulting polymers possess narrow molar mass distributions (D approximate to 1.09-1.25) and high end-group fidelity at high monomer conversions (mostly {\textgreater}95\%). This demonstrated control provides facile access to the in situ generation of complex sequence-defined tetrablock copolymers in one reactor, even while chain extending from less reactive monomers. Polymerizations can be successfully carried out under various irradiation conditions, including using UV, blue, green, and red LED light with more disperse polymers obtained at the longer, less energetic, wavelengths. We observe a red shift and wavelength dependence for the most efficient polymerization using LED illumination in a polymerization reaction. We find that the absorption of the copper(II) complex is not a reliable guide to reaction conditions. Moreover, the reported protocol is readily translated to a flow setup. The prepared AIE-active polymers are demonstrated to exhibit good photopatterning, making them promising materials for applications in advanced optoelectronic devices.},
	number = {22},
	urldate = {2022-12-01},
	journal = {MACROMOLECULES},
	author = {Ma, Congkai and Han, Ting and Efstathiou, Spyridon and Marathianos, Arkadios and Houck, Hannes A. and Haddleton, David M.},
	month = nov,
	year = {2022},
	pages = {9908--9917},
}

A robust wavelength-dependent visible-light-regulated reversible-deactivation radical polymerization protocol is first reported for the batch preparation of \textgreater20 aggregation-induced emission (AIE)active polyacrylates and polymethacrylates. The resulting polymers possess narrow molar mass distributions (D approximate to 1.09-1.25) and high end-group fidelity at high monomer conversions (mostly \textgreater95%). This demonstrated control provides facile access to the in situ generation of complex sequence-defined tetrablock copolymers in one reactor, even while chain extending from less reactive monomers. Polymerizations can be successfully carried out under various irradiation conditions, including using UV, blue, green, and red LED light with more disperse polymers obtained at the longer, less energetic, wavelengths. We observe a red shift and wavelength dependence for the most efficient polymerization using LED illumination in a polymerization reaction. We find that the absorption of the copper(II) complex is not a reliable guide to reaction conditions. Moreover, the reported protocol is readily translated to a flow setup. The prepared AIE-active polymers are demonstrated to exhibit good photopatterning, making them promising materials for applications in advanced optoelectronic devices.

@article{concilio_thermoresponsive_2022,
	title = {Thermoresponsive polymers in non-aqueous solutions},
	volume = {13},
	issn = {1759-9954},
	doi = {10.1039/d2py01147f},
	abstract = {Thermoresponsive polymers are gaining increasing interest for numerous applications especially in the biomedical and nanotechnology fields. The thermoresponsive behaviour of polymers has been extensively studied in pure water or water/organic solvent systems, however, temperature-induced phase transitions in other organic solvents are less common. Polymers in organic solvents exhibit a broad range of temperature-driven solution behaviours, from LCST and UCST, to sol-gel transitions, to micellization processes, among others, with potential applications as smart materials in electronics, in the lubricant industry, and in the biomedical field. This review article will focus on the thermoresponsive behaviour of polymers in different classes of organic solvents and mixtures thereof to emphasize and demonstrate the versatility and potential of these polymers.},
	number = {47},
	urldate = {2022-11-27},
	journal = {POLYMER CHEMISTRY},
	author = {Concilio, Matilde and Beyer, Valentin P. and Becer, C. Remzi},
	month = dec,
	year = {2022},
	pages = {6423--6474},
}

Thermoresponsive polymers are gaining increasing interest for numerous applications especially in the biomedical and nanotechnology fields. The thermoresponsive behaviour of polymers has been extensively studied in pure water or water/organic solvent systems, however, temperature-induced phase transitions in other organic solvents are less common. Polymers in organic solvents exhibit a broad range of temperature-driven solution behaviours, from LCST and UCST, to sol-gel transitions, to micellization processes, among others, with potential applications as smart materials in electronics, in the lubricant industry, and in the biomedical field. This review article will focus on the thermoresponsive behaviour of polymers in different classes of organic solvents and mixtures thereof to emphasize and demonstrate the versatility and potential of these polymers.

@article{dsouza_multifunctional_2022,
	title = {Multifunctional {Composite} {Hydrogels} for {Bacterial} {Capture}, {Growth}/ {Elimination}, and {Sensing} {Applications}},
	issn = {1944-8244},
	doi = {10.1021/acsami.2c08582},
	abstract = {Hydrogels are cross-linked networks of hydrophilic polymer chains with a three-dimensional structure. Owing to their unique features, the application of hydrogels for bacterial/ antibacterial studies and bacterial infection management has grown in importance in recent years. This trend is likely to continue due to the rise in bacterial infections and antimicrobial resistance. By exploiting their physicochemical characteristics and inherent nature, hydrogels have been developed to achieve bacterial capture and detection, bacterial growth or elimination, antibiotic delivery, or bacterial sensing. Traditionally, the development of hydrogels for bacterial/antibacterial studies has focused on achieving a single function such as antibiotic delivery, antibacterial activity, bacterial growth, or bacterial detection. However, recent studies demonstrate the fabrication of multifunctional hydrogels, where a single hydrogel is capable of performing more than one bacterial/antibacterial function, or composite hydrogels consisting of a number of single functionalized hydrogels, which exhibit bacterial/antibacterial function synergistically. In this review, we first highlight the hydrogel features critical for bacterial studies and infection management. Then, we specifically address unique hydrogel properties, their surface/network functionalization, and their mode of action for bacterial capture, adhesion/growth, antibacterial activity, and bacterial sensing, respectively. Finally, we provide insights into different strategies for developing multifunctional hydrogels and how such systems can help tackle, manage, and understand bacterial infections and antimicrobial resistance. We also note that the strategies highlighted in this review can be adapted to other cell types and are therefore likely to find applications beyond the field of microbiology.},
	urldate = {2022-10-29},
	journal = {ACS APPLIED MATERIALS \& INTERFACES},
	author = {Dsouza, Andrea and Constantinidou, Chrystala and Arvanitis, Theodoros N. and Haddleton, David M. and Charmet, Jerome and Hand, Rachel A.},
	month = oct,
	year = {2022},
}

Hydrogels are cross-linked networks of hydrophilic polymer chains with a three-dimensional structure. Owing to their unique features, the application of hydrogels for bacterial/ antibacterial studies and bacterial infection management has grown in importance in recent years. This trend is likely to continue due to the rise in bacterial infections and antimicrobial resistance. By exploiting their physicochemical characteristics and inherent nature, hydrogels have been developed to achieve bacterial capture and detection, bacterial growth or elimination, antibiotic delivery, or bacterial sensing. Traditionally, the development of hydrogels for bacterial/antibacterial studies has focused on achieving a single function such as antibiotic delivery, antibacterial activity, bacterial growth, or bacterial detection. However, recent studies demonstrate the fabrication of multifunctional hydrogels, where a single hydrogel is capable of performing more than one bacterial/antibacterial function, or composite hydrogels consisting of a number of single functionalized hydrogels, which exhibit bacterial/antibacterial function synergistically. In this review, we first highlight the hydrogel features critical for bacterial studies and infection management. Then, we specifically address unique hydrogel properties, their surface/network functionalization, and their mode of action for bacterial capture, adhesion/growth, antibacterial activity, and bacterial sensing, respectively. Finally, we provide insights into different strategies for developing multifunctional hydrogels and how such systems can help tackle, manage, and understand bacterial infections and antimicrobial resistance. We also note that the strategies highlighted in this review can be adapted to other cell types and are therefore likely to find applications beyond the field of microbiology.

@article{aljuaid_photocrosslinking_2022,
	title = {Photocrosslinking of {Polyacrylamides} {Using} [2+2] {Photodimerisation} of {Monothiomaleimides}},
	volume = {55},
	issn = {0024-9297},
	doi = {10.1021/acs.macromol.2c01710},
	abstract = {The [2 + 2] photocycloaddition of monothiomalei-mides (MTMs) has been exploited for the photocrosslinking of polyacrylamides. Polymer scaffolds composed of dimethylacryla-mide and varying amounts of D,L-homocysteine thiolactone acrylamide (5, 10, and 20 mol \%) were synthesized via free-radical polymerization, whereby the latent thiol functionality was exploited to incorporate MTM motifs. Subsequent exposure to UV light (lambda = 365 nm, 15 mW cm-2) triggered intermolecular crosslinking via the photodimerization of MTM side chains, thus resulting in the formation of polyacrylamide gels. The polymer scaffolds were characterized using Fourier transform infrared spectroscopy, UV- visible spectroscopy, 1H NMR spectroscopy, and size exclusion chromatography, confirming the occurrence of the [2 + 2] photocycloaddition between the MTM moieties. The mechanical and physical properties of the resulting gels containing various MTM mol \% were evaluated by rheology, compression testing, and swelling experiments. In addition, scanning electron microscopy was used to characterize the xerogel morphology of 5 and 10 mol \% MTM hydro-and organo-gels. The macro-porous morphology obtained for the hydrogels was attributed to phase separation due to the difference in solubility of the PDMA modified with thiolactone side chains, provided that a more homogeneous morphology was obtained when the photo-gels were prepared in DMF as the solvent.},
	number = {19},
	urldate = {2022-10-24},
	journal = {MACROMOLECULES},
	author = {Aljuaid, Mohammed and Houck, Hannes A. and Efstathiou, Spyridon and Haddleton, David M. and Wilson, Paul},
	month = oct,
	year = {2022},
	pages = {8495--8504},
}

The [2 + 2] photocycloaddition of monothiomalei-mides (MTMs) has been exploited for the photocrosslinking of polyacrylamides. Polymer scaffolds composed of dimethylacryla-mide and varying amounts of D,L-homocysteine thiolactone acrylamide (5, 10, and 20 mol %) were synthesized via free-radical polymerization, whereby the latent thiol functionality was exploited to incorporate MTM motifs. Subsequent exposure to UV light (lambda = 365 nm, 15 mW cm-2) triggered intermolecular crosslinking via the photodimerization of MTM side chains, thus resulting in the formation of polyacrylamide gels. The polymer scaffolds were characterized using Fourier transform infrared spectroscopy, UV- visible spectroscopy, 1H NMR spectroscopy, and size exclusion chromatography, confirming the occurrence of the [2 + 2] photocycloaddition between the MTM moieties. The mechanical and physical properties of the resulting gels containing various MTM mol % were evaluated by rheology, compression testing, and swelling experiments. In addition, scanning electron microscopy was used to characterize the xerogel morphology of 5 and 10 mol % MTM hydro-and organo-gels. The macro-porous morphology obtained for the hydrogels was attributed to phase separation due to the difference in solubility of the PDMA modified with thiolactone side chains, provided that a more homogeneous morphology was obtained when the photo-gels were prepared in DMF as the solvent.

@article{wemyss_oligomeric_2022,
	title = {Oligomeric {Curing} {Activators} {Enable} {Conventional} {Sulfur}-{Vulcanized} {Rubbers} to {Self}-{Heal}},
	issn = {2637-6105},
	doi = {10.1021/acsapm.2c01398},
	abstract = {When introducing self-healing properties to elastomers, it is often difficult to balance their ability to recover properties after damage with a good mechanical strength prior to damage. We demonstrate that by replacing the activator system used in conventional accelerated vulcanization (CV) chemistry, from the traditional zinc oxide (ZnO) and stearic acid to a complex formed between co-propenyl functional oligomers of poly(zinc methacrylate) (pZnMA/ZnO), the self-healing properties of vulcanized natural rubbers are enhanced while maintaining good tensile strengths. The pZnMA oligomers, as synthesized by catalytic chain transfer polymerization (CCTP), act as an activator for the sulfur curing system, while also forming an ionic network in the rubber. The addition of 20 phr of pZnMA/ZnO to a CV system resulted in a cured natural rubber with a tensile strength of 7.47 +/- 0.64 MPa, which recovered 86.7\% after self-healing at 80 degrees C for 2 h. Further addition of 40 phr of carbon black N234 unexpectedly enhanced the self-healing efficiency of these vulcanized rubbers to 92.2\% under the same conditions and also improved the self-healing at room temperature. Finally, dynamic mechanical thermal analysis indicated that the natural rubber formulations containing pZnMA/ZnO showed improved wet traction but with higher rolling resistance to a standard formulation. These results point to an interesting direction for further research into the performance of self-healing composites in vehicle tire applications.},
	urldate = {2022-10-01},
	journal = {ACS APPLIED POLYMER MATERIALS},
	author = {Wemyss, Alan M. and Marathianos, Arkadios and Heeley, Ellen L. and Ekeocha, James and Morishita, Yoshihiro and Di Ronza, Raffaele and Bernal, M. Mar and Haddleton, David M. and Wan, Chaoying},
	month = sep,
	year = {2022},
	note = {Bridgestone EU NV SA},
}

When introducing self-healing properties to elastomers, it is often difficult to balance their ability to recover properties after damage with a good mechanical strength prior to damage. We demonstrate that by replacing the activator system used in conventional accelerated vulcanization (CV) chemistry, from the traditional zinc oxide (ZnO) and stearic acid to a complex formed between co-propenyl functional oligomers of poly(zinc methacrylate) (pZnMA/ZnO), the self-healing properties of vulcanized natural rubbers are enhanced while maintaining good tensile strengths. The pZnMA oligomers, as synthesized by catalytic chain transfer polymerization (CCTP), act as an activator for the sulfur curing system, while also forming an ionic network in the rubber. The addition of 20 phr of pZnMA/ZnO to a CV system resulted in a cured natural rubber with a tensile strength of 7.47 +/- 0.64 MPa, which recovered 86.7% after self-healing at 80 degrees C for 2 h. Further addition of 40 phr of carbon black N234 unexpectedly enhanced the self-healing efficiency of these vulcanized rubbers to 92.2% under the same conditions and also improved the self-healing at room temperature. Finally, dynamic mechanical thermal analysis indicated that the natural rubber formulations containing pZnMA/ZnO showed improved wet traction but with higher rolling resistance to a standard formulation. These results point to an interesting direction for further research into the performance of self-healing composites in vehicle tire applications.

@article{laurel_degradable_2022,
	title = {Degradable thioester core-crosslinked star-shaped polymers},
	volume = {13},
	issn = {1759-9954},
	doi = {10.1039/d2py00901c},
	abstract = {Degradable polymers are considered to present a promising solution to combat plastic pollution. However, many polymers are based on ester and amide bonds, which often require high temperatures and acidic/basic catalysis and hence do not easily degrade under typical environmental conditions. Thus, more readily degradable polymer structures that enable the use of milder conditions are highly sought after. Herein, degradable core-crosslinked star-shaped branched polymers have been synthesised via a two-step one-pot reversible addition-fragmentation chain transfer polymerisation. For the first time, a bifunctional thiomethacrylate crosslinker was used to prepare a range of star-shaped poly(methyl methacrylate) structures which were characterised by advanced viscometry gel permeation chromatography. The increased reactivity of thioesters over their oxoester analogues was exploited to degrade the resulting star-shaped polymers via amidation, as evidenced by the complete degradation of the crosslinked core upon heating in the presence of amines. The successful degradation of polymers containing thioesters shows the potential of thioester chemistry for producing more sustainable/degradable polymers with more complex and defined architectures.},
	number = {39},
	urldate = {2022-09-11},
	journal = {POLYMER CHEMISTRY},
	author = {Laurel, Matthew and MacKinnon, Daniel and Becker, Jonas and Terracciano, Roberto and Drain, Ben and Houck, Hannes A. and Becer, C. Remzi},
	month = oct,
	year = {2022},
	pages = {5579--5589},
}

Degradable polymers are considered to present a promising solution to combat plastic pollution. However, many polymers are based on ester and amide bonds, which often require high temperatures and acidic/basic catalysis and hence do not easily degrade under typical environmental conditions. Thus, more readily degradable polymer structures that enable the use of milder conditions are highly sought after. Herein, degradable core-crosslinked star-shaped branched polymers have been synthesised via a two-step one-pot reversible addition-fragmentation chain transfer polymerisation. For the first time, a bifunctional thiomethacrylate crosslinker was used to prepare a range of star-shaped poly(methyl methacrylate) structures which were characterised by advanced viscometry gel permeation chromatography. The increased reactivity of thioesters over their oxoester analogues was exploited to degrade the resulting star-shaped polymers via amidation, as evidenced by the complete degradation of the crosslinked core upon heating in the presence of amines. The successful degradation of polymers containing thioesters shows the potential of thioester chemistry for producing more sustainable/degradable polymers with more complex and defined architectures.

@article{gurnani_probing_2022,
	title = {Probing the {Effect} of {Rigidity} on the {Cellular} {Uptake} of {Core}-{Shell} {Nanoparticles}: {Stiffness} {Effects} are {Size} {Dependent}},
	volume = {18},
	issn = {1613-6810},
	doi = {10.1002/smll.202203070},
	abstract = {Nanoparticles are well established vectors for the delivery of a wide range of biomedically relevant cargoes. Numerous studies have investigated the impact of size, shape, charge, and surface functionality of nanoparticles on mammalian cellular uptake. Rigidity has been studied to a far lesser extent, and its effects are still unclear. Here, the importance of this property, and its interplay with particle size, is systematically explored using a library of core-shell spherical PEGylated nanoparticles synthesized by RAFT emulsion polymerization. Rigidity of these particles is controlled by altering the intrinsic glass transition temperature of their constituting polymers. Three polymeric core rigidities are tested: hard, medium, and soft using two particle sizes, 50 and 100 nm diameters. Cellular uptake studies indicate that softer particles are taken up faster and threefold more than harder nanoparticles with the larger 100 nm particles. In addition, the study indicates major differences in the cellular uptake pathway, with harder particles being internalized through clathrin- and caveolae-mediated endocytosis as well as macropinocytosis, while softer particles are taken up bycaveolae- and non-receptormediated endocytosis. However, 50 nm derivatives do not show any appreciable differences in uptake efficiency, suggesting that rigidity as a parameter in the biological regime may be size dependent.},
	number = {38},
	urldate = {2022-08-26},
	journal = {SMALL},
	author = {Gurnani, Pratik and Sanchez-Cano, Carlos and Xandri-Monje, Helena and Zhang, Junliang and Ellacott, Sean H. and Mansfield, Edward D. H. and Hartlieb, Matthias and Dallmann, Robert and Perrier, Sebastien},
	month = sep,
	year = {2022},
	note = {Donostia Int Phys Ctr},
}

Nanoparticles are well established vectors for the delivery of a wide range of biomedically relevant cargoes. Numerous studies have investigated the impact of size, shape, charge, and surface functionality of nanoparticles on mammalian cellular uptake. Rigidity has been studied to a far lesser extent, and its effects are still unclear. Here, the importance of this property, and its interplay with particle size, is systematically explored using a library of core-shell spherical PEGylated nanoparticles synthesized by RAFT emulsion polymerization. Rigidity of these particles is controlled by altering the intrinsic glass transition temperature of their constituting polymers. Three polymeric core rigidities are tested: hard, medium, and soft using two particle sizes, 50 and 100 nm diameters. Cellular uptake studies indicate that softer particles are taken up faster and threefold more than harder nanoparticles with the larger 100 nm particles. In addition, the study indicates major differences in the cellular uptake pathway, with harder particles being internalized through clathrin- and caveolae-mediated endocytosis as well as macropinocytosis, while softer particles are taken up bycaveolae- and non-receptormediated endocytosis. However, 50 nm derivatives do not show any appreciable differences in uptake efficiency, suggesting that rigidity as a parameter in the biological regime may be size dependent.

@article{baker_glycosylated_2022,
	title = {Glycosylated gold nanoparticles in point of care diagnostics: from aggregation to lateral flow},
	volume = {51},
	issn = {0306-0012},
	doi = {10.1039/d2cs00267a},
	abstract = {Current point-of-care lateral flow immunoassays, such as the home pregnancy test, rely on proteins as detection units (e.g. antibodies) to sense for analytes. Glycans play a fundamental role in biological signalling and recognition events such as pathogen adhesion and hence they are promising future alternatives to antibody-based biosensing and diagnostics. Here we introduce the potential of glycans coupled to gold nanoparticles as recognition agents for lateral flow diagnostics. We first introduce the concept of lateral flow, including a case study of lateral flow use in the field compared to other diagnostic tools. We then introduce glycosylated materials, the affinity gains achieved by the cluster glycoside effect and the current use of these in aggregation based assays. Finally, the potential role of glycans in lateral flow are explained, and examples of their successful use given.},
	number = {16},
	urldate = {2022-08-02},
	journal = {CHEMICAL SOCIETY REVIEWS},
	author = {Baker, Alexander N. and Hawker-Bond, George W. and Georgiou, Panagiotis G. and Dedola, Simone and Field, Robert A. and Gibson, I, Matthew},
	month = aug,
	year = {2022},
	note = {Iceni Glycosci Ltd},
	pages = {7238--7259},
}

Current point-of-care lateral flow immunoassays, such as the home pregnancy test, rely on proteins as detection units (e.g. antibodies) to sense for analytes. Glycans play a fundamental role in biological signalling and recognition events such as pathogen adhesion and hence they are promising future alternatives to antibody-based biosensing and diagnostics. Here we introduce the potential of glycans coupled to gold nanoparticles as recognition agents for lateral flow diagnostics. We first introduce the concept of lateral flow, including a case study of lateral flow use in the field compared to other diagnostic tools. We then introduce glycosylated materials, the affinity gains achieved by the cluster glycoside effect and the current use of these in aggregation based assays. Finally, the potential role of glycans in lateral flow are explained, and examples of their successful use given.

@article{maset_evaluation_2022,
	title = {Evaluation of the {Antimicrobial} {Activity} in {Host}-{Mimicking} {Media} and {In} {Vivo} {Toxicity} of {Antimicrobial} {Polymers} as {Functional} {Mimics} of {AMPs}},
	volume = {14},
	issn = {1944-8244},
	doi = {10.1021/acsami.2c05979},
	abstract = {Activity tests for synthetic antimicrobial compounds are often limited to the minimal inhibitory concentration assay using standard media and bacterial strains. In this study, a family of acrylamide copolymers that act as synthetic mimics of antimicrobial peptides were synthesized and shown to have a disruptive effect on bacterial membranes and structural integrity through microscopy techniques and membrane polarization experiments. The polymers were tested for their antimicrobial properties using media that mimic clinically relevant conditions. Additionally, their activity was compared in two different strains of the Gram-positive bacterium Staphylococcus aureus and the Gram-negative bacterium Pseudomonas aeruginosa. We showed that the medium composition can have an important influence on the polymer activity as there was a considerable reduction in minimal inhibitory concentrations against S. aureus grown in synthetic wound fluid (SWF), and against P. aeruginosa grown in synthetic cystic fibrosis sputum media (SCFM), compared to the concentrations in standard testing media. In contrast, we observed a complete loss of activity against P. aeruginosa in the serum-containing SWF. Finally, we made use of an emerging invertebrate in vivo model, using Galleria mellonella larvae, to assess toxicity of the polymeric antimicrobials, showing a good correlation with cell line toxicity measurements and demonstrating its potential in the evaluation of novel antimicrobial materials.},
	number = {29},
	urldate = {2022-07-27},
	journal = {ACS APPLIED MATERIALS \& INTERFACES},
	author = {Maset, Ramon Garcia and Hapeshi, Alexia and Hall, Stephen and Dalgliesh, Robert M. and Harrison, Freya and Perrier, Sebastien},
	month = jul,
	year = {2022},
	pages = {32855--32868},
}

Activity tests for synthetic antimicrobial compounds are often limited to the minimal inhibitory concentration assay using standard media and bacterial strains. In this study, a family of acrylamide copolymers that act as synthetic mimics of antimicrobial peptides were synthesized and shown to have a disruptive effect on bacterial membranes and structural integrity through microscopy techniques and membrane polarization experiments. The polymers were tested for their antimicrobial properties using media that mimic clinically relevant conditions. Additionally, their activity was compared in two different strains of the Gram-positive bacterium Staphylococcus aureus and the Gram-negative bacterium Pseudomonas aeruginosa. We showed that the medium composition can have an important influence on the polymer activity as there was a considerable reduction in minimal inhibitory concentrations against S. aureus grown in synthetic wound fluid (SWF), and against P. aeruginosa grown in synthetic cystic fibrosis sputum media (SCFM), compared to the concentrations in standard testing media. In contrast, we observed a complete loss of activity against P. aeruginosa in the serum-containing SWF. Finally, we made use of an emerging invertebrate in vivo model, using Galleria mellonella larvae, to assess toxicity of the polymeric antimicrobials, showing a good correlation with cell line toxicity measurements and demonstrating its potential in the evaluation of novel antimicrobial materials.

@article{zhang_polymerization_2022,
	title = {Polymerization of {Myrcene} in {Both} {Conventional} and {Renewable} {Solvents}: {Postpolymerization} {Modification} via {Regioselective} {Photoinduced} {Thiol}-{Ene} {Chemistry} for {Use} as {Carbon} {Renewable} {Dispersants}},
	volume = {10},
	issn = {2168-0485},
	doi = {10.1021/acssuschemeng.2c03755},
	abstract = {Polymeric dispersants are useful materials used in many different industries and often derived from oil-based chemicals, for example, in automotive fluids so as to prevent particulates from precipitation and causing potential damage. These are very often polyisobutene derivatives, and there is a growing need to replace these using chemicals using renewable resources such as the use of naturally occurring myrcene. Polymyrcene (PMy), with an ordered microstructure, has been successfully synthesized via both anionic and radical polymerization in different solvents and subsequently subjected to functionalization via photoinduced thiol-ene click reactions with a number of thiols, methyl thioglycolate, 3-mercaptopropionic acid, 3-mercapto-1-hexanol, 2-mercaptoethanol, and 1-thioglycerol, using 2,2-dimethoxy-2-phenylacetophenone as a photoinitiator under UV irradiation (lambda = 365 nm) at ambient temperature. The polarity of the solvent has an important impact on the microstructure of the produced polymyrcene and, in particular, 1,2-unit (similar to 4\%), 3,4-unit (similar to 41\%), and 1,4-unit (similar to 51\%) PMy were obtained via anionic polymerization in a polar solvent (THF) at ambient temperature, while 3,4-unit (similar to 6\%) and 1,4-unit (similar to 94\%, including cis and trans ) PMy were obtained with cyclohexane as the solvent. Subsequently, photochemical thiol-ene reactions were carried out on the resulting PMy with different isomers exhibiting different reactivities of the double bonds. This strategy allows for the introduction of functional/polar groups (-COOH, -OH) into hydrophobic PMy in a controlled process. Hydrogenation of PMy and derivatized PMy was carried out to investigate any effects on the stabilities of the products which are desirable for many applications.},
	number = {29},
	urldate = {2022-07-26},
	journal = {ACS SUSTAINABLE CHEMISTRY \& ENGINEERING},
	author = {Zhang, Jirui and Aydogan, Cansu and Patias, Georgios and Smith, Timothy and Al-Shok, Lucas and Liu, Huizhe and Eissa, Ahmed M. and Haddleton, David M.},
	month = jul,
	year = {2022},
	pages = {9654--9664},
}

Polymeric dispersants are useful materials used in many different industries and often derived from oil-based chemicals, for example, in automotive fluids so as to prevent particulates from precipitation and causing potential damage. These are very often polyisobutene derivatives, and there is a growing need to replace these using chemicals using renewable resources such as the use of naturally occurring myrcene. Polymyrcene (PMy), with an ordered microstructure, has been successfully synthesized via both anionic and radical polymerization in different solvents and subsequently subjected to functionalization via photoinduced thiol-ene click reactions with a number of thiols, methyl thioglycolate, 3-mercaptopropionic acid, 3-mercapto-1-hexanol, 2-mercaptoethanol, and 1-thioglycerol, using 2,2-dimethoxy-2-phenylacetophenone as a photoinitiator under UV irradiation (lambda = 365 nm) at ambient temperature. The polarity of the solvent has an important impact on the microstructure of the produced polymyrcene and, in particular, 1,2-unit (similar to 4%), 3,4-unit (similar to 41%), and 1,4-unit (similar to 51%) PMy were obtained via anionic polymerization in a polar solvent (THF) at ambient temperature, while 3,4-unit (similar to 6%) and 1,4-unit (similar to 94%, including cis and trans ) PMy were obtained with cyclohexane as the solvent. Subsequently, photochemical thiol-ene reactions were carried out on the resulting PMy with different isomers exhibiting different reactivities of the double bonds. This strategy allows for the introduction of functional/polar groups (-COOH, -OH) into hydrophobic PMy in a controlled process. Hydrogenation of PMy and derivatized PMy was carried out to investigate any effects on the stabilities of the products which are desirable for many applications.

@article{duman_glycopolymer-functionalized_2022,
	title = {Glycopolymer-{Functionalized} {MOF}-808 {Nanoparticles} as a {Cancer}-{Targeted} {Dual} {Drug} {Delivery} {System} for {Carboplatin} and {Floxuridine}},
	issn = {2574-0970},
	doi = {10.1021/acsanm.2c01632},
	abstract = {Codelivery of chemotherapeutics via nanomaterials has attracted much attention over the last decades due to improved drug delivery to tumor tissues, decreased systemic effects, and increased therapeutic efficacies. High porosities, large pore volumes and surface areas, and tunable structures have positioned metal-organic frameworks (MOFs) as promising drug delivery systems (DDSs). In particular, nanoscale Zr-linked MOFs such as MOF-808 offer notable advantages for biomedical applications such as high porosity, good stability, and biocompatibility. In this study, we report efficient dual drug delivery of floxuridine (FUDR) and carboplatin (CARB) loaded in MOF-808 nanoparticles to cancer cells. The nanoparticles were further functionalized by a poly(acrylic acid-mannose acrylamide) (PAAMAM) glycopolymer coating to obtain a highly selective DDS in cancer cells and enhance the therapeutic efficacy of chemotherapy. While MOF-808 was found to enhance the individual therapeutic effects of FUDR and CARB toward cancerous cells, combining FUDR and CARB was seen to cause a synergistic effect, further enhancing the cytotoxicity of the free drugs. Enhancement of CARB loading and therefore cytotoxicity of the CARB-loaded MOFs could be induced through a modified activation protocol, while coating of MOF-808 with the PAAMAM glycopolymer increased the uptake of the nanoparticles in cancer cells used in the study and offered a particularly significant selective drug delivery with high cytotoxicity in HepG2 human hepatocellular carcinoma cells. These results show how the enhancement of cytotoxicity is possible through both nanovector delivery and synergistic treatment, and that MOF-808 is a viable candidate for future drug delivery studies.},
	urldate = {2022-07-10},
	journal = {ACS APPLIED NANO MATERIALS},
	author = {Duman, Fatma Demir and Monaco, Alessandra and Foulkes, Rachel and Becer, C. Remzi and Forgan, Ross S.},
	month = jun,
	year = {2022},
}

Codelivery of chemotherapeutics via nanomaterials has attracted much attention over the last decades due to improved drug delivery to tumor tissues, decreased systemic effects, and increased therapeutic efficacies. High porosities, large pore volumes and surface areas, and tunable structures have positioned metal-organic frameworks (MOFs) as promising drug delivery systems (DDSs). In particular, nanoscale Zr-linked MOFs such as MOF-808 offer notable advantages for biomedical applications such as high porosity, good stability, and biocompatibility. In this study, we report efficient dual drug delivery of floxuridine (FUDR) and carboplatin (CARB) loaded in MOF-808 nanoparticles to cancer cells. The nanoparticles were further functionalized by a poly(acrylic acid-mannose acrylamide) (PAAMAM) glycopolymer coating to obtain a highly selective DDS in cancer cells and enhance the therapeutic efficacy of chemotherapy. While MOF-808 was found to enhance the individual therapeutic effects of FUDR and CARB toward cancerous cells, combining FUDR and CARB was seen to cause a synergistic effect, further enhancing the cytotoxicity of the free drugs. Enhancement of CARB loading and therefore cytotoxicity of the CARB-loaded MOFs could be induced through a modified activation protocol, while coating of MOF-808 with the PAAMAM glycopolymer increased the uptake of the nanoparticles in cancer cells used in the study and offered a particularly significant selective drug delivery with high cytotoxicity in HepG2 human hepatocellular carcinoma cells. These results show how the enhancement of cytotoxicity is possible through both nanovector delivery and synergistic treatment, and that MOF-808 is a viable candidate for future drug delivery studies.

@article{bui_tailoring_2022,
	title = {Tailoring {Electromechanical} {Properties} of {Natural} {Rubber} {Vitrimers} by {Cross}-{Linkers}},
	volume = {61},
	issn = {0888-5885},
	doi = {10.1021/acs.iecr.2c01229},
	abstract = {The growing demand for smart polymeric transducers such as dielectric elastomer actuators and energy harvesters has urged the use of sustainable and recyclable elastomeric materials. Vitrimer chemistry has shed light on future reprocessable and recyclable thermosets and elastomers. In this work, epoxidized natural rubber (ENR) vitrimers were prepared using diacid or triacid cross-linkers and formed covalently cross-linking networks via thermally triggered reversible beta-hydroxy ester bonds. The cross-linked ENR elastomers exhibited Arrhenius-type viscoelastic behavior with a complete stress relaxation between 140 and 160 degrees C, that is, vitrimer characteristics, which were highly dependent on the cross-linking temperature. The mechanical and dielectric properties of the ENR vitrimers can be tuned by varying the molecular structure and concentration of the cross-linkers. Among the diacid and triacid cross-linkers, Pripol 1017 fatty polyacid (P1017) and 3,3'-dithiopropionic acid (DTPA) had similar effects on the cross-linking density and mechanical properties of the ENR vitrimers. The highest tensile strength of 8.70 +/- 1.9 or 15.6 +/- 2.6 MPa was obtained at 6 mol \% of P1017 or DTPA, respectively. While for diamide-based diacid cross-linker (DME), 8 mol \% was needed to reach the highest tensile strength of 13.1 +/- 2.7 MPa for the elastomer. The three ENR vitrimers showed increased relative permittivity epsilon' = 5 similar to 7 at 1 kHz while maintaining low dielectric losses compared to traditional dicumyl peroxide-cured ENR, with epsilon' = 3.57 at 1 kHz. With the optimized acidic cross-linker concentrations of P1017 at 6 mol 96, DTPA at 6 mol \%, and DME at 8 mol 96, the ENR vitrimers exhibited improved actuation capabilities at lower electrical fields. Utilizing dynamic cross-linkers to tune the electromechanical properties of dielectric elastomers and the reversibly cross-linked polymer networks will open new opportunities for smart and sustainable dielectric elastomer devices.},
	number = {25},
	urldate = {2022-07-08},
	journal = {INDUSTRIAL \& ENGINEERING CHEMISTRY RESEARCH},
	author = {Bui, Khoa and Wemyss, Alan M. and Zhang, Runan and Nguyen, Giao T. M. and Vancaeyzeele, Cedric and Vidal, Frederic and Plesse, Cedric and Wan, Chaoying},
	month = jun,
	year = {2022},
	pages = {8871--8880},
}

The growing demand for smart polymeric transducers such as dielectric elastomer actuators and energy harvesters has urged the use of sustainable and recyclable elastomeric materials. Vitrimer chemistry has shed light on future reprocessable and recyclable thermosets and elastomers. In this work, epoxidized natural rubber (ENR) vitrimers were prepared using diacid or triacid cross-linkers and formed covalently cross-linking networks via thermally triggered reversible beta-hydroxy ester bonds. The cross-linked ENR elastomers exhibited Arrhenius-type viscoelastic behavior with a complete stress relaxation between 140 and 160 degrees C, that is, vitrimer characteristics, which were highly dependent on the cross-linking temperature. The mechanical and dielectric properties of the ENR vitrimers can be tuned by varying the molecular structure and concentration of the cross-linkers. Among the diacid and triacid cross-linkers, Pripol 1017 fatty polyacid (P1017) and 3,3'-dithiopropionic acid (DTPA) had similar effects on the cross-linking density and mechanical properties of the ENR vitrimers. The highest tensile strength of 8.70 +/- 1.9 or 15.6 +/- 2.6 MPa was obtained at 6 mol % of P1017 or DTPA, respectively. While for diamide-based diacid cross-linker (DME), 8 mol % was needed to reach the highest tensile strength of 13.1 +/- 2.7 MPa for the elastomer. The three ENR vitrimers showed increased relative permittivity epsilon' = 5 similar to 7 at 1 kHz while maintaining low dielectric losses compared to traditional dicumyl peroxide-cured ENR, with epsilon' = 3.57 at 1 kHz. With the optimized acidic cross-linker concentrations of P1017 at 6 mol 96, DTPA at 6 mol %, and DME at 8 mol 96, the ENR vitrimers exhibited improved actuation capabilities at lower electrical fields. Utilizing dynamic cross-linkers to tune the electromechanical properties of dielectric elastomers and the reversibly cross-linked polymer networks will open new opportunities for smart and sustainable dielectric elastomer devices.

@article{kim_enabling_2022,
	title = {Enabling {Reversible} {Addition}-{Fragmentation} {Chain}-{Transfer} {Polymerization} for {Brush} {Copolymers} with a {Poly}(2-oxazoline) {Backbone}},
	volume = {55},
	issn = {0024-9297},
	doi = {10.1021/acs.macromol.2c00497},
	abstract = {The combination of different monomer classes has been sought after to access a wider range of brush copolymers owing to their unique properties derived from their dense macromolecular structures. Herein, we report the synthesis of a 2oxazoline monomer (RAFTOx) containing a chain transfer agent at the 2-position and its subsequent utilization in reversible addition-fragmentation chain-transfer (RAFT) polymerization. With the aim of tuning the brush density in these polymers, homopolymers, block copolymers, and gradient copolymers of various ratios with 2-ethyl-2-oxazoline and RAFTOx have been prepared. Selected brush macroCTAs were then used for the RAFT polymerization of N,N-dimethylacrylamide and 2-ethyhexyl acrylate to prepare brush copolymers of different architectures.},
	number = {11},
	urldate = {2022-06-24},
	journal = {MACROMOLECULES},
	author = {Kim, Jungyeon and Cattoz, Beatrice and Leung, Alice H. M. and Parish, James D. and Becer, C. Remzi},
	month = jun,
	year = {2022},
	note = {Infineum UK Ltd},
	pages = {4411--4419},
}

The combination of different monomer classes has been sought after to access a wider range of brush copolymers owing to their unique properties derived from their dense macromolecular structures. Herein, we report the synthesis of a 2oxazoline monomer (RAFTOx) containing a chain transfer agent at the 2-position and its subsequent utilization in reversible addition-fragmentation chain-transfer (RAFT) polymerization. With the aim of tuning the brush density in these polymers, homopolymers, block copolymers, and gradient copolymers of various ratios with 2-ethyl-2-oxazoline and RAFTOx have been prepared. Selected brush macroCTAs were then used for the RAFT polymerization of N,N-dimethylacrylamide and 2-ethyhexyl acrylate to prepare brush copolymers of different architectures.

@article{kerr_polymeric_2022,
	title = {Polymeric {Nanotubes} as {Drug} {Delivery} {Vectors}-{Comparison} of {Covalently} and {Supramolecularly} {Assembled} {Constructs}},
	volume = {23},
	issn = {1525-7797},
	doi = {10.1021/acs.biomac.2c00063},
	abstract = {Rod-shaped nanoparticles have been identified as promising drug delivery candidates. In this report, the in vitro cell uptake and in vivo pharmacokinetic/bio-distribution behavior of molecular bottle-brush (BB) and cyclic peptide self-assembled nanotubes were studied in the size range of 36-41 nm in length. It was found that BB possessed the longest plasma circulation time (t1{\textbackslash}2 {\textgreater} 35 h), with the cyclic peptide system displaying an intermediate half-life (14.6 h), although still substantially elevated over a non-assembling linear control (2.7 h). The covalently bound BB underwent substantial distribution into the liver, whereas the cyclic peptide nanotube was able to mostly circumvent organ accumulation, highlighting the advantage of the inherent degradability of the cyclic peptide systems through their reversible aggregation of hydrogen bonding core units.},
	number = {6},
	urldate = {2022-06-26},
	journal = {BIOMACROMOLECULES},
	author = {Kerr, Andrew and Sagita, Erny and Mansfield, Edward D. H. and Nguyen, Tri-Hung and Feeney, Orlagh M. and Pouton, Colin W. and Porter, Christopher J. H. and Sanchis, Joaquin and Perrier, Sebastien},
	month = jun,
	year = {2022},
	pages = {2315--2328},
}

Rod-shaped nanoparticles have been identified as promising drug delivery candidates. In this report, the in vitro cell uptake and in vivo pharmacokinetic/bio-distribution behavior of molecular bottle-brush (BB) and cyclic peptide self-assembled nanotubes were studied in the size range of 36-41 nm in length. It was found that BB possessed the longest plasma circulation time (t1\2 \textgreater 35 h), with the cyclic peptide system displaying an intermediate half-life (14.6 h), although still substantially elevated over a non-assembling linear control (2.7 h). The covalently bound BB underwent substantial distribution into the liver, whereas the cyclic peptide nanotube was able to mostly circumvent organ accumulation, highlighting the advantage of the inherent degradability of the cyclic peptide systems through their reversible aggregation of hydrogen bonding core units.

@article{du_force-reversible_2022,
	title = {Force-reversible chemical reaction at ambient temperature for designing toughened dynamic covalent polymer networks},
	volume = {13},
	issn = {2041-1723},
	doi = {10.1038/s41467-022-30972-7},
	abstract = {Force-reversible C-N bonds, resulting from the click chemistry reaction between triazolinedione (TAD) and indole derivatives, offer exciting opportunities for molecular-level engineering to design materials that respond to mechanical loads. Here, we displayed that TAD-indole adducts, acting as crosslink points in dry-state covalently crosslinked polymers, enable materials to display reversible stress-responsiveness in real time already at ambient temperature. Whereas the exergonic TAD-indole reaction results in the formation of bench-stable adducts, they were shown to dissociate at ambient temperature when embedded in a polymer network and subjected to a stretching force to recover the original products. Moreover, the nascent TAD moiety can spontaneously and immediately be recombined after dissociation with an indole reaction partners at ambient temperature, thus allowing for the adjustment of the polymer segment conformation and the maintenance of the network integrity by force-reversible behaviors. Overall, our strategy represents a general method to create toughened covalently crosslinked polymer materials with simultaneous enhancement of mechanical strength and ductility, which is quite challenging to achieve by conventional chemical methods.Weak force-activated covalent bonds as crosslink points can increase mechanical strength and ductility in polymers but the bonds, once broken, cannot be reformed in real time under ambient conditions leading to irreversible damage. Here, the authors demonstrate that triazolinedione (TAD)-indole adducts acting as crosslink points enable materials to display already at ambient temperature reversible stress-responsiveness in real time.},
	number = {1},
	urldate = {2022-06-24},
	journal = {NATURE COMMUNICATIONS},
	author = {Du, Mengqi and Houck, Hannes A. and Yin, Qiang and Xu, Yewei and Huang, Ying and Lan, Yang and Yang, Li and Du Prez, Filip E. and Chang, Guanjun},
	month = jun,
	year = {2022},
}

Force-reversible C-N bonds, resulting from the click chemistry reaction between triazolinedione (TAD) and indole derivatives, offer exciting opportunities for molecular-level engineering to design materials that respond to mechanical loads. Here, we displayed that TAD-indole adducts, acting as crosslink points in dry-state covalently crosslinked polymers, enable materials to display reversible stress-responsiveness in real time already at ambient temperature. Whereas the exergonic TAD-indole reaction results in the formation of bench-stable adducts, they were shown to dissociate at ambient temperature when embedded in a polymer network and subjected to a stretching force to recover the original products. Moreover, the nascent TAD moiety can spontaneously and immediately be recombined after dissociation with an indole reaction partners at ambient temperature, thus allowing for the adjustment of the polymer segment conformation and the maintenance of the network integrity by force-reversible behaviors. Overall, our strategy represents a general method to create toughened covalently crosslinked polymer materials with simultaneous enhancement of mechanical strength and ductility, which is quite challenging to achieve by conventional chemical methods.Weak force-activated covalent bonds as crosslink points can increase mechanical strength and ductility in polymers but the bonds, once broken, cannot be reformed in real time under ambient conditions leading to irreversible damage. Here, the authors demonstrate that triazolinedione (TAD)-indole adducts acting as crosslink points enable materials to display already at ambient temperature reversible stress-responsiveness in real time.

@article{topcu_control_2022,
	title = {Control over microphase separation and dielectric properties via para-fluoro thiol click reaction},
	volume = {10},
	issn = {2050-7526},
	doi = {10.1039/d2tc00009a},
	abstract = {Herein, we have reported a para-fluoro thiol click reaction allowing control of the microphase separation and dielectric properties of poly(pentafluorostyrene-b-acrylic acid) copolymers. The block copolymer of pentafluorostyrene and acrylic acid was synthesized with high block incompatibility by nitroxide mediated polymerisation. By using a para-fluoro thiol reaction, 1-dodecanethiol was precisely clicked to block copolymers in various ratios. The microphase structures formed with cylindrical morphologies with a minimum domain size of 5 nm. The orientation of the acrylic acid cylinders varied from horizontal to vertical as the click ratio was increased. The dielectric constant of the copolymers decreases with increasing click ratio because of the low dielectric constant of the dodecane pendant groups and reaches kappa = 2.4 (at 1000 Hz). This study provides insights on one-step control over phase and dielectric properties by using a facile and very effective click reaction strategy for the fabrication of novel polymers for next-generation capacitor films used in directed energy and advanced integrated circuits with smaller feature sizes.},
	number = {24},
	urldate = {2022-06-22},
	journal = {JOURNAL OF MATERIALS CHEMISTRY C},
	author = {Topcu, Gokhan and Arenas, David Reinoso and Huband, Steven and McNally, Tony and Becer, C. Remzi},
	month = jun,
	year = {2022},
	pages = {9356--9363},
}

Herein, we have reported a para-fluoro thiol click reaction allowing control of the microphase separation and dielectric properties of poly(pentafluorostyrene-b-acrylic acid) copolymers. The block copolymer of pentafluorostyrene and acrylic acid was synthesized with high block incompatibility by nitroxide mediated polymerisation. By using a para-fluoro thiol reaction, 1-dodecanethiol was precisely clicked to block copolymers in various ratios. The microphase structures formed with cylindrical morphologies with a minimum domain size of 5 nm. The orientation of the acrylic acid cylinders varied from horizontal to vertical as the click ratio was increased. The dielectric constant of the copolymers decreases with increasing click ratio because of the low dielectric constant of the dodecane pendant groups and reaches kappa = 2.4 (at 1000 Hz). This study provides insights on one-step control over phase and dielectric properties by using a facile and very effective click reaction strategy for the fabrication of novel polymers for next-generation capacitor films used in directed energy and advanced integrated circuits with smaller feature sizes.

@article{henderson_detection_2022,
	title = {Detection of selective androgen receptor modulators ({SARMs}) in serum using a molecularly imprinted nanoparticle surface plasmon resonance sensor},
	volume = {10},
	issn = {2050-750X},
	doi = {10.1039/d2tb00270a},
	abstract = {Selective Androgen Receptor Modulators (SARMs) are a fairly new class of therapeutic compounds that act upon the androgen receptor. They proffer similar anabolic properties to steroids, but with a much-reduced androgenic profile. They have become a popular substance of abuse in competitive sport. Being relatively new, detection systems are limited to chromatographic methods. Here we present a surface plasmon resonance sensor for three commonly-used SARMS, Andarine, Ligandrol and RAD-140, using high-affinity molecularly imprinted nanoparticles (nanoMIPs) as the recognition element. Synthesised nanoMIPS exhibited dissociation constant (K-D) values of 29.3 nM, 52.5 nM and 75.1 nM for Andarine, Ligandrol and RAD-140 nanoMIPs, respectively. Cross-reactivity of the particles was explored using the alternative SARMs, with the nanoMIPs demonstrating good specificity. Fetal Bovine Serum (FBS) was used to assess the ability of the SPR-based nanoMIP sensor to detect the target compounds in a comparable biological matrix, with observed K-D values of 12.3 nM, 31.9 nM and 28.1 nM for Andarine, Ligandrol and RAD-140 nanoMIPs, respectively. Theoretical limits of detection (LoD) were estimated from a calibration plot in FBS and show that the nanoMIP-based sensors have the potential to theoretically measure these SARMs in the low to sub nM range. Crucially these levels are below the minimum required performance limit (MRPL) set for these compounds by WADA. This study highlights the power of modern molecular imprinting to rapidly address required molecular recognition for new compounds of interest.},
	number = {35},
	urldate = {2022-06-18},
	journal = {JOURNAL OF MATERIALS CHEMISTRY B},
	author = {Henderson, Alisha and Sullivan, V, Mark and Hand, Rachel A. and Turner, Nicholas W.},
	month = sep,
	year = {2022},
	pages = {6792--6799},
}

Selective Androgen Receptor Modulators (SARMs) are a fairly new class of therapeutic compounds that act upon the androgen receptor. They proffer similar anabolic properties to steroids, but with a much-reduced androgenic profile. They have become a popular substance of abuse in competitive sport. Being relatively new, detection systems are limited to chromatographic methods. Here we present a surface plasmon resonance sensor for three commonly-used SARMS, Andarine, Ligandrol and RAD-140, using high-affinity molecularly imprinted nanoparticles (nanoMIPs) as the recognition element. Synthesised nanoMIPS exhibited dissociation constant (K-D) values of 29.3 nM, 52.5 nM and 75.1 nM for Andarine, Ligandrol and RAD-140 nanoMIPs, respectively. Cross-reactivity of the particles was explored using the alternative SARMs, with the nanoMIPs demonstrating good specificity. Fetal Bovine Serum (FBS) was used to assess the ability of the SPR-based nanoMIP sensor to detect the target compounds in a comparable biological matrix, with observed K-D values of 12.3 nM, 31.9 nM and 28.1 nM for Andarine, Ligandrol and RAD-140 nanoMIPs, respectively. Theoretical limits of detection (LoD) were estimated from a calibration plot in FBS and show that the nanoMIP-based sensors have the potential to theoretically measure these SARMs in the low to sub nM range. Crucially these levels are below the minimum required performance limit (MRPL) set for these compounds by WADA. This study highlights the power of modern molecular imprinting to rapidly address required molecular recognition for new compounds of interest.

@article{morgan_stochasticity_2022,
	title = {Stochasticity of poly(2-oxazoline) oligomer hydrolysis determined by tandem mass spectrometry},
	volume = {13},
	issn = {1759-9954},
	doi = {10.1039/d2py00437b},
	abstract = {Understanding modification of synthetic polymer structures is necessary for their accurate synthesis and potential applications. In this contribution, a series of partially hydrolyzed poly(2-oxazoline) species were produced forming poly[(2-polyoxazoline)-co-(ethylenimine)] (P(EtOx-co-EI)) copolymers; EI being the hydrolyzed product of Ox. Bulk mass spectrometry (MS) measurements accurately measured the EI content. Tandem mass spectrometry analysis of the EI content in the copolymer samples determined the distribution of each monomer within the copolymer and corresponded to a theoretically modelled random distribution. The EI distribution across the polymers was shown to be effected by the choice of terminus, with a permanent hydrolysis event observed at an OH terminus. A neighbouring group effect wasn't observed at the polymer length analysed (approximately 25-mer species), suggesting that previously observed neighbouring group effects require a larger polymer chain. Although clearly useful for random polymer distribution this approach may be applied to many systems containing non-specific modifications to determine if they are directed or random locations across peptides, proteins, polymers, and nucleic acids.},
	number = {28},
	urldate = {2022-07-06},
	journal = {POLYMER CHEMISTRY},
	author = {Morgan, Tomos E. and Floyd, Thomas G. and Marzullo, Bryan P. and Wootton, Christopher A. and Barrow, Mark P. and Bristow, Anthony W. T. and Perrier, Sebastien and O'Connor, Peter B.},
	month = jul,
	year = {2022},
	pages = {4162--4169},
}

Understanding modification of synthetic polymer structures is necessary for their accurate synthesis and potential applications. In this contribution, a series of partially hydrolyzed poly(2-oxazoline) species were produced forming poly[(2-polyoxazoline)-co-(ethylenimine)] (P(EtOx-co-EI)) copolymers; EI being the hydrolyzed product of Ox. Bulk mass spectrometry (MS) measurements accurately measured the EI content. Tandem mass spectrometry analysis of the EI content in the copolymer samples determined the distribution of each monomer within the copolymer and corresponded to a theoretically modelled random distribution. The EI distribution across the polymers was shown to be effected by the choice of terminus, with a permanent hydrolysis event observed at an OH terminus. A neighbouring group effect wasn't observed at the polymer length analysed (approximately 25-mer species), suggesting that previously observed neighbouring group effects require a larger polymer chain. Although clearly useful for random polymer distribution this approach may be applied to many systems containing non-specific modifications to determine if they are directed or random locations across peptides, proteins, polymers, and nucleic acids.

@article{xin_digital_2022,
	title = {Digital light processing {3D} printing of lightweight {Fe3O4}/{rGO}/resin composites with enhanced microwave absorption},
	volume = {31},
	issn = {2352-4928},
	doi = {10.1016/j.mtcomm.2022.103865},
	abstract = {A Fe3O4/rGO reinforced photocurable resin composite with gyroid structure was firstly fabricated by digital light processing (DLP) 3D printing. The obtained gyroid template was further coated with absorbants and experienced a post-curing treatment for microwave absorption (MA) applications. The minimum reflection loss of the Fe3O4/ rGO/resin gyroid composite coated with Fe3O4/rGO nanoparticles reached 38 dB at 10.8 GHz and a thickness of 2.5 mm, while effective absorption band was 77\% in the X-band, exhibiting the best MA performance. The leverage of DLP 3D printing allows for an optimal structure for absorbants coating and increases the opportunity for electromagnetic wave reflection/refraction/transmission. The synergistic effects of hybrid Fe3O4/rGO/resin template coated with Fe3O4/rGO and gyroid structure effectively promote the MA performance and realize the manufacturing of lightweighting composites for future electromagnetic protection applications.},
	urldate = {2022-08-19},
	journal = {MATERIALS TODAY COMMUNICATIONS},
	author = {Xin, Chenxing and Zhang, Jing and Peijs, Ton and Li, Yan},
	month = jun,
	year = {2022},
}

A Fe3O4/rGO reinforced photocurable resin composite with gyroid structure was firstly fabricated by digital light processing (DLP) 3D printing. The obtained gyroid template was further coated with absorbants and experienced a post-curing treatment for microwave absorption (MA) applications. The minimum reflection loss of the Fe3O4/ rGO/resin gyroid composite coated with Fe3O4/rGO nanoparticles reached 38 dB at 10.8 GHz and a thickness of 2.5 mm, while effective absorption band was 77% in the X-band, exhibiting the best MA performance. The leverage of DLP 3D printing allows for an optimal structure for absorbants coating and increases the opportunity for electromagnetic wave reflection/refraction/transmission. The synergistic effects of hybrid Fe3O4/rGO/resin template coated with Fe3O4/rGO and gyroid structure effectively promote the MA performance and realize the manufacturing of lightweighting composites for future electromagnetic protection applications.

@article{mohammed_current-controlled_2022,
	title = {Current-controlled 'plug-and-play' electrochemical atom transfer radical polymerization of acrylamides in water},
	volume = {13},
	issn = {1759-9954},
	doi = {10.1039/d2py00412g},
	abstract = {Aqueous electrochemical atom transfer radical polymerisation (eATRP) can be challenging due to deleterious side reactions leading to the loss of the omega-chain end, increased rates of activation (k(act)) leading to higher [P-n], increased rates of termination, and the lability of the X-Cu-II/L bond to hydrolysis leading to poor control. Herein, we build on recent advances in eATRP methodology to develop a simplified current-controlled eATRP of acrylamides in water. The simplification arises from the use of commercial, standardised reaction hardware which enables the polymerisations to be performed in a 2-electrode, 'plug-and-play', undivided electrochemical cell configuration. Further simplification is afforded by the design of a single stepwise current profile (I(app)vs. time) capable of mediating current-controlled eATRP of N-hydroethylacrylamide (HEAm). At room temperature, polymerisation of HEAm to target degrees of polymerisation (DPn,th) of 20-100 proceeds with good control (D {\textless}= 1.50). Loss of control when targeting higher DPn at room temperature is circumvented by lowering the reaction temperature (RT to 0 degrees C), increasing the stirring rate (400 rpm to 800 rpm) and increasing the catalyst concentration. Using the best conditions, a linear increase in M-n,M-SEC with DPn (up to DPn = 320) and low dispersity values (DPn,th = 40-160; D = 1.26-1.38) were obtained. Furthermore, the current profile and reaction conditions can support the polymerisation of other primary and secondary acrylamides and the retention of the omega-Br chain end is exemplified by a short in situ chain extension. Overall, this represents further simplification of aqueous eATRP with respect to reaction set up and experimental parameters (single current profile) which has been employed to synthesise polyacrylamides with good efficiency and control.},
	number = {23},
	urldate = {2022-06-10},
	journal = {POLYMER CHEMISTRY},
	author = {Mohammed, Mahir and Jones, Bryn A. and Wilson, Paul},
	month = jun,
	year = {2022},
	pages = {3460--3470},
}

Aqueous electrochemical atom transfer radical polymerisation (eATRP) can be challenging due to deleterious side reactions leading to the loss of the omega-chain end, increased rates of activation (k(act)) leading to higher [P-n], increased rates of termination, and the lability of the X-Cu-II/L bond to hydrolysis leading to poor control. Herein, we build on recent advances in eATRP methodology to develop a simplified current-controlled eATRP of acrylamides in water. The simplification arises from the use of commercial, standardised reaction hardware which enables the polymerisations to be performed in a 2-electrode, 'plug-and-play', undivided electrochemical cell configuration. Further simplification is afforded by the design of a single stepwise current profile (I(app)vs. time) capable of mediating current-controlled eATRP of N-hydroethylacrylamide (HEAm). At room temperature, polymerisation of HEAm to target degrees of polymerisation (DPn,th) of 20-100 proceeds with good control (D \textless= 1.50). Loss of control when targeting higher DPn at room temperature is circumvented by lowering the reaction temperature (RT to 0 degrees C), increasing the stirring rate (400 rpm to 800 rpm) and increasing the catalyst concentration. Using the best conditions, a linear increase in M-n,M-SEC with DPn (up to DPn = 320) and low dispersity values (DPn,th = 40-160; D = 1.26-1.38) were obtained. Furthermore, the current profile and reaction conditions can support the polymerisation of other primary and secondary acrylamides and the retention of the omega-Br chain end is exemplified by a short in situ chain extension. Overall, this represents further simplification of aqueous eATRP with respect to reaction set up and experimental parameters (single current profile) which has been employed to synthesise polyacrylamides with good efficiency and control.

@article{magee_ws2_2022,
	title = {{WS2} {Nanotubes} as a {1D} {Functional} {Filler} for {Melt} {Mixing} with {Poly}(lactic acid):{Implications} for {Composites} {Manufacture}},
	volume = {5},
	issn = {2574-0970},
	doi = {10.1021/acsanm.2c00489},
	abstract = {Multi-walled WS2 nanotubes (NTs) with lengths ranging from 2 to 65 mu m and widths from 50 to 110 nm were synthesized in a horizontal quartz-made reactor by a process yielding NTs with aspect ratios (ARs) between similar to 40 and {\textgreater}1000. The NTs obtained were thermally stable in air up to 400 degrees C but were oxidized within the temperature range 400-550 degrees C to produce yellow WO3 particles. Critically, 400 degrees C is well above the temperature used to mix additives with the majority of meltprocessable polymers. The hydrophilic WS2 NTs were easily dispersed in poly(lactic) acid (PLA) using a twin-screw extruder, but the shear stresses applied during melt mixing resulted in chopping of the NTs such that the AR decreased by {\textgreater}95\% and the tensile mechanical properties of the PLA were unchanged. Although the as-extruded unfilled PLA was {\textgreater}99\% amorphous, the much-shortened WS2 NTs had a significant effect on the crystallization behavior of PLA, inducing heterogeneous nucleation, increasing the crystallization temperature (T-c) by similar to 3 degrees C and the crystalline content by 15\%, and significantly increasing the rate of PLA crystallization, producing smaller and more densely packed spherulites. The reduction in the AR and the nucleating effect of WS2 NTs for PLA are critical considerations in the preparation, by melt mixing, of composites of rigid 1D NTs and polymers, irrespective of the target application, including bone tissue engineering and bioresorbable vascular scaffolds.},
	number = {5},
	urldate = {2022-07-12},
	journal = {ACS APPLIED NANO MATERIALS},
	author = {Magee, Eimear and Tang, Fengzai and Ozdemir, Esra and Walker, Marc and Di Luccio, Tiziana and Kornfield, Julia A. and Zak, Alla and Tenne, Reshef and McNally, Tony},
	month = may,
	year = {2022},
	note = {Holon Inst Technol HIT},
	pages = {6385--6397},
}

Multi-walled WS2 nanotubes (NTs) with lengths ranging from 2 to 65 mu m and widths from 50 to 110 nm were synthesized in a horizontal quartz-made reactor by a process yielding NTs with aspect ratios (ARs) between similar to 40 and \textgreater1000. The NTs obtained were thermally stable in air up to 400 degrees C but were oxidized within the temperature range 400-550 degrees C to produce yellow WO3 particles. Critically, 400 degrees C is well above the temperature used to mix additives with the majority of meltprocessable polymers. The hydrophilic WS2 NTs were easily dispersed in poly(lactic) acid (PLA) using a twin-screw extruder, but the shear stresses applied during melt mixing resulted in chopping of the NTs such that the AR decreased by \textgreater95% and the tensile mechanical properties of the PLA were unchanged. Although the as-extruded unfilled PLA was \textgreater99% amorphous, the much-shortened WS2 NTs had a significant effect on the crystallization behavior of PLA, inducing heterogeneous nucleation, increasing the crystallization temperature (T-c) by similar to 3 degrees C and the crystalline content by 15%, and significantly increasing the rate of PLA crystallization, producing smaller and more densely packed spherulites. The reduction in the AR and the nucleating effect of WS2 NTs for PLA are critical considerations in the preparation, by melt mixing, of composites of rigid 1D NTs and polymers, irrespective of the target application, including bone tissue engineering and bioresorbable vascular scaffolds.

@article{rajagopalan_advancement_2022,
	title = {Advancement of {Electroadhesion} {Technology} for {Intelligent} and {Self}-{Reliant} {Robotic} {Applications}},
	volume = {4},
	issn = {2640-4567},
	doi = {10.1002/aisy.202200064},
	abstract = {The growing need for automation in industries has foreseen drastic advancements in the development of soft robotics in the areas of navigation systems, textiles, healthcare, and biometric monitoring. Electroadhesion (EA)-based robotic applications benefit from ultralow power consumption, low maintenance, choices in versatile surfaces, sustainable life cycles, applicability in harsh and vacuum environments, and exteroceptive/proprioceptive abilities. It is of scientific and technological importance to comprehend the sequence of developments in working mechanisms, modeling, and materials to explore its full potential for future intelligent robotics systems. This review provides an all-inclusive roadmap of EA technology from its inception to unprecedented developments and complex relationships across multidisciplines, viz., robotics, solid and fluid mechanics, electrostatics, haptics, space technologies, nanotechnology, and IoT.},
	number = {7},
	urldate = {2022-05-21},
	journal = {ADVANCED INTELLIGENT SYSTEMS},
	author = {Rajagopalan, Pandey and Muthu, Manikandan and Liu, Yulu and Luo, Jikui and Wang, Xiaozhi and Wan, Chaoying},
	month = jul,
	year = {2022},
}

The growing need for automation in industries has foreseen drastic advancements in the development of soft robotics in the areas of navigation systems, textiles, healthcare, and biometric monitoring. Electroadhesion (EA)-based robotic applications benefit from ultralow power consumption, low maintenance, choices in versatile surfaces, sustainable life cycles, applicability in harsh and vacuum environments, and exteroceptive/proprioceptive abilities. It is of scientific and technological importance to comprehend the sequence of developments in working mechanisms, modeling, and materials to explore its full potential for future intelligent robotics systems. This review provides an all-inclusive roadmap of EA technology from its inception to unprecedented developments and complex relationships across multidisciplines, viz., robotics, solid and fluid mechanics, electrostatics, haptics, space technologies, nanotechnology, and IoT.

@article{zhao_aqueous_2022,
	title = {Aqueous electrochemically-triggered atom transfer radical polymerization},
	volume = {13},
	issn = {2041-6520},
	doi = {10.1039/d2sc01832b},
	abstract = {Simplified electrochemical atom transfer radical polymerization (seATRP) using Cu-II-N-propyl pyridineimine complexes (Cu-II(NPPI)(2)) is reported for the first time. In aqueous solution, using oligo(ethylene glycol) methyl ether methacrylate (OEGMA), standard electrolysis conditions yield POEGMA with good control over molecular weight distribution (D-m {\textless} 1.35). Interestingly, the polymerizations are not under complete electrochemical control, as monomer conversion continues when electrolysis is halted. Alternatively, it is shown that the extent and rate of polymerization depends upon an initial period of electrolysis. Thus, it is proposed that seATRP using Cu-II(NPPI)(2) follows an electrochemically-triggered, rather than electrochemically mediated, ATRP mechanism, which distinguishes them from other (CuL)-L-II complexes that have been previously reported in the literature.},
	number = {19},
	urldate = {2022-05-05},
	journal = {CHEMICAL SCIENCE},
	author = {Zhao, Boyu and Pashley-Johnson, Fred and Jones, Bryn A. and Wilson, Paul},
	month = may,
	year = {2022},
	pages = {5741--5749},
}

Simplified electrochemical atom transfer radical polymerization (seATRP) using Cu-II-N-propyl pyridineimine complexes (Cu-II(NPPI)(2)) is reported for the first time. In aqueous solution, using oligo(ethylene glycol) methyl ether methacrylate (OEGMA), standard electrolysis conditions yield POEGMA with good control over molecular weight distribution (D-m \textless 1.35). Interestingly, the polymerizations are not under complete electrochemical control, as monomer conversion continues when electrolysis is halted. Alternatively, it is shown that the extent and rate of polymerization depends upon an initial period of electrolysis. Thus, it is proposed that seATRP using Cu-II(NPPI)(2) follows an electrochemically-triggered, rather than electrochemically mediated, ATRP mechanism, which distinguishes them from other (CuL)-L-II complexes that have been previously reported in the literature.

@article{liarou_reversible_2022,
	title = {Reversible {Transformations} of {Polymer} {Topologies} through {Visible} {Light} and {Darkness}},
	volume = {144},
	issn = {0002-7863},
	doi = {10.1021/jacs.2c01622},
	abstract = {A fundamentally important characteristic of a macromolecule is its shape. Herein, visible light and darkness are used as the only stimuli to reversibly alter the topology of well-defined polymers in a one-pot procedure. For this, linear naphthalene-containing polyacrylates are used as scaffolds for the visible light-induced cycloaddition with various substituted triazolinediones (i.e., butyl, stearyl, perfluoro, and polymeric), resulting in differently shaped graft polymers, including brushes and combs. The thus-formed cydoadduct linkages dissociate in the dark, resulting in the regeneration of the parent linear polymer at ambient temperature, establishing a dual-topology transformation by only switching green light on and off By applying different temperatures during the cycloreversion process, the dissociation rate of the cydoadducts can be tuned in a facile manner, thus allowing for time control over the regeneration of the parent polymer. By engineering a polymer that consists of differently substituted naphthalenes at the chain ends and on the side chains, the inherently different cydoreversion rates of the formed cydoadducts are leveraged to achieve in situ multi-topology transformations without external stimuli. The shape transformations have been repeated up to 4 times sequentially in one pot without the need of any purification. The topological alterations are microscopically depicted through reversible self-assembly, with the polymers adopting different morphologies upon visible light or darkness. The versatile yet practical nature of this polymer "reshaping" strategy provides facile access to multifaceted polymer systems and, consequently, to a plethora of potential applications thereof.},
	number = {15},
	urldate = {2022-06-01},
	journal = {JOURNAL OF THE AMERICAN CHEMICAL SOCIETY},
	author = {Liarou, Evelina and Houck, Hannes A. and Du Prez, Filip E.},
	month = apr,
	year = {2022},
	pages = {6954--6963},
}

A fundamentally important characteristic of a macromolecule is its shape. Herein, visible light and darkness are used as the only stimuli to reversibly alter the topology of well-defined polymers in a one-pot procedure. For this, linear naphthalene-containing polyacrylates are used as scaffolds for the visible light-induced cycloaddition with various substituted triazolinediones (i.e., butyl, stearyl, perfluoro, and polymeric), resulting in differently shaped graft polymers, including brushes and combs. The thus-formed cydoadduct linkages dissociate in the dark, resulting in the regeneration of the parent linear polymer at ambient temperature, establishing a dual-topology transformation by only switching green light on and off By applying different temperatures during the cycloreversion process, the dissociation rate of the cydoadducts can be tuned in a facile manner, thus allowing for time control over the regeneration of the parent polymer. By engineering a polymer that consists of differently substituted naphthalenes at the chain ends and on the side chains, the inherently different cydoreversion rates of the formed cydoadducts are leveraged to achieve in situ multi-topology transformations without external stimuli. The shape transformations have been repeated up to 4 times sequentially in one pot without the need of any purification. The topological alterations are microscopically depicted through reversible self-assembly, with the polymers adopting different morphologies upon visible light or darkness. The versatile yet practical nature of this polymer "reshaping" strategy provides facile access to multifaceted polymer systems and, consequently, to a plethora of potential applications thereof.

@article{baker_end-functionalized_2022,
	title = {End-{Functionalized} {Poly}(vinylpyrrolidone) for {Ligand} {Display} in {Lateral} {Flow} {Device} {Test} {Lines}},
	volume = {2},
	issn = {2694-2453},
	doi = {10.1021/acspolymersau.1c00032},
	abstract = {Lateral flow devices are rapid (and often low cost) point-of-care diagnostics-the classic example being the home pregnancy test. A test line (the stationary phase) is typically prepared by the physisorption of an antibody, which binds to analytes/antigens such as viruses, toxins, or hormones. However, there is no intrinsic requirement for the detection unit to be an antibody, and incorporating other ligand classes may bring new functionalities or detection capabilities. To enable other (non-protein) ligands to be deployed in lateral flow devices, they must be physiosorbed to the stationary phase as a conjugate, which currently would be a high-molecular-weight carrier protein, which requires (challenging) chemoselective modifications and purification. Here, we demonstrate that poly(vinylpyrrolidone), PVP, is a candidate for a polymeric, protein-free test line, owing to its unique balance of water solubility (for printing) and adhesion to the nitrocellulose stationary phase. End-functionalized PVPs were prepared by RAFT polymerization, and the model capture ligands of biotin and galactosamine were installed on PVP and subsequently immobilized on nitrocellulose. This polymeric test line was validated in both flow-through and full lateral flow formats using streptavidin and soybean agglutinin and is the first demonstration of an "all-polymer" approach for installation of capture units. This work illustrates the potential of polymeric scaffolds as anchoring agents for small-molecule capture agents in the next generation of robust and modular lateral flow devices and that macromolecular engineering may provide real benefit.},
	number = {2},
	urldate = {2022-10-15},
	journal = {ACS POLYMERS AU},
	author = {Baker, Alexander N. and Congdon, Thomas R. and Richards, Sarah-Jane and Georgiou, Panagiotis G. and Walker, Marc and Dedola, Simone and Field, Robert A. and Gibson, I, Matthew},
	month = apr,
	year = {2022},
	note = {Iceni Diagnost Ltd},
	pages = {69--79},
}

Lateral flow devices are rapid (and often low cost) point-of-care diagnostics-the classic example being the home pregnancy test. A test line (the stationary phase) is typically prepared by the physisorption of an antibody, which binds to analytes/antigens such as viruses, toxins, or hormones. However, there is no intrinsic requirement for the detection unit to be an antibody, and incorporating other ligand classes may bring new functionalities or detection capabilities. To enable other (non-protein) ligands to be deployed in lateral flow devices, they must be physiosorbed to the stationary phase as a conjugate, which currently would be a high-molecular-weight carrier protein, which requires (challenging) chemoselective modifications and purification. Here, we demonstrate that poly(vinylpyrrolidone), PVP, is a candidate for a polymeric, protein-free test line, owing to its unique balance of water solubility (for printing) and adhesion to the nitrocellulose stationary phase. End-functionalized PVPs were prepared by RAFT polymerization, and the model capture ligands of biotin and galactosamine were installed on PVP and subsequently immobilized on nitrocellulose. This polymeric test line was validated in both flow-through and full lateral flow formats using streptavidin and soybean agglutinin and is the first demonstration of an "all-polymer" approach for installation of capture units. This work illustrates the potential of polymeric scaffolds as anchoring agents for small-molecule capture agents in the next generation of robust and modular lateral flow devices and that macromolecular engineering may provide real benefit.

@article{hu_tuning_2022,
	title = {Tuning triboelectric and energy harvesting properties of dielectric elastomers via dynamic ionic crosslinks},
	volume = {3},
	issn = {2633-5409},
	doi = {10.1039/d2ma00124a},
	abstract = {The bromination of poly(isobutylene-co-isoprene) rubber introduces a small amount of bromide groups (1-2 mol\%) to the elastomer backbone and creates new opportunities for functionalisation, as compared to other saturated and diene elastomers. In this work, three types of nucleophile reagents: namely pyridine, triphenylphosphine and imidazoles bearing four types of side groups of methyl, ethyl, hydroxyl or vinyl group were introduced to brominated poly(isobutylene-co-isoprene) rubber (BIIR) through nucleophile substitution with the bromine via solid-state rubber compounding and curing processes. The resulted ionic aggregates act as physical crosslinks and their size and density directly affected the mechanical reinforcement, self-healing and dynamic mechanical properties of the elastomers. The smaller and polar imidazolyl/bromine pairs led to the highest reinforcement beyond even the sulfur-cured BIIR counterparts. The 1-ethyl imidazole (EIm) modified BIIR showed the highest tensile strength of 17.01 +/- 1.89 MPa and elongation at break of 1402 +/- 69\% with self-healing efficiency of 63.7\%, after being treated at 140 degrees C for 30 min. In addition, the inclusion of the ionic clusters enhanced the relative permittivity of the elastomer, thereby enhancing the energy conversion efficiencies. The nucleophile substitution reaction via conventional solid-state rubber compounding processes provides a facile crosslinking and reinforcement strategy for halogen-containing polymers. In addition, the dynamic ionic crosslinking networks spontaneously benefit electromechanical and self-healing properties of the dielectric elastomers.},
	number = {10},
	urldate = {2022-04-25},
	journal = {MATERIALS ADVANCES},
	author = {Hu, Xiao and Zhang, Runan and Wemyss, Alan M. and Elbanna, Mohamed A. and Heeley, Ellen L. and Arafa, Mustafa and Bowen, Chris and Wang, Shifeng and Geng, Xueyu and Wan, Chaoying},
	month = may,
	year = {2022},
	pages = {4213--4226},
}

The bromination of poly(isobutylene-co-isoprene) rubber introduces a small amount of bromide groups (1-2 mol%) to the elastomer backbone and creates new opportunities for functionalisation, as compared to other saturated and diene elastomers. In this work, three types of nucleophile reagents: namely pyridine, triphenylphosphine and imidazoles bearing four types of side groups of methyl, ethyl, hydroxyl or vinyl group were introduced to brominated poly(isobutylene-co-isoprene) rubber (BIIR) through nucleophile substitution with the bromine via solid-state rubber compounding and curing processes. The resulted ionic aggregates act as physical crosslinks and their size and density directly affected the mechanical reinforcement, self-healing and dynamic mechanical properties of the elastomers. The smaller and polar imidazolyl/bromine pairs led to the highest reinforcement beyond even the sulfur-cured BIIR counterparts. The 1-ethyl imidazole (EIm) modified BIIR showed the highest tensile strength of 17.01 +/- 1.89 MPa and elongation at break of 1402 +/- 69% with self-healing efficiency of 63.7%, after being treated at 140 degrees C for 30 min. In addition, the inclusion of the ionic clusters enhanced the relative permittivity of the elastomer, thereby enhancing the energy conversion efficiencies. The nucleophile substitution reaction via conventional solid-state rubber compounding processes provides a facile crosslinking and reinforcement strategy for halogen-containing polymers. In addition, the dynamic ionic crosslinking networks spontaneously benefit electromechanical and self-healing properties of the dielectric elastomers.

@article{peijs_chapter_2022,
	title = {Chapter 5: {A} critical review of carbon fiber and related products from an industrial perspective},
	volume = {5},
	issn = {2542-5048},
	doi = {10.1016/j.aiepr.2022.03.0082542-5048},
	abstract = {Because of their exceptional mechanical properties, carbon fibers are being used in composite applications where weight saving is key such as in the aerospace and sports sector, with increasing demands coming from wind energy, aerospace and defense. However, an even more significant increase in demand in automotive is foreseen if the cost price of carbon fiber could come down substantially. In 2012 the US Department of Energy set a target price level of 10 USD/kg to get carbon fiber into mainstream cars. These low-cost carbon fibers should possess a tenacity of at least 1.7 GPa with a corresponding elastic modulus of 170 GPa. Carbon fibers are currently predominantly based on polyacrylonitrile (PAN) precursor fibers, while pitch is used for some high-modulus fibers. The cost price of PAN-based carbon fibers is determined for at least 50\% by the PAN precursor. Consequently, over the last decade huge R\&D programs have been undertaken in search of cheaper and more sustainable precursors such as lignin and polyethylene. Despite major efforts no significant commercial successes have been obtained up to now in stark contrast with numerous claims in the scientific literature regarding so-called breakthrough technologies. Next to the recent revival in carbon fiber research another carbon allotrope, the carbon nanotube (CNT), has received huge attention as the 'next generation' reinforcing element for composites. Fibers and yarns have been made directly from CNTs or have been added into other high-performance fibers to boost their properties. However, also here despite major research efforts and numerous high impact publications the results obtained were at best interesting or doubtful with little commercial success. (c) 2022 Kingfa Scientific and Technological Co. Ltd. Publishing services by Elsevier B.V. on behalf of KeAi Communications Co. Ltd. This is an open access article under the CC BY-NC-ND license (http:// creativecommons.org/licenses/by-nc-nd/4.0/).},
	number = {2},
	urldate = {2022-04-01},
	journal = {ADVANCED INDUSTRIAL AND ENGINEERING POLYMER RESEARCH},
	author = {Peijs, Ton and Kirschbaum, Robert and Lemstra, Pieter Jan},
	month = apr,
	year = {2022},
	note = {PlemPolco BV},
	pages = {90--106},
}

Because of their exceptional mechanical properties, carbon fibers are being used in composite applications where weight saving is key such as in the aerospace and sports sector, with increasing demands coming from wind energy, aerospace and defense. However, an even more significant increase in demand in automotive is foreseen if the cost price of carbon fiber could come down substantially. In 2012 the US Department of Energy set a target price level of 10 USD/kg to get carbon fiber into mainstream cars. These low-cost carbon fibers should possess a tenacity of at least 1.7 GPa with a corresponding elastic modulus of 170 GPa. Carbon fibers are currently predominantly based on polyacrylonitrile (PAN) precursor fibers, while pitch is used for some high-modulus fibers. The cost price of PAN-based carbon fibers is determined for at least 50% by the PAN precursor. Consequently, over the last decade huge R&D programs have been undertaken in search of cheaper and more sustainable precursors such as lignin and polyethylene. Despite major efforts no significant commercial successes have been obtained up to now in stark contrast with numerous claims in the scientific literature regarding so-called breakthrough technologies. Next to the recent revival in carbon fiber research another carbon allotrope, the carbon nanotube (CNT), has received huge attention as the 'next generation' reinforcing element for composites. Fibers and yarns have been made directly from CNTs or have been added into other high-performance fibers to boost their properties. However, also here despite major research efforts and numerous high impact publications the results obtained were at best interesting or doubtful with little commercial success. (c) 2022 Kingfa Scientific and Technological Co. Ltd. Publishing services by Elsevier B.V. on behalf of KeAi Communications Co. Ltd. This is an open access article under the CC BY-NC-ND license (http:// creativecommons.org/licenses/by-nc-nd/4.0/).

@article{bhatti_light-driven_2022,
	title = {Light-{Driven} {Actuation} in {Synthetic} {Polymers}: {A} {Review} from {Fundamental} {Concepts} to {Applications}},
	volume = {10},
	issn = {2195-1071},
	doi = {10.1002/adom.202102186},
	abstract = {Light-driven actuation of synthetic polymers is an emerging field of interest because it offers simple remote addressing without complicated hydraulic, electric, or magnetic systems. Reviews on this area predominantly emphasize on the development of mechanical motions like bending, twisting, folding, etc. However, the scientific and fundamental aspects of these materials are critical in order to expand applications and industrial relevance. Polymer actuators driven by light, not only comprise soft actuators (large deformations at low stress) but also include stiff actuators (high actuation stress at low strain). Synthetic polymeric materials with photo-responsive additives together with underlying mechanisms, processing parameters, and final properties are required to broaden the scope of the field. In particular, parameters like actuation stress, actuation strain, and work capacity have been given limited attention in the past and are discussed extensively. This work gives a comprehensive critical review on all light-driven synthetic polymer actuators, their actuating mechanisms, and materials. A holistic perspective together with an insight into future prospects can lead academia and industry toward future innovations and applications of these exciting functional materials.},
	number = {10},
	urldate = {2022-04-07},
	journal = {ADVANCED OPTICAL MATERIALS},
	author = {Bhatti, Muhammad Rehan Asghar and Kernin, Arnaud and Tausif, Muhammad and Zhang, Han and Papageorgiou, Dimitrios and Bilotti, Emiliano and Peijs, Ton and Bastiaansen, Cees W. M.},
	month = may,
	year = {2022},
	note = {Univ Engn \& Technol Lahore},
}

Light-driven actuation of synthetic polymers is an emerging field of interest because it offers simple remote addressing without complicated hydraulic, electric, or magnetic systems. Reviews on this area predominantly emphasize on the development of mechanical motions like bending, twisting, folding, etc. However, the scientific and fundamental aspects of these materials are critical in order to expand applications and industrial relevance. Polymer actuators driven by light, not only comprise soft actuators (large deformations at low stress) but also include stiff actuators (high actuation stress at low strain). Synthetic polymeric materials with photo-responsive additives together with underlying mechanisms, processing parameters, and final properties are required to broaden the scope of the field. In particular, parameters like actuation stress, actuation strain, and work capacity have been given limited attention in the past and are discussed extensively. This work gives a comprehensive critical review on all light-driven synthetic polymer actuators, their actuating mechanisms, and materials. A holistic perspective together with an insight into future prospects can lead academia and industry toward future innovations and applications of these exciting functional materials.

@article{desire_styrene-based_2022,
	title = {Styrene-based polymerised high internal phase emulsions using monomers in the internal phase as co-surfactants for improved liquid chromatography},
	volume = {12},
	issn = {2046-2069},
	doi = {10.1039/d1ra07705h},
	abstract = {Poly(styrene-co-divinylbenzene)-based monoliths were prepared from the polymerisation of water-in-monomer high internal phase emulsions, where the water-soluble monomers acrylamide (AAm) or poly(ethylene glycol) diacrylate (PEGDA) (M-w 258) were also included in the 90 vol\% internal phase. Both AAm and PEGDA were found to act as co-surfactants, resulting in the obtainment of monoliths with greater homogeneity in some cases. As a result these materials demonstrated significantly improved chromatographic performance for the separation of a standard mixture of proteins using reversed-phase liquid chromatography, in comparison to monoliths prepared with no internal phase monomer. In particular, the columns grafted with PEGDA were capable of separating a more complex mixture consisting of seven components. The inclusion of monomers in the internal phase also allowed for the functionalisation of the monolith's surface where the degree of polymerisation that occurred in the internal phase, which was governed by the monomer content in the internal phase and initiation location, determined whether polymeric chains or a hydrogel were grafted to the surface. A monolith grafted with AAm was also found to be capable of retaining polar analytes as a result of the increase in surface hydrophilicity.},
	number = {16},
	urldate = {2022-04-08},
	journal = {RSC ADVANCES},
	author = {Desire, Christopher T. and Arrua, R. Dario and Mansour, Fotouh R. and Bon, Stefan A. F. and Hilder, Emily F.},
	month = mar,
	year = {2022},
	pages = {9773--9785},
}

Poly(styrene-co-divinylbenzene)-based monoliths were prepared from the polymerisation of water-in-monomer high internal phase emulsions, where the water-soluble monomers acrylamide (AAm) or poly(ethylene glycol) diacrylate (PEGDA) (M-w 258) were also included in the 90 vol% internal phase. Both AAm and PEGDA were found to act as co-surfactants, resulting in the obtainment of monoliths with greater homogeneity in some cases. As a result these materials demonstrated significantly improved chromatographic performance for the separation of a standard mixture of proteins using reversed-phase liquid chromatography, in comparison to monoliths prepared with no internal phase monomer. In particular, the columns grafted with PEGDA were capable of separating a more complex mixture consisting of seven components. The inclusion of monomers in the internal phase also allowed for the functionalisation of the monolith's surface where the degree of polymerisation that occurred in the internal phase, which was governed by the monomer content in the internal phase and initiation location, determined whether polymeric chains or a hydrogel were grafted to the surface. A monolith grafted with AAm was also found to be capable of retaining polar analytes as a result of the increase in surface hydrophilicity.

@article{sullivan_molecularly_2022,
	title = {A molecularly imprinted polymer nanoparticle-based surface plasmon resonance sensor platform for antibiotic detection in river water and milk},
	volume = {414},
	issn = {1618-2642},
	doi = {10.1007/s00216-022-04012-8},
	abstract = {Using a solid-phase molecular imprinting technique, high-affinity nanoparticles (nanoMIPs) selective for the target antibiotics, ciprofloxacin, moxifloxacin, and ofloxacin have been synthesised. These have been applied in the development of a surface plasmon resonance (SPR) sensor for the detection of the three antibiotics in both river water and milk. The particles produced demonstrated good uniformity with approximate sizes of 65.8 +/- 1.8 nm, 76.3 +/- 4.1 nm, and 85.7 +/- 2.5 nm, and were demonstrated to have affinities of 36.2 nM, 54.7 nM, and 34.6 nM for the ciprofloxacin, moxifloxacin, and ofloxacin nanoMIPs, respectively. Cross-reactivity studies highlighted good selectivity towards the target antibiotic compared with a non-target antibiotic. Using spiked milk and river water samples, the nanoMIP-based SPR sensor offered comparable affinity with 66.8 nM, 33.4 nM, and 55.0 nM (milk) and 39.3 nM, 26.1 nM, and 42.7 nM (river water) for ciprofloxacin, moxifloxacin, and ofloxacin nanoMIPs, respectively, to that seen within a buffer standard. Estimated LODs for the three antibiotic targets in both milk and river water were low nM or below. The developed SPR sensor showed good potential for using the technology for the capture and detection of antibiotics from food and environmental samples.},
	number = {12},
	urldate = {2022-03-31},
	journal = {ANALYTICAL AND BIOANALYTICAL CHEMISTRY},
	author = {Sullivan, V, Mark and Henderson, Alisha and Hand, Rachel A. and Turner, Nicholas W.},
	month = may,
	year = {2022},
	pages = {3687--3696},
}

Using a solid-phase molecular imprinting technique, high-affinity nanoparticles (nanoMIPs) selective for the target antibiotics, ciprofloxacin, moxifloxacin, and ofloxacin have been synthesised. These have been applied in the development of a surface plasmon resonance (SPR) sensor for the detection of the three antibiotics in both river water and milk. The particles produced demonstrated good uniformity with approximate sizes of 65.8 +/- 1.8 nm, 76.3 +/- 4.1 nm, and 85.7 +/- 2.5 nm, and were demonstrated to have affinities of 36.2 nM, 54.7 nM, and 34.6 nM for the ciprofloxacin, moxifloxacin, and ofloxacin nanoMIPs, respectively. Cross-reactivity studies highlighted good selectivity towards the target antibiotic compared with a non-target antibiotic. Using spiked milk and river water samples, the nanoMIP-based SPR sensor offered comparable affinity with 66.8 nM, 33.4 nM, and 55.0 nM (milk) and 39.3 nM, 26.1 nM, and 42.7 nM (river water) for ciprofloxacin, moxifloxacin, and ofloxacin nanoMIPs, respectively, to that seen within a buffer standard. Estimated LODs for the three antibiotic targets in both milk and river water were low nM or below. The developed SPR sensor showed good potential for using the technology for the capture and detection of antibiotics from food and environmental samples.

@article{efstathiou_functional_2022,
	title = {Functional {pH}-responsive polymers containing dynamic enaminone linkages for the release of active organic amines},
	volume = {13},
	issn = {1759-9954},
	doi = {10.1039/d2py00167e},
	abstract = {Dynamic covalent bonds have attracted considerable attention for the development of pH-responsive polymers, however, studies using acid-cleavable enaminone linkages as a means of controlled release are limited. Herein, we report pH-sensitive benzocaine-modified poly(ethylene glycol) monomethyl ether-block-poly[2-(acetoacetoxy)ethyl methacrylate] (mPEG(x)-b-pAEMA(y))/BNZ nanoparticles (NPs) for the aqueous controlled release of benzocaine through enaminone bond cleavage. The system is based on the commercially available monomer 2-(acetoacetoxy)ethyl methacrylate (AEMA) which contains free pendant beta-ketoester functionality. Well-defined poly[2-(acetoacetoxy)ethyl methacrylate] (pAEMA) homopolymers and poly[(ethylene glycol) monomethyl ether]-block-poly[2-(acetoacetoxy)ethyl methacrylate] (mPEG(x)-b-pAEMA(y)) amphiphilic block copolymers were prepared by photoinduced Cu(ii)-mediated RDRP to investigate their modification with propylamine (a model amine) and benzocaine (a primary amine containing API) through an enaminone bond. Block copolymers were prepared via two poly(ethylene glycol) monomethyl ether-2-bromo-2-phenylacetate (mPEG(x)-BPA, x = 43 or 113) macroinitiators synthesised by esterification which acted as the hydrophilic coronas of the ensuing NPs. The self-assembly of both mPEG(x)-b-pAEMA(y) and (mPEG(x)-b-pAEMA(y))/BNZ was assessed in water by the direct dilution approach forming spherical NPs as characterised by dynamic light scattering (DLS) and dry-state transmission electron microscopy (TEM). Finally, the in vitro controlled release of benzocaine from mPEG(x)-b-pAEMA(y)/BNZ NPs was examined at different pH environments demonstrating faster release kinetics at lower pH with potential utility in applications with relevant chemical environments.},
	number = {16},
	urldate = {2022-04-20},
	journal = {POLYMER CHEMISTRY},
	author = {Efstathiou, Spyridon and Ma, Congkai and Coursari, Despina and Patias, Georgios and Al-Shok, Lucas and Eissa, Ahmed M. and Haddleton, David M.},
	month = apr,
	year = {2022},
	pages = {2362--2374},
}

Dynamic covalent bonds have attracted considerable attention for the development of pH-responsive polymers, however, studies using acid-cleavable enaminone linkages as a means of controlled release are limited. Herein, we report pH-sensitive benzocaine-modified poly(ethylene glycol) monomethyl ether-block-poly[2-(acetoacetoxy)ethyl methacrylate] (mPEG(x)-b-pAEMA(y))/BNZ nanoparticles (NPs) for the aqueous controlled release of benzocaine through enaminone bond cleavage. The system is based on the commercially available monomer 2-(acetoacetoxy)ethyl methacrylate (AEMA) which contains free pendant beta-ketoester functionality. Well-defined poly[2-(acetoacetoxy)ethyl methacrylate] (pAEMA) homopolymers and poly[(ethylene glycol) monomethyl ether]-block-poly[2-(acetoacetoxy)ethyl methacrylate] (mPEG(x)-b-pAEMA(y)) amphiphilic block copolymers were prepared by photoinduced Cu(ii)-mediated RDRP to investigate their modification with propylamine (a model amine) and benzocaine (a primary amine containing API) through an enaminone bond. Block copolymers were prepared via two poly(ethylene glycol) monomethyl ether-2-bromo-2-phenylacetate (mPEG(x)-BPA, x = 43 or 113) macroinitiators synthesised by esterification which acted as the hydrophilic coronas of the ensuing NPs. The self-assembly of both mPEG(x)-b-pAEMA(y) and (mPEG(x)-b-pAEMA(y))/BNZ was assessed in water by the direct dilution approach forming spherical NPs as characterised by dynamic light scattering (DLS) and dry-state transmission electron microscopy (TEM). Finally, the in vitro controlled release of benzocaine from mPEG(x)-b-pAEMA(y)/BNZ NPs was examined at different pH environments demonstrating faster release kinetics at lower pH with potential utility in applications with relevant chemical environments.

@article{georgiou_plasmonic_2022,
	title = {Plasmonic {Detection} of {SARS}-{CoV}-2 {Spike} {Protein} with {Polymer}-{Stabilized} {Glycosylated} {Gold} {Nanorods}},
	volume = {11},
	issn = {2161-1653},
	doi = {10.1021/acsmacrolett.1c00716},
	abstract = {The COVID-19 pandemic has highlighted the need for innovative biosensing, diagnostic, and surveillance platforms. Here we report that glycosylated, polymer-stabilized, gold nanorods can bind the SARS-CoV-2 spike protein and show correlation to the presence of SARS-CoV-2 in primary COVID-19 clinical samples. Telechelic polymers were prepared by reversible addition-fragmentation chain-transfer polymerization, enabling the capture of 2,3-sialyllactose and immobilization onto gold nanorods. Control experiments with a panel of lectins and a galactosamine-terminated polymer confirmed the selective binding. The glycosylated rods were shown to give dose-dependent responses against recombinant truncated SARS-CoV-2 spike protein, and the responses were further correlated using primary patient swab samples. The essentiality of the anisotropic particles for reducing the background interference is demonstrated. This highlights the utility of polymer tethering of glycans for plasmonic biosensors of infection.},
	number = {3},
	urldate = {2022-04-01},
	journal = {ACS MACRO LETTERS},
	author = {Georgiou, Panagiotis G. and Guy, Collette S. and Hasan, Muhammad and Ahmad, Ashfaq and Richards, Sarah-Jane and Baker, Alexander N. and Thakkar, V, Neer and Walker, Marc and Pandey, Sarojini and Anderson, Neil R. and Grammatopoulos, Dimitris and Gibson, I, Matthew},
	month = mar,
	year = {2022},
	pages = {317--322},
}

The COVID-19 pandemic has highlighted the need for innovative biosensing, diagnostic, and surveillance platforms. Here we report that glycosylated, polymer-stabilized, gold nanorods can bind the SARS-CoV-2 spike protein and show correlation to the presence of SARS-CoV-2 in primary COVID-19 clinical samples. Telechelic polymers were prepared by reversible addition-fragmentation chain-transfer polymerization, enabling the capture of 2,3-sialyllactose and immobilization onto gold nanorods. Control experiments with a panel of lectins and a galactosamine-terminated polymer confirmed the selective binding. The glycosylated rods were shown to give dose-dependent responses against recombinant truncated SARS-CoV-2 spike protein, and the responses were further correlated using primary patient swab samples. The essentiality of the anisotropic particles for reducing the background interference is demonstrated. This highlights the utility of polymer tethering of glycans for plasmonic biosensors of infection.

@article{xiong_simultaneous_2022,
	title = {Simultaneous strength and ductility enhancements of high thermal conductive {Ag7}.{5Cu} alloy by selective laser melting},
	volume = {12},
	issn = {2045-2322},
	doi = {10.1038/s41598-022-08182-4},
	abstract = {High electrical and thermal conductive metals (HETCM) play a key role in smart electronics, green energy, modern communications and healthcare, however, typical HETCM (e.g., Ag, Au, Cu) usually have relatively low mechanical strength, hindering further applications. Selective laser melting (SLM) is a potentially transformative manufacturing technology that is expected to address the issue. Ag is the metal with the highest thermal conductivity, which induces microscale grain refinement, but also leads to high internal stresses by SLM. Here, we select Ag7.5Cu alloy as an example to demonstrate that multi-scale (micro/meso/macro) synergies can take advantage of high thermal conductivity and internal stresses to effectively strengthen Ag alloy. The mimicry of metal-hardened structures (e.g., large-angle boundary) is extended to the mesoscale by controlling the laser energy density and laser scanning strategy to manipulate the macroscale internal stress intensity and mesoscale internal stress direction, respectively, to form mesoscale large-angle "grains", resulting in multiple mutual perpendicular shear bands during fracture. The presented approach achieved a significant enhancement of yield strength (+ 145\%) and ductility (+ 28\%) without post-treatment. The results not only break the strength-ductility trade-off of conventional SLM alloys, but also demonstrate a multi-scale synergistic enhancement strategy that exploits high thermal conductivity and internal stresses.},
	number = {1},
	urldate = {2022-03-26},
	journal = {SCIENTIFIC REPORTS},
	author = {Xiong, Wei and Hao, Liang and Peijs, Ton and Yan, Chunze and Cheng, Kaka and Gong, Ping and Cui, Qian and Tang, Danna and Al Islam, Shamoon and Li, Yan},
	month = mar,
	year = {2022},
	note = {Hubei Gem \& Jewelry Engn Technol Res Ctr},
}

High electrical and thermal conductive metals (HETCM) play a key role in smart electronics, green energy, modern communications and healthcare, however, typical HETCM (e.g., Ag, Au, Cu) usually have relatively low mechanical strength, hindering further applications. Selective laser melting (SLM) is a potentially transformative manufacturing technology that is expected to address the issue. Ag is the metal with the highest thermal conductivity, which induces microscale grain refinement, but also leads to high internal stresses by SLM. Here, we select Ag7.5Cu alloy as an example to demonstrate that multi-scale (micro/meso/macro) synergies can take advantage of high thermal conductivity and internal stresses to effectively strengthen Ag alloy. The mimicry of metal-hardened structures (e.g., large-angle boundary) is extended to the mesoscale by controlling the laser energy density and laser scanning strategy to manipulate the macroscale internal stress intensity and mesoscale internal stress direction, respectively, to form mesoscale large-angle "grains", resulting in multiple mutual perpendicular shear bands during fracture. The presented approach achieved a significant enhancement of yield strength (+ 145%) and ductility (+ 28%) without post-treatment. The results not only break the strength-ductility trade-off of conventional SLM alloys, but also demonstrate a multi-scale synergistic enhancement strategy that exploits high thermal conductivity and internal stresses.

@article{hernandez_internal_2022,
	title = {Internal catalysis on the opposite side of the fence in non-isocyanate polyurethane covalent adaptable networks},
	volume = {168},
	issn = {0014-3057},
	doi = {10.1016/j.eurpolymj.2022.111100},
	abstract = {Within the context of covalent adaptable networks (CANs), we developed in this study a novel methodology to provide non-isocyanate polyurethane-based CANs with embedded tertiary amines that serve as internal catalytic moieties for the dynamic bond exchange processes. For the CAN design, we made use of multifunctional N-substituted 8-membered cyclic carbonates that are ring-opened by macromolecular amines. Several model re-actions were conducted to investigate transcarbamoylation bond exchange reactions at elevated temperatures and assess the influence of catalytic moieties within the urethane structure. This led us to design a non-isocyanate polyurethane CAN wherein the position of the internal catalyst was changed with respect to previous reported polyhydroxyurethane CANs, while maintaining close proximity to the dynamic carbamate linkages. It is shown that this positioning change of the tertiary amines still resulted in an internal catalytic effect on the dynamic exchange reactions, hence providing a better understanding of the role of tertiary amines as internal catalysts during the reprocessing of polyurethane networks. Moreover, the model experiments and thermomechanical investigations of the (re)processed networks allowed to identify the occurrence of competing reactions, involving a dissociative mechanism giving rise to urea formation, which significantly impacts the materials' reprocess-ability and properties.},
	urldate = {2022-04-27},
	journal = {EUROPEAN POLYMER JOURNAL},
	author = {Hernandez, Aitor and Houck, Hannes A. and Elizalde, Fermin and Guerre, Marc and Sardon, Haritz and Du Prez, Filip E.},
	month = apr,
	year = {2022},
}

Within the context of covalent adaptable networks (CANs), we developed in this study a novel methodology to provide non-isocyanate polyurethane-based CANs with embedded tertiary amines that serve as internal catalytic moieties for the dynamic bond exchange processes. For the CAN design, we made use of multifunctional N-substituted 8-membered cyclic carbonates that are ring-opened by macromolecular amines. Several model re-actions were conducted to investigate transcarbamoylation bond exchange reactions at elevated temperatures and assess the influence of catalytic moieties within the urethane structure. This led us to design a non-isocyanate polyurethane CAN wherein the position of the internal catalyst was changed with respect to previous reported polyhydroxyurethane CANs, while maintaining close proximity to the dynamic carbamate linkages. It is shown that this positioning change of the tertiary amines still resulted in an internal catalytic effect on the dynamic exchange reactions, hence providing a better understanding of the role of tertiary amines as internal catalysts during the reprocessing of polyurethane networks. Moreover, the model experiments and thermomechanical investigations of the (re)processed networks allowed to identify the occurrence of competing reactions, involving a dissociative mechanism giving rise to urea formation, which significantly impacts the materials' reprocess-ability and properties.

@article{mutlu_introduction_2022,
	title = {Introduction to the themed collection on synthetic methodologies for complex macromolecular structures in honour of {Prof}. {Yusuf} {Yagci}'s 70th birthday},
	volume = {13},
	issn = {1759-9954},
	doi = {10.1039/d2py90035a},
	abstract = {Hatice Mutlu, Filip Du Prez and Remzi Becer present the Polymer Chemistry themed collection on synthetic methodologies for complex macromolecular structures in honour of Prof. Yusuf Yagci's 70(th) birthday.},
	number = {11},
	urldate = {2022-03-16},
	journal = {POLYMER CHEMISTRY},
	author = {Mutlu, Hatice and Du Prez, Filip E. and Becer, C. Remzi},
	month = mar,
	year = {2022},
	pages = {1456--1457},
}

Hatice Mutlu, Filip Du Prez and Remzi Becer present the Polymer Chemistry themed collection on synthetic methodologies for complex macromolecular structures in honour of Prof. Yusuf Yagci's 70(th) birthday.

@article{hu_damping_2022,
	title = {Damping and {Electromechanical} {Behavior} of {Ionic}-{Modified} {Brominated} {Poly}(isobutylene-co-isoprene) {Rubber} {Containing} {Petroleum} {Resin} {C5}},
	volume = {61},
	issn = {0888-5885},
	doi = {10.1021/acs.iecr.1c04790},
	abstract = {To improve the damping properties of rubbers, organic tackifiers such as hydrocarbon resins, rosin esters, and polyterpenes are often incorporated to increase the intermolecular friction of the rubber, thus increasing the energy dissipation (damping) during dynamic loading. However, this is often at the expense of the cross-linking density and mechanical properties of the rubbers. Ionic cross-links introduce unique properties to rubbers, such as a combination of mechanical reinforcement and high extensibility, as well as self-healing and damping, thanks to the reversible ionic association. Hence creating an ionic network would be an interesting alternative to adding small molecular tackifiers to rubbers. The reversible ionic association inevitably causes structural instability over time (i.e., creep) or at elevated temperatures (ionic transition generally happens at 60-80 degrees C). To balance the dynamic damping, viscoelasticity, and mechanical stability of these materials, we prepared 1-vinyl imidazole modified brominated poly(isobutylene-co-isoprene) (BIIR) elastomers by solid-state rubber compounding and curing processes, and we investigated the effects of ionic networks and an aliphatic petroleum resin (C5) on the viscoelastic and electromechanical properties of the ionic-cross-linked elastomers. We found that the mechanical reinforcement can be achieved simultaneously with a broad effective damping temperature range through optimizing the ionic network and C5 concentrations. The polar ionic clusters also increased the dielectric permittivity while maintaining a low dielectric loss of the elastomers. The ionic modified BIIR exhibited actuation and energy harvesting properties similar to those of the commercial VHB-4910 elastomer under similar configurations, which provides alternative dielectric elastomers with reprocessability for vibration and energy harvesting applications.},
	number = {8},
	urldate = {2022-03-22},
	journal = {INDUSTRIAL \& ENGINEERING CHEMISTRY RESEARCH},
	author = {Hu, Xiao and Zhang, Runan and Wemyss, Alan M. and Du, Aihua and Bao, Xujin and Geng, Xueyu and Wan, Chaoying},
	month = mar,
	year = {2022},
	pages = {3063--3074},
}

To improve the damping properties of rubbers, organic tackifiers such as hydrocarbon resins, rosin esters, and polyterpenes are often incorporated to increase the intermolecular friction of the rubber, thus increasing the energy dissipation (damping) during dynamic loading. However, this is often at the expense of the cross-linking density and mechanical properties of the rubbers. Ionic cross-links introduce unique properties to rubbers, such as a combination of mechanical reinforcement and high extensibility, as well as self-healing and damping, thanks to the reversible ionic association. Hence creating an ionic network would be an interesting alternative to adding small molecular tackifiers to rubbers. The reversible ionic association inevitably causes structural instability over time (i.e., creep) or at elevated temperatures (ionic transition generally happens at 60-80 degrees C). To balance the dynamic damping, viscoelasticity, and mechanical stability of these materials, we prepared 1-vinyl imidazole modified brominated poly(isobutylene-co-isoprene) (BIIR) elastomers by solid-state rubber compounding and curing processes, and we investigated the effects of ionic networks and an aliphatic petroleum resin (C5) on the viscoelastic and electromechanical properties of the ionic-cross-linked elastomers. We found that the mechanical reinforcement can be achieved simultaneously with a broad effective damping temperature range through optimizing the ionic network and C5 concentrations. The polar ionic clusters also increased the dielectric permittivity while maintaining a low dielectric loss of the elastomers. The ionic modified BIIR exhibited actuation and energy harvesting properties similar to those of the commercial VHB-4910 elastomer under similar configurations, which provides alternative dielectric elastomers with reprocessability for vibration and energy harvesting applications.

@article{hancox_microphase_2022,
	title = {Microphase separation of highly amphiphilic, low {N} polymers by photoinduced copper-mediated polymerization, achieving sub-2 nm domains at half-pitch (vol 10, pg 6254, 2019)},
	volume = {13},
	issn = {1759-9954},
	doi = {10.1039/d2py90019j},
	number = {7},
	urldate = {2022-02-10},
	journal = {POLYMER CHEMISTRY},
	author = {Hancox, Ellis and Liarou, Evelina and Town, James S. and Jones, Glen R. and Layton, Sian A. and Huband, Steven and Greenall, Martin J. and Topham, Paul D. and Haddleton, David M.},
	month = feb,
	year = {2022},
	pages = {998--1000},
}

@article{booth_-unsaturated_2022,
	title = {ω-{Unsaturated} methacrylate macromonomers as reactive polymeric stabilizers in mini-emulsion polymerization},
	volume = {13},
	issn = {1759-9954},
	doi = {10.1039/d1py01664d},
	abstract = {Polymer latexes of poly(benzyl methacrylate) P(BzMA) were synthesized by mini-emulsion polymerization, using hexadecane as the hydrophobe and omega-unsaturated methacrylate-based macromonomers as a reactive stabilizer. The amphiphilic macromonomers were synthesized by catalytic chain transfer emulsion polymerization (CCTP) and subsequent chain extension via sulfur-free reversible addition-fragmentation chain transfer (SF-RAFT). Their critical micelle concentration (CMC) was determined by dynamic light scattering (DLS), and micelle size was measured using DLS and small angle X-ray scattering (SAXS). The surface activity of the stabilizers was measured by pendant drop tensiometry and compared to modelled behaviour. For the mini-emulsion polymerizations, macromonomer stabilizers were added at a range of concentrations, with respect to the dispersed phase. Using less than 5 wt\% stabilizer, SEM micrographs showed many of the particles were bowl-shaped. This morphology was studied in depth and we propose that monomer transport occurs between particles during polymerization towards the smaller particles as a direct result of compartmentalization. At concentrations of 5 wt\% and higher, bimodal droplet and particle distributions were observed by DLS and SEM. We propose shear-dependent depletion flocculation as the explanation. Lastly, the effectiveness of the reactive stabilizers was tested in terms of latex stability and molecular weight control. Resistance to coagulation during freeze-thaw cycles and prolonged dialysis were tested. Examination of P(BzMA) reaction kinetics and molecular weight indicated that the incorporation of macromonomer is gradual and less than quantitative at the end of the polymerization process, in agreement with the mechanistic understanding.},
	number = {10},
	urldate = {2022-02-15},
	journal = {POLYMER CHEMISTRY},
	author = {Booth, Joshua R. and Davies, Joshua D. and Bon, Stefan A. F.},
	month = mar,
	year = {2022},
	pages = {1335--1349},
}

Polymer latexes of poly(benzyl methacrylate) P(BzMA) were synthesized by mini-emulsion polymerization, using hexadecane as the hydrophobe and omega-unsaturated methacrylate-based macromonomers as a reactive stabilizer. The amphiphilic macromonomers were synthesized by catalytic chain transfer emulsion polymerization (CCTP) and subsequent chain extension via sulfur-free reversible addition-fragmentation chain transfer (SF-RAFT). Their critical micelle concentration (CMC) was determined by dynamic light scattering (DLS), and micelle size was measured using DLS and small angle X-ray scattering (SAXS). The surface activity of the stabilizers was measured by pendant drop tensiometry and compared to modelled behaviour. For the mini-emulsion polymerizations, macromonomer stabilizers were added at a range of concentrations, with respect to the dispersed phase. Using less than 5 wt% stabilizer, SEM micrographs showed many of the particles were bowl-shaped. This morphology was studied in depth and we propose that monomer transport occurs between particles during polymerization towards the smaller particles as a direct result of compartmentalization. At concentrations of 5 wt% and higher, bimodal droplet and particle distributions were observed by DLS and SEM. We propose shear-dependent depletion flocculation as the explanation. Lastly, the effectiveness of the reactive stabilizers was tested in terms of latex stability and molecular weight control. Resistance to coagulation during freeze-thaw cycles and prolonged dialysis were tested. Examination of P(BzMA) reaction kinetics and molecular weight indicated that the incorporation of macromonomer is gradual and less than quantitative at the end of the polymerization process, in agreement with the mechanistic understanding.

@article{yan_synthesis_2022,
	title = {Synthesis of a castor oil-based quaternary ammonium surfactant and its application in the modification of attapulgite},
	volume = {59},
	issn = {0932-3414},
	doi = {10.1515/tsd-2021-2345},
	abstract = {Castor oil-based quaternary ammonium surfactant (COQA) was synthesized by an ester-exchange reaction of refined castor oil (CO) (raw material) with N,N-dimethyl ethanol amine followed by quaternization with epichlorohydrin (ECH). Its surface activity and structural features were determined. The critical micelle concentration (CMC) of the surfactant at 25 degrees C was 1.79 x 10(-3) mol/L. The surface tension of an aqueous COQA solution at CMC was 38.19 mN/m. Subsequently, the synthesized COQA was used to modify attapulgite (ATP) by binding it to the surface of ATP. The change in the morphology of the modified-ATP (M-ATP) was attributed to the presence of the COQA bound to the surface of the rod-shaped crystals, although the crystal structure of the silicate did not change. Compared to ATP, the microstructure of the M-ATP was less rigid.},
	number = {1},
	urldate = {2022-01-30},
	journal = {TENSIDE SURFACTANTS DETERGENTS},
	author = {Yan, Xiuhua and Xu, Wei and Shao, Rong and Haddleton, David M.},
	month = jan,
	year = {2022},
	pages = {31--38},
}

Castor oil-based quaternary ammonium surfactant (COQA) was synthesized by an ester-exchange reaction of refined castor oil (CO) (raw material) with N,N-dimethyl ethanol amine followed by quaternization with epichlorohydrin (ECH). Its surface activity and structural features were determined. The critical micelle concentration (CMC) of the surfactant at 25 degrees C was 1.79 x 10(-3) mol/L. The surface tension of an aqueous COQA solution at CMC was 38.19 mN/m. Subsequently, the synthesized COQA was used to modify attapulgite (ATP) by binding it to the surface of ATP. The change in the morphology of the modified-ATP (M-ATP) was attributed to the presence of the COQA bound to the surface of the rod-shaped crystals, although the crystal structure of the silicate did not change. Compared to ATP, the microstructure of the M-ATP was less rigid.

@article{malina_metallohelix_2022,
	title = {Metallohelix vectors for efficient gene delivery via cationic {DNA} nanoparticles},
	volume = {50},
	issn = {0305-1048},
	doi = {10.1093/nar/gkab1277},
	abstract = {The design of efficient and safe gene delivery vehicles remains a major challenge for the application of gene therapy. Of the many reported gene delivery systems, metal complexes with high affinity for nucleic acids are emerging as an attractive option. We have discovered that certain metallohelices-optically pure, self-assembling triple-stranded arrays of fully encapsulated Fe-act as nonviral DNA delivery vectors capable of mediating efficient gene transfection. They induce formation of globular DNA particles which protect the DNA from degradation by various restriction endonucleases, are of suitable size and electrostatic potential for efficient membrane transport and are successfully processed by cells. The activity is highly structure-dependent-compact and shorter metallohelix enantiomers are far less efficient than less compact and longer enantiomers.},
	number = {2},
	urldate = {2022-03-21},
	journal = {NUCLEIC ACIDS RESEARCH},
	author = {Malina, Jaroslav and Kostrhunova, Hana and Novohradsky, Vojtech and Scott, Peter and Brabec, Viktor},
	month = jan,
	year = {2022},
	pages = {674--683},
}

The design of efficient and safe gene delivery vehicles remains a major challenge for the application of gene therapy. Of the many reported gene delivery systems, metal complexes with high affinity for nucleic acids are emerging as an attractive option. We have discovered that certain metallohelices-optically pure, self-assembling triple-stranded arrays of fully encapsulated Fe-act as nonviral DNA delivery vectors capable of mediating efficient gene transfection. They induce formation of globular DNA particles which protect the DNA from degradation by various restriction endonucleases, are of suitable size and electrostatic potential for efficient membrane transport and are successfully processed by cells. The activity is highly structure-dependent-compact and shorter metallohelix enantiomers are far less efficient than less compact and longer enantiomers.

@article{limas_impact_2022,
	title = {The {Impact} of {Research} {Culture} on {Mental} {Health} \& {Diversity} in {STEM}},
	volume = {28},
	issn = {0947-6539},
	doi = {10.1002/chem.202102957},
	abstract = {The onset of COVID-19, coupled with the finer lens placed on systemic racial disparities within our society, has resulted in increased discussions around mental health. Despite this, mental health struggles in research are still often viewed as individual weaknesses and not the result of a larger dysfunctional research culture. Mental health interventions in the science, technology, engineering, and mathematics (STEM) academic community often focus on what individuals can do to improve their mental health instead of focusing on improving the research environment. In this paper, we present four aspects of research that may heavily impact mental health based on our experiences as research scientists: bullying and harassment; precarity of contracts; diversity, inclusion, and accessibility; and the competitive research landscape. Based on these aspects, we propose systemic changes that institutions must adopt to ensure their research culture is supportive and allows everyone to thrive.},
	number = {9},
	urldate = {2022-01-29},
	journal = {CHEMISTRY-A EUROPEAN JOURNAL},
	author = {Limas, Juanita C. and Corcoran, Linda C. and Baker, Alexander N. and Cartaya, Ana E. and Ayres, Zoe J.},
	month = feb,
	year = {2022},
}

The onset of COVID-19, coupled with the finer lens placed on systemic racial disparities within our society, has resulted in increased discussions around mental health. Despite this, mental health struggles in research are still often viewed as individual weaknesses and not the result of a larger dysfunctional research culture. Mental health interventions in the science, technology, engineering, and mathematics (STEM) academic community often focus on what individuals can do to improve their mental health instead of focusing on improving the research environment. In this paper, we present four aspects of research that may heavily impact mental health based on our experiences as research scientists: bullying and harassment; precarity of contracts; diversity, inclusion, and accessibility; and the competitive research landscape. Based on these aspects, we propose systemic changes that institutions must adopt to ensure their research culture is supportive and allows everyone to thrive.

@article{tian_peano-hydraulically_2022,
	title = {Peano-{Hydraulically} {Amplified} {Self}-{Healing} {Electrostatic} {Actuators} {Based} on a {Novel} {Bilayer} {Polymer} {Shell} for {Enhanced} {Strain}, {Load}, and {Rotary} {Motion}},
	volume = {4},
	issn = {2640-4567},
	doi = {10.1002/aisy.202100239},
	abstract = {The hydraulically amplified self-healing electrostatic actuator is an emerging driving component for soft robotics, which is composed of a flexible dielectric polymer shell that is partially covered by conductive electrodes and filled with a liquid dielectric. However, the low permittivity and dielectric strength of the polymer shell remain a challenge that limits the actuator performance. Herein, a Peano-hydraulically amplified self-healing electrostatic actuator is constructed by innovatively integrating a bilayer polymer shell for combined favorable properties of high dielectric strength, dielectric permittivity, and elastic modulus. Compared with a traditional single-layer shell actuator, the new bilayer actuator architecture generates an increased strain (164\%) at 5 kV and improves load-bearing capability (620 mN) at 6 kV, thereby providing a significantly enhanced actuation performance. The new actuator is further applied in driving a ratchet system, which converts the reciprocating motion of the actuator into a rotating motion and a flexible output torque, in order to protect the rotating components from impact. The high strain and load characteristics of the bilayer configuration and the easy-to-deform characteristics of the new actuator design make it an attractive approach to fabricate complex geometries and achieve a variety of motion modes in soft systems.},
	number = {5},
	urldate = {2022-02-02},
	journal = {ADVANCED INTELLIGENT SYSTEMS},
	author = {Tian, Ye and Liu, Junjie and Wu, Wenjie and Liang, Xianrong and Pan, Min and Bowen, Chris and Jiang, Yong and Sun, Jingyao and McNally, Tony and Wu, Daming and Huang, Yao and Wan, Chaoying},
	month = may,
	year = {2022},
}

The hydraulically amplified self-healing electrostatic actuator is an emerging driving component for soft robotics, which is composed of a flexible dielectric polymer shell that is partially covered by conductive electrodes and filled with a liquid dielectric. However, the low permittivity and dielectric strength of the polymer shell remain a challenge that limits the actuator performance. Herein, a Peano-hydraulically amplified self-healing electrostatic actuator is constructed by innovatively integrating a bilayer polymer shell for combined favorable properties of high dielectric strength, dielectric permittivity, and elastic modulus. Compared with a traditional single-layer shell actuator, the new bilayer actuator architecture generates an increased strain (164%) at 5 kV and improves load-bearing capability (620 mN) at 6 kV, thereby providing a significantly enhanced actuation performance. The new actuator is further applied in driving a ratchet system, which converts the reciprocating motion of the actuator into a rotating motion and a flexible output torque, in order to protect the rotating components from impact. The high strain and load characteristics of the bilayer configuration and the easy-to-deform characteristics of the new actuator design make it an attractive approach to fabricate complex geometries and achieve a variety of motion modes in soft systems.

@article{yan_stretchable_2022,
	title = {Stretchable and {Durable} {Inverse} {Vulcanized} {Polymers} with {Chemical} and {Thermal} {Recycling}},
	volume = {34},
	issn = {0897-4756},
	doi = {10.1021/acs.chemmater.1c03662},
	abstract = {Inverse vulcanized polymer materials have received considerable attention as a way to use sulfur, an industrial byproduct, as a starting material for synthesis. The resulting highsulfur content polymers have also been investigated because their properties give rise to promising applications such as infrared imaging, energy storage, and heavy metal capture due to their unique structure. However, synthesis of a flexible sulfur polymer network which shows good mechanical properties combining high strength, high elongation, and high toughness is still a significant challenge. Moreover, further exploration of the properties of sulfur polymers to better understand the relationship between the polymers' structure with their performance is still needed. Here, a range of cross-linked sulfur polymers with high tensile elongation and toughness and without losing high strength were successfully synthesized. The obtained cross-linked sulfur polymers show high solvent tolerance in most organic solvents but are demonstrated to be chemically de-cross-linked in polar solvents dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone and can be re-cross-linked after removing the solvent due to the high sulfur ranks present in the polymer network. Despite the significantly improved mechanical properties, highly efficient thermal recycling performance typical of inverse vulcanized polymers was retained. Flexibility and durability, combined with chemical and thermal recycling, could open a new door for wider applications of inverse vulcanized polymers.},
	number = {3},
	urldate = {2022-01-29},
	journal = {CHEMISTRY OF MATERIALS},
	author = {Yan, Peiyao and Zhao, Wei and Tonkin, Samuel J. and Chalker, Justin M. and Schiller, Tara L. and Hasell, Tom},
	month = feb,
	year = {2022},
	pages = {1167--1178},
}

Inverse vulcanized polymer materials have received considerable attention as a way to use sulfur, an industrial byproduct, as a starting material for synthesis. The resulting highsulfur content polymers have also been investigated because their properties give rise to promising applications such as infrared imaging, energy storage, and heavy metal capture due to their unique structure. However, synthesis of a flexible sulfur polymer network which shows good mechanical properties combining high strength, high elongation, and high toughness is still a significant challenge. Moreover, further exploration of the properties of sulfur polymers to better understand the relationship between the polymers' structure with their performance is still needed. Here, a range of cross-linked sulfur polymers with high tensile elongation and toughness and without losing high strength were successfully synthesized. The obtained cross-linked sulfur polymers show high solvent tolerance in most organic solvents but are demonstrated to be chemically de-cross-linked in polar solvents dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone and can be re-cross-linked after removing the solvent due to the high sulfur ranks present in the polymer network. Despite the significantly improved mechanical properties, highly efficient thermal recycling performance typical of inverse vulcanized polymers was retained. Flexibility and durability, combined with chemical and thermal recycling, could open a new door for wider applications of inverse vulcanized polymers.

@article{samantaray_electron_2022,
	title = {Electron {Beam}-{Mediated} {Cross}-{Linking} of {Blown} {Film}-{Extruded} {Biodegradable} {PGA}/{PBAT} {Blends} toward {High} {Toughness} and {Low} {Oxygen} {Permeation}},
	volume = {10},
	issn = {2168-0485},
	doi = {10.1021/acssuschemeng.1c07376},
	abstract = {Due to its high crystallinity, tailored compostability, and superior barrier performance, poly(glycolic acid) (PGA) has great potential as a substitute for current single-use plastics used in food packaging applications and with a lower carbon footprint. However, its susceptibility to hydrolysis and mechanical brittleness hinders its direct suitability in packaging. In this work, we circumvent this limitation by first blending PGA with a thermoplastic polyester, poly(butylene adipate-co-terephthalate) (PBAT), and a glycidyl cross-linker via industrial-scale twin-screw extrusion and then converting to a film by blown film extrusion. The surface of the films was then chemically cross-linked using electron beam treatment (EBT) to impart excellent barrier properties. Here, the electron beam plays a dual role. Firstly, it cross-links the surface of the films and improves the oxygen and moisture barrier performance, both improved due to blending with PBAT. Second, it does not compromise the toughness or extension at break of the polymer blend, both desirable for flexible packaging applications. A dosage of 250 kGy EBT resulted in the film having an oxygen barrier permeation of 57.0-59.8 cm(3) mm m(-2) 24 h(-1) atm(-1) and a water vapor permeation of 26.8 g m(-2) 24 h(-1) while maintaining a high toughness of 75 MPa. At dosages higher than 300 kGy, inhomogeneities formed on the surface of the films and some degradation in the mechanical properties of the films is observed. This work highlights the possibility of deriving superior biopolymer barrier performance while retaining the mechanical properties required for food packaging using a combination of blending and electron beam treatment, both scalable processes.},
	number = {3},
	urldate = {2022-01-22},
	journal = {ACS SUSTAINABLE CHEMISTRY \& ENGINEERING},
	author = {Samantaray, Paresh Kumar and Ellingford, Christopher and Farris, Stefano and O'Sullivan, Donal and Tan, Bowen and Sun, Zhaoyang and McNally, Tony and Wan, Chaoying},
	month = jan,
	year = {2022},
	note = {Sherkin Technol UK Ltd
PJIM Polymer Sci Co Ltd},
	pages = {1267--1276},
}

Due to its high crystallinity, tailored compostability, and superior barrier performance, poly(glycolic acid) (PGA) has great potential as a substitute for current single-use plastics used in food packaging applications and with a lower carbon footprint. However, its susceptibility to hydrolysis and mechanical brittleness hinders its direct suitability in packaging. In this work, we circumvent this limitation by first blending PGA with a thermoplastic polyester, poly(butylene adipate-co-terephthalate) (PBAT), and a glycidyl cross-linker via industrial-scale twin-screw extrusion and then converting to a film by blown film extrusion. The surface of the films was then chemically cross-linked using electron beam treatment (EBT) to impart excellent barrier properties. Here, the electron beam plays a dual role. Firstly, it cross-links the surface of the films and improves the oxygen and moisture barrier performance, both improved due to blending with PBAT. Second, it does not compromise the toughness or extension at break of the polymer blend, both desirable for flexible packaging applications. A dosage of 250 kGy EBT resulted in the film having an oxygen barrier permeation of 57.0-59.8 cm(3) mm m(-2) 24 h(-1) atm(-1) and a water vapor permeation of 26.8 g m(-2) 24 h(-1) while maintaining a high toughness of 75 MPa. At dosages higher than 300 kGy, inhomogeneities formed on the surface of the films and some degradation in the mechanical properties of the films is observed. This work highlights the possibility of deriving superior biopolymer barrier performance while retaining the mechanical properties required for food packaging using a combination of blending and electron beam treatment, both scalable processes.

@article{mackinnon_tuneable_2022,
	title = {Tuneable {N}-{Substituted} {Polyamides} with {High} {Biomass} {Content} via {Ugi} 4 {Component} {Polymerization}},
	volume = {223},
	issn = {1022-1352},
	doi = {10.1002/macp.202100408},
	abstract = {Ugi 4-component reaction (Ugi 4CR) is an efficient tool which benefits from high atom efficiency, compatibility with green solvents such as methanol, simple purification, and a water side-product. By using two bifunctional starting materials for Ugi 4CR, N-substituted polyamides can be prepared via a step-growth process. As polyamides play important roles in applications including films, and adhesives, the preparation of N-substituted functional polyamides from largely sustainable monomers is investigated. Herein, the combination of renewable diamine, diacid, and aldehydes with commercially available isocyanides yield polyamides with tuneable side chain functionalities and approximate to 80\% biomass content. Relatively high yields (up to 96\%) are recorded for polymers of moderate molecular weights (M-w up to 8100 g mol(-1)). The prepared polyamides possess backbones which exhibit excellent thermal stability (T-d(eg) = 440 +/- 10 degrees C), while functional side chains result in additional lower-temperature degradations (215-285 degrees C). Side-group variation enables shifting of the glass transition temperature (T-g) between 9 and 38 degrees C and causes variation in hydrophobicity resulting in water contact angles ranging from 47 (o) to 105 (o). This work presents a reliable approach to prepare sustainable polymers with diverse side chain functionalities in a short reaction time and without need for catalysts or complicated purifications.},
	number = {13},
	urldate = {2022-01-12},
	journal = {MACROMOLECULAR CHEMISTRY AND PHYSICS},
	author = {MacKinnon, Daniel and Zhao, Tieshuai and Becer, C. Remzi},
	month = jul,
	year = {2022},
}

Ugi 4-component reaction (Ugi 4CR) is an efficient tool which benefits from high atom efficiency, compatibility with green solvents such as methanol, simple purification, and a water side-product. By using two bifunctional starting materials for Ugi 4CR, N-substituted polyamides can be prepared via a step-growth process. As polyamides play important roles in applications including films, and adhesives, the preparation of N-substituted functional polyamides from largely sustainable monomers is investigated. Herein, the combination of renewable diamine, diacid, and aldehydes with commercially available isocyanides yield polyamides with tuneable side chain functionalities and approximate to 80% biomass content. Relatively high yields (up to 96%) are recorded for polymers of moderate molecular weights (M-w up to 8100 g mol(-1)). The prepared polyamides possess backbones which exhibit excellent thermal stability (T-d(eg) = 440 +/- 10 degrees C), while functional side chains result in additional lower-temperature degradations (215-285 degrees C). Side-group variation enables shifting of the glass transition temperature (T-g) between 9 and 38 degrees C and causes variation in hydrophobicity resulting in water contact angles ranging from 47 (o) to 105 (o). This work presents a reliable approach to prepare sustainable polymers with diverse side chain functionalities in a short reaction time and without need for catalysts or complicated purifications.

@article{zhao_hierarchy_2022,
	title = {Hierarchy of {Complex} {Glycomacromolecules}: {From} {Controlled} {Topologies} to {Biomedical} {Applications}},
	volume = {23},
	issn = {1525-7797},
	doi = {10.1021/acs.biomac.1c01294},
	abstract = {Carbohydrates bearing a distinct complexity use a special code (Glycocode) to communicate with carbohydrate-binding proteins at a high precision to manipulate biological activities in complex biological environments. The level of complexity in carbohydrate-containing macromolecules controls the amount and specificity of information that can be stored in biomacromolecules. Therefore, a better understanding of the glycocode is crucial to open new areas of biomedical applications by controlling or manipulating the interaction between immune cells and pathogens in terms of trafficking and signaling, which would become a powerful tool to prevent infectious diseases. Even though a certain level of progress has been achieved over the past decade, synthetic glycomacromolecules are still lagging far behind naturally existing glycans in terms of complexity and precision because of insufficient and inefficient synthetic techniques. Currently, specific targeting at a cellular level using synthetic glycomacromolecules is still challenging. It is obvious that multidisciplinary collaborations are essential between different specialized disciplines to enhance the carbohydrate receptor-targeting paradigm for new biomedical applications. In this Perspective, recent developments in the synthesis of sophisticated glycomacromolecules are highlighted, and their biological and biomedical applications are also discussed in detail.},
	number = {3},
	urldate = {2022-01-17},
	journal = {BIOMACROMOLECULES},
	author = {Zhao, Tieshuai and Terracciano, Roberto and Becker, Jonas and Monaco, Alessandra and Yilmaz, Gokhan and Becer, C. Remzi},
	month = mar,
	year = {2022},
	pages = {543--575},
}

Carbohydrates bearing a distinct complexity use a special code (Glycocode) to communicate with carbohydrate-binding proteins at a high precision to manipulate biological activities in complex biological environments. The level of complexity in carbohydrate-containing macromolecules controls the amount and specificity of information that can be stored in biomacromolecules. Therefore, a better understanding of the glycocode is crucial to open new areas of biomedical applications by controlling or manipulating the interaction between immune cells and pathogens in terms of trafficking and signaling, which would become a powerful tool to prevent infectious diseases. Even though a certain level of progress has been achieved over the past decade, synthetic glycomacromolecules are still lagging far behind naturally existing glycans in terms of complexity and precision because of insufficient and inefficient synthetic techniques. Currently, specific targeting at a cellular level using synthetic glycomacromolecules is still challenging. It is obvious that multidisciplinary collaborations are essential between different specialized disciplines to enhance the carbohydrate receptor-targeting paradigm for new biomedical applications. In this Perspective, recent developments in the synthesis of sophisticated glycomacromolecules are highlighted, and their biological and biomedical applications are also discussed in detail.

@article{hayes_multiarm_2022,
	title = {Multiarm {Core} {Cross}-{Linked} {Star}-{Shaped} {Poly}(2-oxazoline)s {Using} a {Bisfunctional} 2-{Oxazoline} {Monomer}},
	volume = {55},
	issn = {0024-9297},
	doi = {10.1021/acs.macromol.1c02245},
	abstract = {Poly(2-oxazoline)s are an attractive class of polymers that have a potential for biomedical applications. However, synthetic approaches for the preparation of 2-oxazoline-based star-shaped polymers are quite limited and are usually based on either end-capping of a living chain with a multifunctional terminator or utilizing a multifunctional initiator. Up until now, the use of a bis-oxazoline monomer as a cross-linking agent for the synthesis of core cross-linked star shaped poly(2-oxazoline) polymers has not been reported. Herein, we have developed a new bis-oxazoline cross-linker via a fast and efficient thiol click reaction with no catalyst and purification required. Moreover, we have utilized this cross-linker to prepare well-controlled core cross-linked star polymers with poly(2-oxazoline) arms in a straightforward manner. Synthesized star-shaped polymers were characterized in detail using an advanced gel permeation chromatography technique and were found to have a range of arms from {\textless}10 to over 1000. Furthermore, the effect of the reaction concentration, amount of cross-linker, and arm length on star formation were analyzed and the stars' potential for dihydroxyanthroquinone encapsulation was explored.},
	number = {1},
	urldate = {2022-01-09},
	journal = {MACROMOLECULES},
	author = {Hayes, Graham and Drain, Ben and Becer, C. Remzi},
	month = jan,
	year = {2022},
	pages = {146--155},
}

Poly(2-oxazoline)s are an attractive class of polymers that have a potential for biomedical applications. However, synthetic approaches for the preparation of 2-oxazoline-based star-shaped polymers are quite limited and are usually based on either end-capping of a living chain with a multifunctional terminator or utilizing a multifunctional initiator. Up until now, the use of a bis-oxazoline monomer as a cross-linking agent for the synthesis of core cross-linked star shaped poly(2-oxazoline) polymers has not been reported. Herein, we have developed a new bis-oxazoline cross-linker via a fast and efficient thiol click reaction with no catalyst and purification required. Moreover, we have utilized this cross-linker to prepare well-controlled core cross-linked star polymers with poly(2-oxazoline) arms in a straightforward manner. Synthesized star-shaped polymers were characterized in detail using an advanced gel permeation chromatography technique and were found to have a range of arms from \textless10 to over 1000. Furthermore, the effect of the reaction concentration, amount of cross-linker, and arm length on star formation were analyzed and the stars' potential for dihydroxyanthroquinone encapsulation was explored.

@article{dhara_development_2022,
	title = {Development of a novel testing methodology for in-situ microstructural characterisation during continuous strain path change},
	volume = {183},
	issn = {1044-5803},
	doi = {10.1016/j.matchar.2021.111610},
	abstract = {Strain path transition is a common phenomenon during continuous stamping operations of sheet metal and can potentially alter the forming limit of the material. Enabling strain path change in a single experiment is a key challenge faced by several researchers. To understand the effect of continuous strain path change on material forming limits, detailed material characterisation is needed where the material is deformed while the strain path of the material is changed continuously. In this work, a test method was developed, which consisted of a novel mechanical rig and specimen design. The mechanism allowed DP600 steel and AA5182-O aluminium samples to change strain paths continuously without unloading the specimen. Digital image correlation measurements of the strain evolution of the samples during tests showed that the technique was able to alter the strain path of the sample from uniaxial to biaxial strain path. In particular, the measurements showed that the transition from uniaxial to biaxial strain paths was sharper in DP600 than AA5182-O. The test was repeated in a scanning electron microscope (SEM) chamber to observe the behaviour of the microstructure during the strain path transition. The microstructural strain evolution showed rotation of strain bands while the evolution of electron back scattered diffraction (EBSD) maps conveyed grain rotation during continuous strain path change in both the materials. The strain path transition controlled the rotation of grains with preferred crystallographic orientations.},
	urldate = {2022-01-07},
	journal = {MATERIALS CHARACTERIZATION},
	author = {Dhara, Sisir and Taylor, Scott and Figiel, Lukasz and Hughes, Darren and Hazra, Sumit},
	month = jan,
	year = {2022},
}

Strain path transition is a common phenomenon during continuous stamping operations of sheet metal and can potentially alter the forming limit of the material. Enabling strain path change in a single experiment is a key challenge faced by several researchers. To understand the effect of continuous strain path change on material forming limits, detailed material characterisation is needed where the material is deformed while the strain path of the material is changed continuously. In this work, a test method was developed, which consisted of a novel mechanical rig and specimen design. The mechanism allowed DP600 steel and AA5182-O aluminium samples to change strain paths continuously without unloading the specimen. Digital image correlation measurements of the strain evolution of the samples during tests showed that the technique was able to alter the strain path of the sample from uniaxial to biaxial strain path. In particular, the measurements showed that the transition from uniaxial to biaxial strain paths was sharper in DP600 than AA5182-O. The test was repeated in a scanning electron microscope (SEM) chamber to observe the behaviour of the microstructure during the strain path transition. The microstructural strain evolution showed rotation of strain bands while the evolution of electron back scattered diffraction (EBSD) maps conveyed grain rotation during continuous strain path change in both the materials. The strain path transition controlled the rotation of grains with preferred crystallographic orientations.

@article{baker_lateral_2022,
	title = {Lateral {Flow} {Glyco}-{Assays} for the {Rapid} and {Low}-{Cost} {Detection} of {Lectins}-{Polymeric} {Linkers} and {Particle} {Engineering} {Are} {Essential} for {Selectivity} and {Performance}},
	volume = {11},
	issn = {2192-2640},
	doi = {10.1002/adhm.202101784},
	abstract = {Lateral flow immuno-assays, such as the home pregnancy test, are rapid point-of-care diagnostics that use antibody-coated nanoparticles to bind antigens/analytes (e.g., viruses, toxins or hormones). Ease of use, no need for centralized infrastructure and low-cost, makes these devices appealing for rapid disease identification, especially in low-resource environments. Here glycosylated polymer-coated nanoparticles are demonstrated for the sensitive, label-free detection of lectins in lateral flow and flow-through. The systems introduced here use glycans, not antibodies, to provide recognition: a "lateral flow glyco-assay," providing unique biosensing opportunities. Glycans are installed onto polymer termini and immobilized onto gold nanoparticles, providing colloidal stability but crucially also introducing assay tunability and selectivity. Using soybean agglutinin and Ricinus communis agglutinin I (RCA(120)) as model analytes, the impact of polymer chain length and nanoparticle core size are evaluated, with chain length found to have a significant effect on signal generation-highlighting the need to control the macromolecular architecture to tune response. With optimized systems, lectins are detectable at subnanomolar concentrations, comparable to antibody-based systems. Complete lateral flow devices are also assembled to show how these devices can be deployed in the "real world." This work shows that glycan-binding can be a valuable tool in rapid diagnostics.},
	number = {4},
	urldate = {2021-11-21},
	journal = {ADVANCED HEALTHCARE MATERIALS},
	author = {Baker, Alexander N. and Muguruza, Asier R. and Richards, Sarah-Jane and Georgiou, Panagiotis G. and Goetz, Stephen and Walker, Marc and Dedola, Simone and Field, Robert A. and Gibson, I, Matthew},
	month = feb,
	year = {2022},
	note = {Iceni Diagnost Ltd},
}

Lateral flow immuno-assays, such as the home pregnancy test, are rapid point-of-care diagnostics that use antibody-coated nanoparticles to bind antigens/analytes (e.g., viruses, toxins or hormones). Ease of use, no need for centralized infrastructure and low-cost, makes these devices appealing for rapid disease identification, especially in low-resource environments. Here glycosylated polymer-coated nanoparticles are demonstrated for the sensitive, label-free detection of lectins in lateral flow and flow-through. The systems introduced here use glycans, not antibodies, to provide recognition: a "lateral flow glyco-assay," providing unique biosensing opportunities. Glycans are installed onto polymer termini and immobilized onto gold nanoparticles, providing colloidal stability but crucially also introducing assay tunability and selectivity. Using soybean agglutinin and Ricinus communis agglutinin I (RCA(120)) as model analytes, the impact of polymer chain length and nanoparticle core size are evaluated, with chain length found to have a significant effect on signal generation-highlighting the need to control the macromolecular architecture to tune response. With optimized systems, lectins are detectable at subnanomolar concentrations, comparable to antibody-based systems. Complete lateral flow devices are also assembled to show how these devices can be deployed in the "real world." This work shows that glycan-binding can be a valuable tool in rapid diagnostics.

@article{poluektov_cut_2022,
	title = {A cut finite-element method for fracture and contact problems in large-deformation solid mechanics},
	volume = {388},
	issn = {0045-7825},
	doi = {10.1016/j.cma.2021.114234},
	abstract = {Cut finite-element methods (CutFEMs) belong to the class of methods that allow boundaries/interfaces to cut through the elements, which avoids any meshing/remeshing problems. This is highly convenient from a practical point of view, especially when non-stationary interfaces are considered, e.g. phase boundaries in solids, as the interfaces can move independently of the mesh. There are many research directions related to CutFEM, one of which focuses on the equations of solid mechanics. Initially, the developments centred on linear elasticity and, in the previous publication by the authors, the method has been extended to large deformations and arbitrary constitutive relations, while the focus has been on phase boundaries in solids and on localised chemical reaction fronts in coupled mechanics-diffusion-reaction systems. In this paper, the method is further extended to more complex physics of the interfaces - fracture, i.e. separation of the interface into two surfaces in the current configuration, and contact between the separated surfaces. Several cases are considered - fracture with linear and non-linear traction separation, contact without and with adhesion. Each incremental generalisation of the approach contains a prior approach as a particular case, e.g. the phase boundary problem is a particular case of the fracture problem. The contact problem is treated in an unbiased way - the weak form is symmetric with respect to the choice of the contact surfaces for the integration. The weak forms are derived from the total energy functional. The proposed method has been tested computationally for the case of linear elements and passed the so-called patch tests and the convergence rate tests demonstrating the asymptotically optimal rates. (C) 2021 The Author(s). Published by Elsevier B.V.},
	urldate = {2021-11-28},
	journal = {COMPUTER METHODS IN APPLIED MECHANICS AND ENGINEERING},
	author = {Poluektov, Michael and Figiel, Lukasz},
	month = jan,
	year = {2022},
}

Cut finite-element methods (CutFEMs) belong to the class of methods that allow boundaries/interfaces to cut through the elements, which avoids any meshing/remeshing problems. This is highly convenient from a practical point of view, especially when non-stationary interfaces are considered, e.g. phase boundaries in solids, as the interfaces can move independently of the mesh. There are many research directions related to CutFEM, one of which focuses on the equations of solid mechanics. Initially, the developments centred on linear elasticity and, in the previous publication by the authors, the method has been extended to large deformations and arbitrary constitutive relations, while the focus has been on phase boundaries in solids and on localised chemical reaction fronts in coupled mechanics-diffusion-reaction systems. In this paper, the method is further extended to more complex physics of the interfaces - fracture, i.e. separation of the interface into two surfaces in the current configuration, and contact between the separated surfaces. Several cases are considered - fracture with linear and non-linear traction separation, contact without and with adhesion. Each incremental generalisation of the approach contains a prior approach as a particular case, e.g. the phase boundary problem is a particular case of the fracture problem. The contact problem is treated in an unbiased way - the weak form is symmetric with respect to the choice of the contact surfaces for the integration. The weak forms are derived from the total energy functional. The proposed method has been tested computationally for the case of linear elements and passed the so-called patch tests and the convergence rate tests demonstrating the asymptotically optimal rates. (C) 2021 The Author(s). Published by Elsevier B.V.

@article{rovera_enzymatic_2022,
	title = {Enzymatic hydrolysis of bacterial cellulose in the presence of a non-catalytic cerato-platanin protein},
	volume = {139},
	issn = {0021-8995},
	doi = {10.1002/app.51886},
	abstract = {In this work, the effect of an expansin-like cerato-platanin (CP) protein as a pre-treatment for the enzymatic hydrolysis of bacterial cellulose (BC) is investigated. To this scope, cellulases from Trichoderma reesei are used as hydrolyzing agent using different enzyme/BC formulations. Turbidity experiments reveal that for the higher enzyme concentrations (formulations 0.5:1 and 1:1) the enzymatic hydrolysis of BC show similar hydrolysis kinetics and is not dependent of the CP. However, at higher BC concentrations (formulations 0.25:1 and 0.33:1), the hydrolysis of BC is hindered by the non-catalytic protein, as confirmed by the lower content of cellobiose and glucose in the presence of CP. Light scattering experiments show that the addition of CP led to an increase of the BC particle size from (445-630 nm) to (890-1.26 mu m) for the formulation 1:1, which is also corroborated by atomic force microscopy and transmission electron microscopy analyses. These results suggest that CP did not positively affect the hydrolysis of BC, in contrast to what was previously observed for plant-derived cellulose. This work for the first time investigates the anomalous behavior of cerato platanin family members with regard to its loosening activity on the structure of bacterial cellulose.},
	number = {14},
	urldate = {2021-11-13},
	journal = {JOURNAL OF APPLIED POLYMER SCIENCE},
	author = {Rovera, Cesare and Luti, Simone and Pazzagli, Luigia and Heeley, Ellen L. and Wan, Chaoying and Romano, Diego and Farris, Stefano},
	month = apr,
	year = {2022},
}

In this work, the effect of an expansin-like cerato-platanin (CP) protein as a pre-treatment for the enzymatic hydrolysis of bacterial cellulose (BC) is investigated. To this scope, cellulases from Trichoderma reesei are used as hydrolyzing agent using different enzyme/BC formulations. Turbidity experiments reveal that for the higher enzyme concentrations (formulations 0.5:1 and 1:1) the enzymatic hydrolysis of BC show similar hydrolysis kinetics and is not dependent of the CP. However, at higher BC concentrations (formulations 0.25:1 and 0.33:1), the hydrolysis of BC is hindered by the non-catalytic protein, as confirmed by the lower content of cellobiose and glucose in the presence of CP. Light scattering experiments show that the addition of CP led to an increase of the BC particle size from (445-630 nm) to (890-1.26 mu m) for the formulation 1:1, which is also corroborated by atomic force microscopy and transmission electron microscopy analyses. These results suggest that CP did not positively affect the hydrolysis of BC, in contrast to what was previously observed for plant-derived cellulose. This work for the first time investigates the anomalous behavior of cerato platanin family members with regard to its loosening activity on the structure of bacterial cellulose.

@article{ellingford_reactive_2022,
	title = {Reactive extrusion of biodegradable {PGA}/{PBAT} blends to enhance flexibility and gas barrier properties},
	volume = {139},
	issn = {0021-8995},
	doi = {10.1002/app.51617},
	abstract = {Among commercial biodegradable polyesters, poly(glycolic acid) (PGA) has been rarely investigated for packaging applications, despite its unique advantages such as 100\% compostability, high degree of crystallinity, high thermal stability and high gas barrier properties. The application of PGA has been limited by its mechanical brittleness, moisture sensitivity, and high melting temperature (similar to 240 degrees C), restricting its processing and applications for film packaging. In this study, PGA was modified by blending with poly (butylene adipate-co-terephthalate) (PBAT) via melt-extrusion. A commercial terpolymer of ethylene, acrylic ester and glycidyl methacrylate (EMA-GMA) was selected for compatibilization. The phase morphology, rheology, thermal, mechanical and gas barrier properties of the blends were investigated. With addition of 20 wt. \% EMA-GMA, the elongation of PGA/PBAT (50/50 wt. \%) blends was improved from 10.7\% to 145\%, the oxygen permeability was reduced from 125 to 103 (cm(3) mm)/(m(2) 24 h atm), and the water vapor barrier performance was improved by similar to 47\%. The enhancement in ductility, oxygen and water vapor barrier properties of the flexible blends were ascribed to the interfacial bonding between PBAT and PGA enabled by EMA-GMA. The compatibilized PGA/PBAT blends with high thermal stability up to 300 degrees C are preferable for high temperature or hot food packaging.},
	number = {6},
	urldate = {2021-09-12},
	journal = {JOURNAL OF APPLIED POLYMER SCIENCE},
	author = {Ellingford, Christopher and Samantaray, Paresh Kumar and Farris, Stefano and McNally, Tony and Tan, Bowen and Sun, Zhaoyang and Huang, Weijie and Ji, Yang and Wan, Chaoying},
	month = feb,
	year = {2022},
	note = {PJIM Polymer Sci Co Ltd},
}

Among commercial biodegradable polyesters, poly(glycolic acid) (PGA) has been rarely investigated for packaging applications, despite its unique advantages such as 100% compostability, high degree of crystallinity, high thermal stability and high gas barrier properties. The application of PGA has been limited by its mechanical brittleness, moisture sensitivity, and high melting temperature (similar to 240 degrees C), restricting its processing and applications for film packaging. In this study, PGA was modified by blending with poly (butylene adipate-co-terephthalate) (PBAT) via melt-extrusion. A commercial terpolymer of ethylene, acrylic ester and glycidyl methacrylate (EMA-GMA) was selected for compatibilization. The phase morphology, rheology, thermal, mechanical and gas barrier properties of the blends were investigated. With addition of 20 wt. % EMA-GMA, the elongation of PGA/PBAT (50/50 wt. %) blends was improved from 10.7% to 145%, the oxygen permeability was reduced from 125 to 103 (cm(3) mm)/(m(2) 24 h atm), and the water vapor barrier performance was improved by similar to 47%. The enhancement in ductility, oxygen and water vapor barrier properties of the flexible blends were ascribed to the interfacial bonding between PBAT and PGA enabled by EMA-GMA. The compatibilized PGA/PBAT blends with high thermal stability up to 300 degrees C are preferable for high temperature or hot food packaging.

@article{athanasiou_gold_2021,
	title = {Gold {Nanoparticles} and {Nanoshells} {Embedded} as {Core}-{Shell} {Architectures} in {Hybrid} {Poly}({L}-{Histidine})-{Containing} {Polymers} for {Photothermal} {Therapies}},
	volume = {4},
	issn = {2574-0970},
	doi = {10.1021/acsanm.1c03769},
	abstract = {We present a facile strategy for the synthesis of hybrid nanoparticles containing gold nanoshells (AuNSs) that absorb at near-infrared (NIR). Polyethylene oxide)-b-poly(L-histidine), poly(ethylene oxide)-b-poly(L-histidine)-b-poly(L-phenylalanine), and poly(ethylene oxide)-b-poly(L-histidine )-b-poly(gamma-benzyl-L-glutamate) hybrid copolypeptides were used for the development of AuNSs. Spherical nanoparticles (NPs) were initially formed by the self-assembly of the amphiphilic hybrid polypeptides in water. The addition of HAuCl4 followed by heating, resulted in the red uction of the Au(III) by poly(L-histidine) (PHis), leading to the formation of AuNSs only at the PHis layer, thus forming a nanoshell within the preformed NPs. The NPs formed are composed of a poly(ethylene oxide) (PEO) shell, a PHis layer containing the nanoshell and a poly(L-phenylalanine) (PPhe) or poly(gamma-benzyl-L-glutamate) (PBLG) core. By controlling the AuNS thickness and the core diameter by the molecular characteristics of the polymeric precursors as well as the PHis/Au(III) ratio, the optical properties of the AuNSs can be fine-tuned to absorb at a specific wavelength. Thus, we achieved a shift of the absorption peak corresponding to longitudinal surface plasmon resonance to NIR wavelengths. The size and the morphology of the polymeric NPs containing AuNSs were examined by TEM and Dynamic Light Scattering. Studies on a dilute solution of polymeric nanoparticles containing AuNSs showed that by irradiation with a low power laser at 808 nm, results to significant increase of its temperature. We present an approach for the design and facile synthesis of biocompatible polymeric nanoparticles featuring AuNSs with a peak optical absorption in the NIR that can be fine-tuned. Therefore, our aim is to present a novel and facile approach for the formation of AuNSs to be used for photothermal therapy.},
	number = {12},
	urldate = {2022-02-19},
	journal = {ACS APPLIED NANO MATERIALS},
	author = {Athanasiou, Varvara and Stavroulaki, Dimitra and Arfara, Foteini and Kampras, Dimitrios and Kleideris, Ioannis and Roumelioti, Niki and Fragouli, Panagiota G. and Patias, Georgios and Haddleton, David and Iatrou, Hermis},
	month = dec,
	year = {2021},
	pages = {14217--14230},
}

We present a facile strategy for the synthesis of hybrid nanoparticles containing gold nanoshells (AuNSs) that absorb at near-infrared (NIR). Polyethylene oxide)-b-poly(L-histidine), poly(ethylene oxide)-b-poly(L-histidine)-b-poly(L-phenylalanine), and poly(ethylene oxide)-b-poly(L-histidine )-b-poly(gamma-benzyl-L-glutamate) hybrid copolypeptides were used for the development of AuNSs. Spherical nanoparticles (NPs) were initially formed by the self-assembly of the amphiphilic hybrid polypeptides in water. The addition of HAuCl4 followed by heating, resulted in the red uction of the Au(III) by poly(L-histidine) (PHis), leading to the formation of AuNSs only at the PHis layer, thus forming a nanoshell within the preformed NPs. The NPs formed are composed of a poly(ethylene oxide) (PEO) shell, a PHis layer containing the nanoshell and a poly(L-phenylalanine) (PPhe) or poly(gamma-benzyl-L-glutamate) (PBLG) core. By controlling the AuNS thickness and the core diameter by the molecular characteristics of the polymeric precursors as well as the PHis/Au(III) ratio, the optical properties of the AuNSs can be fine-tuned to absorb at a specific wavelength. Thus, we achieved a shift of the absorption peak corresponding to longitudinal surface plasmon resonance to NIR wavelengths. The size and the morphology of the polymeric NPs containing AuNSs were examined by TEM and Dynamic Light Scattering. Studies on a dilute solution of polymeric nanoparticles containing AuNSs showed that by irradiation with a low power laser at 808 nm, results to significant increase of its temperature. We present an approach for the design and facile synthesis of biocompatible polymeric nanoparticles featuring AuNSs with a peak optical absorption in the NIR that can be fine-tuned. Therefore, our aim is to present a novel and facile approach for the formation of AuNSs to be used for photothermal therapy.

@article{brodie_controlled_2021,
	title = {Controlled {Synthesis} of {Well}-{Defined} {Polyaminoboranes} on {Scale} {Using} a {Robust} and {Efficient} {Catalyst}},
	volume = {143},
	issn = {0002-7863},
	doi = {10.1021/jacs.1c10888},
	abstract = {The air tolerant precatalyst, [Rh(L)(NBD)]Cl ([1]Cl) [L =kappa(3)(iPr(2)PCH(2)CH(2))(2)NH, NBD = norbornadiene], mediates the selective synthesis of N-methylpolyaminoborane, (H2BNMeH)(n), by dehydropolymerization of H3B.NMeH2. Kinetic, speciation, and DFT studies show an induction period in which the active catalyst, Rh(L)H3 (3), forms, which sits as an outer-sphere adduct 3.H3BNMeH2 as the resting state. At the end of catalysis, dormant Rh(L)H2Cl (2) is formed. Reaction of 2 with H3B.NMeH2 returns 3, alongside the proposed formation of boronium [8H82B(NMeH2)(2)]Cl. Aided by isotopic labeling, Eyring analysis, and DFT calculations, a mechanism is proposed in which the cooperative "PNHP" ligand templates dehydrogenation, releasing (H)2B.NMeH (Delta G Phi calc = 19.6 kcal mol(-1)). H2B.NMeH is proposed to undergo rapid, low barrier, head-to-tail chain propagation for which 3 is the catalyst/initiator. A high molecular weight polymer is formed that is relatively insensitive to catalyst loading (M-n similar to 71 000 g mo(l)-(1); D, of similar to 1.6). The molecular weight can be controlled using [H2B(NMe2H)(2)]Cl as a chain transfer agent, M-n = 37 900-78 100 g mol(-1). This polymerization is suggested to arise from an ensemble of processes (catalyst speciation, dehydrogenation, propagation, chain transfer) that are geared around the concentration of H3B.NMeH2. TGA and DSC thermal analysis of polymer produced on scale (10 g, 0.01 mol \% [1]Cl) show a processing window that allows for melt extrusion of polyaminoborane strands, as well as hot pressing, drop casting, and electrospray deposition. By variation of conditions in the latter, smooth or porous microstructured films or spherical polyaminoboranes beads},
	number = {49},
	urldate = {2022-03-08},
	journal = {JOURNAL OF THE AMERICAN CHEMICAL SOCIETY},
	author = {Brodie, Claire N. and Boyd, Timothy M. and Sotorrios, Lia and Ryan, David E. and Magee, Eimear and Huband, Steven and Town, James S. and Lloyd-Jones, Guy C. and Haddleton, David M. and Macgregor, Stuart A. and Weller, Andrew S.},
	month = dec,
	year = {2021},
	pages = {21010--21023},
}

The air tolerant precatalyst, [Rh(L)(NBD)]Cl ([1]Cl) [L =kappa(3)(iPr(2)PCH(2)CH(2))(2)NH, NBD = norbornadiene], mediates the selective synthesis of N-methylpolyaminoborane, (H2BNMeH)(n), by dehydropolymerization of H3B.NMeH2. Kinetic, speciation, and DFT studies show an induction period in which the active catalyst, Rh(L)H3 (3), forms, which sits as an outer-sphere adduct 3.H3BNMeH2 as the resting state. At the end of catalysis, dormant Rh(L)H2Cl (2) is formed. Reaction of 2 with H3B.NMeH2 returns 3, alongside the proposed formation of boronium [8H82B(NMeH2)(2)]Cl. Aided by isotopic labeling, Eyring analysis, and DFT calculations, a mechanism is proposed in which the cooperative "PNHP" ligand templates dehydrogenation, releasing (H)2B.NMeH (Delta G Phi calc = 19.6 kcal mol(-1)). H2B.NMeH is proposed to undergo rapid, low barrier, head-to-tail chain propagation for which 3 is the catalyst/initiator. A high molecular weight polymer is formed that is relatively insensitive to catalyst loading (M-n similar to 71 000 g mo(l)-(1); D, of similar to 1.6). The molecular weight can be controlled using [H2B(NMe2H)(2)]Cl as a chain transfer agent, M-n = 37 900-78 100 g mol(-1). This polymerization is suggested to arise from an ensemble of processes (catalyst speciation, dehydrogenation, propagation, chain transfer) that are geared around the concentration of H3B.NMeH2. TGA and DSC thermal analysis of polymer produced on scale (10 g, 0.01 mol % [1]Cl) show a processing window that allows for melt extrusion of polyaminoborane strands, as well as hot pressing, drop casting, and electrospray deposition. By variation of conditions in the latter, smooth or porous microstructured films or spherical polyaminoboranes beads

@article{ma_well-defined_2021,
	title = {Well-defined polyacrylamides with {AIE} properties via rapid {Cu}-mediated living radical polymerization in aqueous solution: thermoresponsive nanoparticles for bioimaging},
	volume = {13},
	issn = {1759-9954},
	doi = {10.1039/d1py01432c},
	abstract = {There is a requirement for the development of methods for the preparation of well-controlled polymers with aggregation-induced emission (AIE) properties. This requirement directed this current work towards a robust synthetic route, which would be applicable for preparation in water and the presence of many types of functional groups. Herein, aqueous Cu-mediated living radical polymerization (LRP) has been optimized to provide facile and rapid access to a diverse range of water-soluble AIE polymers at sub-ambient temperatures. Homo-, block and statistical copolymerization all proceeded to a near full monomer conversion ({\textgreater}= 99\%) within 1 or 2 h and exhibited narrow dispersity, even when DP was targeted up to 1000. This excellent control associated with this polymerisation technique and the high-end group fidelity achieved were further demonstrated by linear first order kinetics and successful in situ block copolymerization, respectively. Fine-tuning the monomer sequence and composition of poly(N-isopropylacrylamide) (PNIPAM) copolymers allows for different lower critical solution temperature (LCST) and fluorescent thermoresponsive nanoparticles, which spontaneously self-assembled to varying sizes in water as determined by a combination of techniques (DLS, SAXS and TEM). Additionally, the fluorescence intensity was demonstrated to depend on the polymer concentration, architecture of the side chains and temperature. Particularly, PNIPAM-containing polymers were resistant to reduction in thermo-induced emission. The good biocompatibility, photostability and high specificity make them promising candidates as lysosome-specific probes for application in bioimaging.},
	number = {1},
	urldate = {2021-12-18},
	journal = {POLYMER CHEMISTRY},
	author = {Ma, Congkai and Han, Ting and Niu, Niu and Al-Shok, Lucas and Efstathiou, Spyridon and Lester, Daniel and Huband, Steven and Haddleton, David},
	month = dec,
	year = {2021},
	pages = {58--68},
}

There is a requirement for the development of methods for the preparation of well-controlled polymers with aggregation-induced emission (AIE) properties. This requirement directed this current work towards a robust synthetic route, which would be applicable for preparation in water and the presence of many types of functional groups. Herein, aqueous Cu-mediated living radical polymerization (LRP) has been optimized to provide facile and rapid access to a diverse range of water-soluble AIE polymers at sub-ambient temperatures. Homo-, block and statistical copolymerization all proceeded to a near full monomer conversion (\textgreater= 99%) within 1 or 2 h and exhibited narrow dispersity, even when DP was targeted up to 1000. This excellent control associated with this polymerisation technique and the high-end group fidelity achieved were further demonstrated by linear first order kinetics and successful in situ block copolymerization, respectively. Fine-tuning the monomer sequence and composition of poly(N-isopropylacrylamide) (PNIPAM) copolymers allows for different lower critical solution temperature (LCST) and fluorescent thermoresponsive nanoparticles, which spontaneously self-assembled to varying sizes in water as determined by a combination of techniques (DLS, SAXS and TEM). Additionally, the fluorescence intensity was demonstrated to depend on the polymer concentration, architecture of the side chains and temperature. Particularly, PNIPAM-containing polymers were resistant to reduction in thermo-induced emission. The good biocompatibility, photostability and high specificity make them promising candidates as lysosome-specific probes for application in bioimaging.

@article{lindley-hatcher_monitoring_2021,
	title = {Monitoring the {Effect} of {Transdermal} {Drug} {Delivery} {Patches} on the {Skin} {Using} {Terahertz} {Sensing}},
	volume = {13},
	issn = {1999-4923},
	doi = {10.3390/pharmaceutics13122052},
	abstract = {Water content of the skin is an important parameter for controlling the penetration rate of chemicals through the skin barrier; therefore, for transdermal patches designed for drug delivery to be successful, the effects of the patches on the water content of the skin must be understood. Terahertz (THz) spectroscopy is a technique which is being increasingly investigated for biomedical applications due to its high sensitivity to water content and non-ionizing nature. In this study, we used THz measurements of the skin (in vivo) to observe the effect of partially and fully occlusive skin patches on the THz response of the skin after the patches had been applied for 24 h. We were able to observe an increase in the water content of the skin following the application of the patches and to identify that the skin remained hyper-hydrated for four hours after the removal of the fully occlusive patches. Herein, we show that THz spectroscopy has potential for increasing the understanding of how transdermal patches affect the skin, how long the skin takes to recover following patch removal, and what implications these factors might have for how transdermal drug patches are designed and used.},
	number = {12},
	urldate = {2022-01-06},
	journal = {PHARMACEUTICS},
	author = {Lindley-Hatcher, Hannah and Wang, Jiarui and Hernandez-Serrano, Arturo I. and Hardwicke, Joseph and Nurumbetov, Gabit and Haddleton, David M. and Pickwell-MacPherson, Emma},
	month = dec,
	year = {2021},
}

Water content of the skin is an important parameter for controlling the penetration rate of chemicals through the skin barrier; therefore, for transdermal patches designed for drug delivery to be successful, the effects of the patches on the water content of the skin must be understood. Terahertz (THz) spectroscopy is a technique which is being increasingly investigated for biomedical applications due to its high sensitivity to water content and non-ionizing nature. In this study, we used THz measurements of the skin (in vivo) to observe the effect of partially and fully occlusive skin patches on the THz response of the skin after the patches had been applied for 24 h. We were able to observe an increase in the water content of the skin following the application of the patches and to identify that the skin remained hyper-hydrated for four hours after the removal of the fully occlusive patches. Herein, we show that THz spectroscopy has potential for increasing the understanding of how transdermal patches affect the skin, how long the skin takes to recover following patch removal, and what implications these factors might have for how transdermal drug patches are designed and used.

@article{wellings_understanding_2021,
	title = {Understanding the {Future} {Impacts} of {Electric} {Vehicles}-{An} {Analysis} of {Multiple} {Factors} {That} {Influence} the {Market}},
	volume = {3},
	issn = {2624-8921},
	doi = {10.3390/vehicles3040051},
	abstract = {The electric vehicle market is an increasingly important aspect of the automotive industry. However, as a relatively new technology, several issues remain present within the industry. An analysis is utilised to examine these issues, along with how they affect the industry and how they can be tackled. Several key issues that affect the electric vehicle market, as well as how efforts to address these issues influence the market, are identified. The analysis also includes the examination of ethical issues, with the issues that arise from the production of raw materials for electric vehicles. The analysis and examination of ethical issues display a wide range of problems in the industry. However, it did highlight the efforts being made to lessen the effect of these problems by various groups, such as regulation by EU and US governing bodies on the materials mined. From this analysis, this paper identifies that many of the other factors examined are directly or indirectly influenced by political and economic factors, also examined in this review. This highlights the impact that governing bodies and businesses have on a vast number of issues that are present within the market and how they can resolve the harmful factors examined.},
	number = {4},
	urldate = {2022-01-28},
	journal = {VEHICLES},
	author = {Wellings, Jonathan and Greenwood, David and Coles, Stuart R.},
	month = dec,
	year = {2021},
	pages = {851--871},
}

The electric vehicle market is an increasingly important aspect of the automotive industry. However, as a relatively new technology, several issues remain present within the industry. An analysis is utilised to examine these issues, along with how they affect the industry and how they can be tackled. Several key issues that affect the electric vehicle market, as well as how efforts to address these issues influence the market, are identified. The analysis also includes the examination of ethical issues, with the issues that arise from the production of raw materials for electric vehicles. The analysis and examination of ethical issues display a wide range of problems in the industry. However, it did highlight the efforts being made to lessen the effect of these problems by various groups, such as regulation by EU and US governing bodies on the materials mined. From this analysis, this paper identifies that many of the other factors examined are directly or indirectly influenced by political and economic factors, also examined in this review. This highlights the impact that governing bodies and businesses have on a vast number of issues that are present within the market and how they can resolve the harmful factors examined.

@article{song_molecular_2021,
	title = {Molecular {Self}-{Assembly} and {Supramolecular} {Chemistry} of {Cyclic} {Peptides}},
	volume = {121},
	issn = {0009-2665},
	doi = {10.1021/acs.chemrev.0c01291},
	abstract = {This Review focuses on the establishment and development of self-assemblies governed by the supramolecular interactions between cyclic peptides. The Review first describes the type of cyclic peptides able to assemble into tubular structures to form supramolecular cyclic peptide nanotubes. A range of cyclic peptides have been identified to have such properties, including alpha-peptides, beta-peptides, alpha,gamma-peptides, and peptides based on delta- and epsilon-amino acids. The Review covers the design and functionalization of these cyclic peptides and expands to a recent advance in the design and application of these materials through their conjugation to polymer chains to generate cyclic peptide-polymer conjugates nanostructures. The Review, then, concentrates on the challenges in characterizing these systems and presents an overview of the various analytical and characterization techniques used to date. This overview concludes with a critical survey of the various applications of the nanomaterials obtained from supramolecular cyclic peptide nanotubes, with a focus on biological and medical applications, ranging from ion channels and membrane insertion to antibacterial materials, anticancer drug delivery, gene delivery, and antiviral applications.},
	number = {22},
	urldate = {2022-03-02},
	journal = {CHEMICAL REVIEWS},
	author = {Song, Qiao and Cheng, Zihe and Kariuki, Maria and Hall, Stephen C. L. and Hill, Sophie K. and Rho, Julia Y. and Perrier, Sebastien},
	month = nov,
	year = {2021},
	pages = {13936--13995},
}

This Review focuses on the establishment and development of self-assemblies governed by the supramolecular interactions between cyclic peptides. The Review first describes the type of cyclic peptides able to assemble into tubular structures to form supramolecular cyclic peptide nanotubes. A range of cyclic peptides have been identified to have such properties, including alpha-peptides, beta-peptides, alpha,gamma-peptides, and peptides based on delta- and epsilon-amino acids. The Review covers the design and functionalization of these cyclic peptides and expands to a recent advance in the design and application of these materials through their conjugation to polymer chains to generate cyclic peptide-polymer conjugates nanostructures. The Review, then, concentrates on the challenges in characterizing these systems and presents an overview of the various analytical and characterization techniques used to date. This overview concludes with a critical survey of the various applications of the nanomaterials obtained from supramolecular cyclic peptide nanotubes, with a focus on biological and medical applications, ranging from ion channels and membrane insertion to antibacterial materials, anticancer drug delivery, gene delivery, and antiviral applications.

@article{zhao_one-pot_2021,
	title = {One-pot synthesis of amphiphilic multiblock poly(2-oxazoline)s via para-fluoro-thiol click reactions},
	volume = {12},
	issn = {1759-9954},
	doi = {10.1039/d1py00944c},
	abstract = {A clickable initiator, pentafluoro benzyl bromide, has been investigated for the cationic ring opening polymerization of poly(2-oxazolines). Additionally, the clickable alpha end group was then utilized in a para-fluoro-thiol click reaction to synthesise linear diblock, tetrablock, multiblock copolymers as well as star shaped poly(2-oxazoline)s using dithiol compounds as terminating agents. Thus, a one-pot approach combining the para-fluoro-thiol click reaction and direct termination of the poly(2-oxazoline) living chain end with 4,4-thiobisbenzenethiol has been performed to prepare multiblock copolymers of poly(2-ethyl-2-oxazoline) (PEtOx) and poly((2-ethyl-2-oxazoline)-b-(2-methyl-2-oxazoline) (PEtOx-mb-PMeOx). All obtained polymers were characterized by Size Exclusion Chromatography (SEC), H-1 Nuclear Magnetic Resonance (NMR) and Matrix-Assisted Laser Desorption/Ionization-Time of Flight (MALDI-ToF) mass spectrometry. Last but not least, the self-assembly properties of prepared amphiphilic polymers were studied with DLS and TEM. Nanoparticles with a diameter ranging from 184 nm to 250 nm were observed in TEM for PEtOx-mb-PMeOx copolymers.},
	number = {44},
	urldate = {2021-11-21},
	journal = {POLYMER CHEMISTRY},
	author = {Zhao, Tieshuai and Drain, Ben and Yilmaz, Gokhan and Becer, C. Remzi},
	month = nov,
	year = {2021},
	pages = {6392--6403},
}

A clickable initiator, pentafluoro benzyl bromide, has been investigated for the cationic ring opening polymerization of poly(2-oxazolines). Additionally, the clickable alpha end group was then utilized in a para-fluoro-thiol click reaction to synthesise linear diblock, tetrablock, multiblock copolymers as well as star shaped poly(2-oxazoline)s using dithiol compounds as terminating agents. Thus, a one-pot approach combining the para-fluoro-thiol click reaction and direct termination of the poly(2-oxazoline) living chain end with 4,4-thiobisbenzenethiol has been performed to prepare multiblock copolymers of poly(2-ethyl-2-oxazoline) (PEtOx) and poly((2-ethyl-2-oxazoline)-b-(2-methyl-2-oxazoline) (PEtOx-mb-PMeOx). All obtained polymers were characterized by Size Exclusion Chromatography (SEC), H-1 Nuclear Magnetic Resonance (NMR) and Matrix-Assisted Laser Desorption/Ionization-Time of Flight (MALDI-ToF) mass spectrometry. Last but not least, the self-assembly properties of prepared amphiphilic polymers were studied with DLS and TEM. Nanoparticles with a diameter ranging from 184 nm to 250 nm were observed in TEM for PEtOx-mb-PMeOx copolymers.

@article{smith_isocyanate-functionalised_2021,
	title = {Isocyanate-functionalised graphene oxide and poly(vinyl alcohol) nacre-mimetic inspired freestanding films},
	volume = {4},
	issn = {2516-0230},
	doi = {10.1039/d1na00792k},
	abstract = {Nacre mimetic films based on 2-ureido-4[1H]-pyrimidinone (UPy) functionalised graphene oxide (GO) and poly(vinyl alcohol) (PVA) were readily prepared by self-assembly using a vacuum filtration method. The isocyanate (UPy) functionalisation of the PVA was confirmed from a combination of Fourier transform infrared spectroscopy (FTIR) and changes in d-spacing from X-ray diffraction (XRD) measurements and, of the GO by solid-state NMR measurements reported by the authors previously. This is the first example of nacre mimetic structures where both the nanoplatelet (GO) and polymer (PVA) components are functionalised with complimentary groups. The resulting films displayed substantial increases in Young's modulus (E) of 392\% (GO1/PVA1), ultimate tensile strength (UTS, sigma) of 535\% (GO1/PVA1), elongation at break (epsilon(max)) of 598\% (GO10/PVA5) and tensile toughness (U-T) of 1789\% (GO1/PVA10) compared to the un-functionalised GO analogues. The binding of UPy to both the GO and the PVA provides multiple routes by which these freestanding nacre mimetic films can dissipate applied loads.},
	number = {1},
	urldate = {2021-11-24},
	journal = {NANOSCALE ADVANCES},
	author = {Smith, Andrew J. and Figiel, Lukasz and Wan, Chaoying and McNally, Tony},
	month = dec,
	year = {2021},
	pages = {49--57},
}

Nacre mimetic films based on 2-ureido-4[1H]-pyrimidinone (UPy) functionalised graphene oxide (GO) and poly(vinyl alcohol) (PVA) were readily prepared by self-assembly using a vacuum filtration method. The isocyanate (UPy) functionalisation of the PVA was confirmed from a combination of Fourier transform infrared spectroscopy (FTIR) and changes in d-spacing from X-ray diffraction (XRD) measurements and, of the GO by solid-state NMR measurements reported by the authors previously. This is the first example of nacre mimetic structures where both the nanoplatelet (GO) and polymer (PVA) components are functionalised with complimentary groups. The resulting films displayed substantial increases in Young's modulus (E) of 392% (GO1/PVA1), ultimate tensile strength (UTS, sigma) of 535% (GO1/PVA1), elongation at break (epsilon(max)) of 598% (GO10/PVA5) and tensile toughness (U-T) of 1789% (GO1/PVA10) compared to the un-functionalised GO analogues. The binding of UPy to both the GO and the PVA provides multiple routes by which these freestanding nacre mimetic films can dissipate applied loads.

@article{baffie_block_2021,
	title = {Block {Copolymers} {Based} on {Ethylene} and {Methacrylates} {Using} a {Combination} of {Catalytic} {Chain} {Transfer} {Polymerisation} ({CCTP}) and {Radical} {Polymerisation}},
	volume = {60},
	issn = {1433-7851},
	doi = {10.1002/anie.202108996},
	abstract = {Two scalable polymerisation methods are used in combination for the synthesis of ethylene and methacrylate block copolymers. omega-Unsaturated methacrylic oligomers (MMA(n)) produced by catalytic chain transfer (co)polymerisation (CCTP) of methyl methacrylate (MMA) and methacrylic acid (MAA) are used as reagents in the radical polymerisation of ethylene (E) in dimethyl carbonate solvent under relatively mild conditions (80 bar, 70 degrees C). Kinetic measurements and analyses of the produced copolymers by size exclusion chromatography (SEC) and a combination of nuclear magnetic resonance (NMR) techniques indicate that MMA(n) is involved in a degradative chain transfer process resulting in the formation of (MMA)(n)-b-PE block copolymers. Molecular modelling performed by DFT supports the overall reactivity scheme and observed selectivities. The effect of MMA(n) molar mass and composition is also studied. The block copolymers were characterised by differential scanning calorimetry (DSC) and their bulk behaviour studied by SAXS/WAXS analysis.},
	number = {48},
	urldate = {2021-11-02},
	journal = {ANGEWANDTE CHEMIE-INTERNATIONAL EDITION},
	author = {Baffie, Florian and Patias, Georgios and Shegiwal, Ataulla and Brunel, Fabrice and Monteil, Vincent and Verrieux, Ludmilla and Perrin, Lionel and Haddleton, David M. and D'Agosto, Franck},
	month = nov,
	year = {2021},
	pages = {25356--25364},
}

Two scalable polymerisation methods are used in combination for the synthesis of ethylene and methacrylate block copolymers. omega-Unsaturated methacrylic oligomers (MMA(n)) produced by catalytic chain transfer (co)polymerisation (CCTP) of methyl methacrylate (MMA) and methacrylic acid (MAA) are used as reagents in the radical polymerisation of ethylene (E) in dimethyl carbonate solvent under relatively mild conditions (80 bar, 70 degrees C). Kinetic measurements and analyses of the produced copolymers by size exclusion chromatography (SEC) and a combination of nuclear magnetic resonance (NMR) techniques indicate that MMA(n) is involved in a degradative chain transfer process resulting in the formation of (MMA)(n)-b-PE block copolymers. Molecular modelling performed by DFT supports the overall reactivity scheme and observed selectivities. The effect of MMA(n) molar mass and composition is also studied. The block copolymers were characterised by differential scanning calorimetry (DSC) and their bulk behaviour studied by SAXS/WAXS analysis.

@article{baker_glycan-based_2021,
	title = {Glycan-{Based} {Flow}-{Through} {Device} for the {Detection} of {SARS}-{COV}-2},
	volume = {6},
	issn = {2379-3694},
	doi = {10.1021/acssensors.1c01470},
	abstract = {The COVID-19 pandemic, and future pandemics, require diagnostic tools to track disease spread and guide the isolation of (a)symptomatic individuals. Lateral-flow diagnostics (LFDs) are rapid and of lower cost than molecular (genetic) tests, with current LFDs using antibodies as their recognition units. Herein, we develop a prototype flow-through device (related, but distinct to LFDs), utilizing N-acetyl neuraminic acid-functionalized, polymer-coated, gold nanoparticles as the detection/capture unit for SARS-COV-2, by targeting the sialic acid-binding site of the spike protein. The prototype device can give rapid results, with higher viral loads being faster than lower viral loads. The prototype's effectiveness is demonstrated using spike protein, lentiviral models, and a panel of heat-inactivated primary patient nasal swabs. The device was also shown to retain detection capability toward recombinant spike proteins from several variants (mutants) of concern. This study provides the proof of principle that glyco-lateral-flow devices could be developed to be used in the tracking monitoring of infectious agents, to complement, or as alternatives to antibody-based systems.},
	number = {10},
	urldate = {2021-10-11},
	journal = {ACS SENSORS},
	author = {Baker, Alexander N. and Richards, Sarah-Jane and Pandey, Sarojini and Guy, Collette S. and Ahmad, Ashfaq and Hasan, Muhammad and Biggs, I, Caroline and Georgiou, Panagiotis G. and Zwetsloot, Alexander J. and Straube, Anne and Dedola, Simone and Field, Robert A. and Anderson, Neil R. and Walker, Marc and Grammatopoulos, Dimitris and Gibson, I, Matthew},
	month = oct,
	year = {2021},
	note = {Iceni Diagnost Ltd},
	pages = {3696--3705},
}

The COVID-19 pandemic, and future pandemics, require diagnostic tools to track disease spread and guide the isolation of (a)symptomatic individuals. Lateral-flow diagnostics (LFDs) are rapid and of lower cost than molecular (genetic) tests, with current LFDs using antibodies as their recognition units. Herein, we develop a prototype flow-through device (related, but distinct to LFDs), utilizing N-acetyl neuraminic acid-functionalized, polymer-coated, gold nanoparticles as the detection/capture unit for SARS-COV-2, by targeting the sialic acid-binding site of the spike protein. The prototype device can give rapid results, with higher viral loads being faster than lower viral loads. The prototype's effectiveness is demonstrated using spike protein, lentiviral models, and a panel of heat-inactivated primary patient nasal swabs. The device was also shown to retain detection capability toward recombinant spike proteins from several variants (mutants) of concern. This study provides the proof of principle that glyco-lateral-flow devices could be developed to be used in the tracking monitoring of infectious agents, to complement, or as alternatives to antibody-based systems.

@article{floyd_cationic_2021,
	title = {Cationic {Bottlebrush} {Copolymers} from {Partially} {Hydrolyzed} {Poly}(oxazoline)s},
	volume = {54},
	issn = {0024-9297},
	doi = {10.1021/acs.macromol.1c01458},
	abstract = {Cationically charged bottlebrush copolymers were produced by hydrolysis of poly(2-ethyl-2-oxazoline) (PEtOx). The cationic ring-opening polymerization of EtOx was initiated using a styrene derivative to produce PEtOx macromonomers with two different lengths. After detailed characterization, these macromonomers were polymerized via reversible addition-fragmentation chain transfer (RAFT) polymerization in a grafting-through process. The length of the bottlebrush backbone was varied, and it was found that a good control over the polymerization could be retained up to backbone DP 50. Hydrolysis of PEtOx repeating units under acidic conditions afforded cationic bottlebrushes, with a defined charge content that could be adjusted by changing the hydrolysis reaction time. Bottlebrush copolymers were analyzed in detail using size-exclusion chromatography, small-angle neutron scattering, and atomic force microscopy indicating a cylindrical topology and an increasing flexibility with increasing chain length.},
	number = {20},
	urldate = {2021-11-11},
	journal = {MACROMOLECULES},
	author = {Floyd, Thomas G. and Hakkinen, Satu and Hall, Stephen C. L. and Dalgliesh, Robert M. and Lehnen, Anne-Catherine and Hartlieb, Matthias and Perrier, Sebastien},
	month = oct,
	year = {2021},
	pages = {9461--9473},
}

Cationically charged bottlebrush copolymers were produced by hydrolysis of poly(2-ethyl-2-oxazoline) (PEtOx). The cationic ring-opening polymerization of EtOx was initiated using a styrene derivative to produce PEtOx macromonomers with two different lengths. After detailed characterization, these macromonomers were polymerized via reversible addition-fragmentation chain transfer (RAFT) polymerization in a grafting-through process. The length of the bottlebrush backbone was varied, and it was found that a good control over the polymerization could be retained up to backbone DP 50. Hydrolysis of PEtOx repeating units under acidic conditions afforded cationic bottlebrushes, with a defined charge content that could be adjusted by changing the hydrolysis reaction time. Bottlebrush copolymers were analyzed in detail using size-exclusion chromatography, small-angle neutron scattering, and atomic force microscopy indicating a cylindrical topology and an increasing flexibility with increasing chain length.

@article{risangud_synthesis_2021,
	title = {Synthesis of biodegradable liquid-core microcapsules composed of isocyanate functionalized poly(ε-caprolactone)-containing copolymers},
	volume = {159},
	issn = {0014-3057},
	doi = {10.1016/j.eurpolymj.2021.110739},
	abstract = {A combination of reversible deactivation radical polymerization (RDRP), isocyanate chemistry, and a convenient drying process via spray drying is employed to fabricate powder-form biodegradable liquid-core microcapsules. Two different molecular weight alpha,omega-poly(epsilon caprolactone) RDRP macroinitiators were first prepared through esterification to obtain the degradable a-halo ester initiators. Subsequently, poly(benzyl methacrylate-co-iso-cyanatoethyl methacrylate) (P(BnMA(a)-co-IEMb)) copolymers were synthesized from the RDRP macroinitiators using a copper(0)-mediated polymerization system at ambient temperature. By controlling the macroinitiator to monomer feeding ratio from 1:50 to 1:100, the resultant copolymers had number average molecular weights (M-n) in the range of 7900-17800 g mol(-1) with dispersities (D) of 1.42-1.52. Afterward, the isocyanate-containing copolymers were employed in the fabrication of particles via interfacial polymerization, followed by a water removal process using spray drying. All polymers and particles were thoroughly characterized using a range of spectroscopic, chromatographic and microscopy analyses.},
	urldate = {2021-09-25},
	journal = {EUROPEAN POLYMER JOURNAL},
	author = {Risangud, Nuttapol and de Jongh, Patrick A. J. M. and Wilson, Paul and Haddleton, David M.},
	month = oct,
	year = {2021},
}

A combination of reversible deactivation radical polymerization (RDRP), isocyanate chemistry, and a convenient drying process via spray drying is employed to fabricate powder-form biodegradable liquid-core microcapsules. Two different molecular weight alpha,omega-poly(epsilon caprolactone) RDRP macroinitiators were first prepared through esterification to obtain the degradable a-halo ester initiators. Subsequently, poly(benzyl methacrylate-co-iso-cyanatoethyl methacrylate) (P(BnMA(a)-co-IEMb)) copolymers were synthesized from the RDRP macroinitiators using a copper(0)-mediated polymerization system at ambient temperature. By controlling the macroinitiator to monomer feeding ratio from 1:50 to 1:100, the resultant copolymers had number average molecular weights (M-n) in the range of 7900-17800 g mol(-1) with dispersities (D) of 1.42-1.52. Afterward, the isocyanate-containing copolymers were employed in the fabrication of particles via interfacial polymerization, followed by a water removal process using spray drying. All polymers and particles were thoroughly characterized using a range of spectroscopic, chromatographic and microscopy analyses.

@article{monaco_detailed_2021,
	title = {Detailed {GPC} analysis of poly({N}-isopropylacrylamide) with core cross-linked star architecture},
	volume = {12},
	issn = {1759-9954},
	doi = {10.1039/d1py00966d},
	abstract = {Core cross-linked star shaped polymers possess unique physical properties that can be utilized as drug transporters for biomedical applications. However, detailed analysis of these polymer structures is not straightforward. Herein, we employ multi-detector gel permeation chromatography (GPC) to elucidate structural features of cross-linked stars prepared from the polymerisation of NIPAM via Cu(0)-mediated Reversible Deactivation Radical Polymerisation. Furthermore, we aim to show how varying the arm length and the core size of the star polymers can not only affect their structural properties but also their capacity to encapsulate drug-like molecules.},
	number = {36},
	urldate = {2021-09-07},
	journal = {POLYMER CHEMISTRY},
	author = {Monaco, Alessandra and Drain, Ben and Becer, C. Remzi},
	month = sep,
	year = {2021},
	pages = {5229--5238},
}

Core cross-linked star shaped polymers possess unique physical properties that can be utilized as drug transporters for biomedical applications. However, detailed analysis of these polymer structures is not straightforward. Herein, we employ multi-detector gel permeation chromatography (GPC) to elucidate structural features of cross-linked stars prepared from the polymerisation of NIPAM via Cu(0)-mediated Reversible Deactivation Radical Polymerisation. Furthermore, we aim to show how varying the arm length and the core size of the star polymers can not only affect their structural properties but also their capacity to encapsulate drug-like molecules.

@article{tao_recent_2021,
	title = {Recent progress in acoustic materials and noise control strategies-{A} review},
	volume = {24},
	issn = {2352-9407},
	doi = {10.1016/j.apmt.2021.101141},
	abstract = {Noise pollution impacts the well-being of millions of people on a daily basis and can lead to serious health issues such as hearing loss and stress. Developing efficient yet cost-effective sound absorbing materials for noise reduction in vehicles, buildings and large spaces has become an important research area. The present review focuses on the latest developments in sound absorbing products based on engineering materials solutions as well as tailored micro and nanostructures. In addition, modelling techniques for simulating sound wave propagation through porous media are briefly introduced. Various materials such as polyurethane foam, thermoplastic foams, textile fabrics and composites are reviewed with different design strategies and structures ranging from foam structures to micro-perforated panels summarized and compared. The effect of different types of micro-and nanofillers, hierarchical and sandwich structures and synergistic effects of combining multiple constituents with structural designs at different length scales to achieve the desired acoustic properties are discussed. Mechanisms of each are analysed with the aim of exploring new strategies based on existing knowledge. Opportunities and obstacles are identified, while engineering applications ranging from automotive to built environment are reviewed, together with their desired properties and functions to shed light on future research directions towards advanced acoustic materials. (c) 2021 Elsevier Ltd. All rights reserved.},
	urldate = {2021-10-03},
	journal = {APPLIED MATERIALS TODAY},
	author = {Tao, Yinping and Ren, Musu and Zhang, Han and Peijs, Ton},
	month = sep,
	year = {2021},
}

Noise pollution impacts the well-being of millions of people on a daily basis and can lead to serious health issues such as hearing loss and stress. Developing efficient yet cost-effective sound absorbing materials for noise reduction in vehicles, buildings and large spaces has become an important research area. The present review focuses on the latest developments in sound absorbing products based on engineering materials solutions as well as tailored micro and nanostructures. In addition, modelling techniques for simulating sound wave propagation through porous media are briefly introduced. Various materials such as polyurethane foam, thermoplastic foams, textile fabrics and composites are reviewed with different design strategies and structures ranging from foam structures to micro-perforated panels summarized and compared. The effect of different types of micro-and nanofillers, hierarchical and sandwich structures and synergistic effects of combining multiple constituents with structural designs at different length scales to achieve the desired acoustic properties are discussed. Mechanisms of each are analysed with the aim of exploring new strategies based on existing knowledge. Opportunities and obstacles are identified, while engineering applications ranging from automotive to built environment are reviewed, together with their desired properties and functions to shed light on future research directions towards advanced acoustic materials. (c) 2021 Elsevier Ltd. All rights reserved.

@article{hartweg_synthetic_2021,
	title = {Synthetic {Glycomacromolecules} of {Defined} {Valency}, {Absolute} {Configuration}, and {Topology} {Distinguish} between {Human} {Lectins}},
	volume = {1},
	issn = {2691-3704},
	doi = {10.1021/jacsau.1c00255},
	abstract = {Carbohydrate-binding proteins (lectins) play vital roles in cell recognition and signaling, including pathogen binding and innate immunity. Thus, targeting lectins, especially those on the surface of immune cells, could advance immunology and drug discovery. Lectins are typically oligomeric; therefore, many of the most potent ligands are multivalent. An effective strategy for lectin targeting is to display multiple copies of a single glycan epitope on a polymer backbone; however, a drawback to such multivalent ligands is they cannot distinguish between lectins that share monosaccharide binding selectivity (e.g., mannose-binding lectins) as they often lack molecular precision. Here, we describe the development of an iterative exponential growth (IEG) synthetic strategy that enables facile access to synthetic glycomacromolecules with precisely defined and tunable sizes up to 22.5 kDa, compositions, topologies, and absolute configurations. Twelve discrete mannosylated "glyco-IEGmers" are synthesized and screened for binding to a panel of mannoside-binding immune lectins (DC-SIGN, DC-SIGNR, MBL, SP-D, langerin, dectin-2, mincle, and DEC-205). In many cases, the glyco-IEGmers had distinct length, stereochemistry, and topology-dependent lectin-binding preferences. To understand these differences, we used molecular dynamics and density functional theory simulations of octameric glyco-IEGmers, which revealed dramatic effects of glyco-IEGmer stereochemistry and topology on solution structure and reveal an interplay between conformational diversity and chiral recognition in selective lectin binding. Ligand function also could be controlled by chemical substitution: by tuning the side chains of glycoIEGmers that bind DC-SIGN, we could alter their cellular trafficking through alteration of their aggregation state. These results highlight the power of precision synthetic oligomer/polymer synthesis for selective biological targeting, motivating the development of next-generation glycomacromolecules tailored for specific immunological or other therapeutic applications.},
	number = {10},
	urldate = {2021-12-10},
	journal = {JACS AU},
	author = {Hartweg, Manuel and Jiang, Yivan and Yilmaz, Gokhan and Jarvis, Cassie M. and Nguyen, Hung V-T and Primo, Gaston A. and Monaco, Alessandra and Beyer, Valentin P. and Chen, Kathleen K. and Mohapatra, Somesh and Axelrod, Simon and Gomez-Bombarelli, Rafael and Kiessling, Laura L. and Becer, C. Remzi and Johnson, Jeremiah A.},
	month = oct,
	year = {2021},
	pages = {1621--1630},
}

Carbohydrate-binding proteins (lectins) play vital roles in cell recognition and signaling, including pathogen binding and innate immunity. Thus, targeting lectins, especially those on the surface of immune cells, could advance immunology and drug discovery. Lectins are typically oligomeric; therefore, many of the most potent ligands are multivalent. An effective strategy for lectin targeting is to display multiple copies of a single glycan epitope on a polymer backbone; however, a drawback to such multivalent ligands is they cannot distinguish between lectins that share monosaccharide binding selectivity (e.g., mannose-binding lectins) as they often lack molecular precision. Here, we describe the development of an iterative exponential growth (IEG) synthetic strategy that enables facile access to synthetic glycomacromolecules with precisely defined and tunable sizes up to 22.5 kDa, compositions, topologies, and absolute configurations. Twelve discrete mannosylated "glyco-IEGmers" are synthesized and screened for binding to a panel of mannoside-binding immune lectins (DC-SIGN, DC-SIGNR, MBL, SP-D, langerin, dectin-2, mincle, and DEC-205). In many cases, the glyco-IEGmers had distinct length, stereochemistry, and topology-dependent lectin-binding preferences. To understand these differences, we used molecular dynamics and density functional theory simulations of octameric glyco-IEGmers, which revealed dramatic effects of glyco-IEGmer stereochemistry and topology on solution structure and reveal an interplay between conformational diversity and chiral recognition in selective lectin binding. Ligand function also could be controlled by chemical substitution: by tuning the side chains of glycoIEGmers that bind DC-SIGN, we could alter their cellular trafficking through alteration of their aggregation state. These results highlight the power of precision synthetic oligomer/polymer synthesis for selective biological targeting, motivating the development of next-generation glycomacromolecules tailored for specific immunological or other therapeutic applications.

@article{lunn_dual_2021,
	title = {Dual {pH}-{Responsive} {Macrophage}-{Targeted} {Isoniazid} {Glycoparticles} for {Intracellular} {Tuberculosis} {Therapy}},
	volume = {22},
	issn = {1525-7797},
	doi = {10.1021/acs.biomac.1c00554},
	abstract = {Tuberculosis (TB) is a global epidemic that kills over a million people every year, particularly in low-resource communities. Mycobacterium tuberculosis, the most common bacterium that causes TB, is difficult to treat, particularly in its latent phase, in part due to its ability to survive and replicate within the host macrophage. New therapeutic approaches resulting in better tolerated and shorter antibiotic courses that target intracellular bacteria are critical to effective treatment. The development of a novel, pH-responsive, mannosylated nanoparticle, covalently linked with isoniazid, a first-line TB antibiotic, is presented. This nanoparticle drug delivery agent has increased macrophage uptake and, upon exposure to the acidic phagolysosome, releases isoniazid through hydrolysis of a hydrazone bond, and disintegrates into a linear polymer. Full antibiotic activity is shown to be retained, with mannosylated isoniazid particles being the only treatment exhibiting complete bacterial eradication of intracellular bacteria, compared to an equivalent PEGylated system and free isoniazid. Such a system, able to effectively kill intracellular mycobacteria, holds promise for improved outcomes in TB infection.},
	number = {9},
	urldate = {2021-09-28},
	journal = {BIOMACROMOLECULES},
	author = {Lunn, Andrew M. and Unnikrishnan, Meera and Perrier, Sebastien},
	month = sep,
	year = {2021},
	pages = {3756--3768},
}

Tuberculosis (TB) is a global epidemic that kills over a million people every year, particularly in low-resource communities. Mycobacterium tuberculosis, the most common bacterium that causes TB, is difficult to treat, particularly in its latent phase, in part due to its ability to survive and replicate within the host macrophage. New therapeutic approaches resulting in better tolerated and shorter antibiotic courses that target intracellular bacteria are critical to effective treatment. The development of a novel, pH-responsive, mannosylated nanoparticle, covalently linked with isoniazid, a first-line TB antibiotic, is presented. This nanoparticle drug delivery agent has increased macrophage uptake and, upon exposure to the acidic phagolysosome, releases isoniazid through hydrolysis of a hydrazone bond, and disintegrates into a linear polymer. Full antibiotic activity is shown to be retained, with mannosylated isoniazid particles being the only treatment exhibiting complete bacterial eradication of intracellular bacteria, compared to an equivalent PEGylated system and free isoniazid. Such a system, able to effectively kill intracellular mycobacteria, holds promise for improved outcomes in TB infection.

@article{little_synthesis_2021,
	title = {Synthesis of {Poly}({Lactic} {Acid}-co-{Glycolic} {Acid}) {Copolymers} with {High} {Glycolide} {Ratio} by {Ring}-{Opening} {Polymerisation}},
	volume = {13},
	issn = {2073-4360},
	doi = {10.3390/polym13152458},
	abstract = {The rise in demand for biodegradable plastic packaging with high barrier properties has spurred interest in poly(lactic acid-co-glycolic acid) (PLGA) copolymers with a relatively high glycolide content. In this work, we examined how reaction conditions affect the synthesis of PLGA25 (L:G 25:75) through the ring-opening polymerisation of d-l-lactide (L) and glycolide (G), using tin 2-ethylhexanoate (Sn(Oct)(2)) as the catalyst and 1-dodecanol as the initiator. The effects of varying the initiator concentration, catalyst concentration, reaction time, and temperature on the molecular weight, monomer conversion, and thermal properties of PLGA25 were investigated. Increasing the reaction temperature from 130 to 205 degrees C significantly reduced the time required for high monomer conversions but caused greater polymer discolouration. Whilst increasing the [M]:[C] from 6500:1 to 50,000:1 reduced polymer discolouration, it also resulted in longer reaction times and higher reaction temperatures being required to achieve high conversions. High M-n and M-w values of 136,000 and 399,000 g mol(-1) were achieved when polymerisations were performed in the solid state at 150 degrees C using low initiator concentrations. These copolymers were analysed using high temperature SEC at 80 degrees C, employing DMSO instead of HFIP as the eluent.},
	number = {15},
	urldate = {2021-08-15},
	journal = {POLYMERS},
	author = {Little, Alastair and Wemyss, Alan M. and Haddleton, David M. and Tan, Bowen and Sun, Zhaoyang and Ji, Yang and Wan, Chaoying},
	month = aug,
	year = {2021},
	note = {PJIM Polymer Sci Co Ltd},
}

The rise in demand for biodegradable plastic packaging with high barrier properties has spurred interest in poly(lactic acid-co-glycolic acid) (PLGA) copolymers with a relatively high glycolide content. In this work, we examined how reaction conditions affect the synthesis of PLGA25 (L:G 25:75) through the ring-opening polymerisation of d-l-lactide (L) and glycolide (G), using tin 2-ethylhexanoate (Sn(Oct)(2)) as the catalyst and 1-dodecanol as the initiator. The effects of varying the initiator concentration, catalyst concentration, reaction time, and temperature on the molecular weight, monomer conversion, and thermal properties of PLGA25 were investigated. Increasing the reaction temperature from 130 to 205 degrees C significantly reduced the time required for high monomer conversions but caused greater polymer discolouration. Whilst increasing the [M]:[C] from 6500:1 to 50,000:1 reduced polymer discolouration, it also resulted in longer reaction times and higher reaction temperatures being required to achieve high conversions. High M-n and M-w values of 136,000 and 399,000 g mol(-1) were achieved when polymerisations were performed in the solid state at 150 degrees C using low initiator concentrations. These copolymers were analysed using high temperature SEC at 80 degrees C, employing DMSO instead of HFIP as the eluent.

@article{pan_piezoelectric-driven_2021,
	title = {Piezoelectric-{Driven} {Self}-{Sensing} {Leaf}-{Mimic} {Actuator} {Enabled} by {Integration} of a {Self}-{Healing} {Dielectric} {Elastomer} and a {Piezoelectric} {Composite}},
	volume = {3},
	issn = {2640-4567},
	doi = {10.1002/aisy.202000248},
	abstract = {Soft robots and devices exploit highly deformable materials that are capable of changes in shape to allow conformable physical contact for controlled manipulation. While soft robots are resilient to mechanical impact, they are susceptible to mechanical damage, such as tears and punctures. The development of self-healing materials and actuators continues to attract increasing interest, in particular, with respect to integrating self-healing polymers to create bioinspired soft self-healing devices. Herein, a novel piezoelectric-driven self-healing leaf-motion mimic actuator is designed by combining a thermoplastic methyl thioglycolate-modified styrene-butadiene-styrene (MGSBS) elastomer with a piezoelectric macrofiber composite (MFC) for self-sensing applications. This article is the first demonstration of a self-sensing and self-healing actuator-sensor system, which is driven by a piezoelectric actuator and can mimic leaf motion. The leaf-motion actuator combines built-in dynamic sensing and room-temperature self-healing capabilities to restore macroscale cutting damage with an intrinsically high bandwidth of up to 10 kHz. The feasibility and potential of the new actuator for use in complex soft autonomous systems are demonstrated. These new results help to address the emerging influence of self-healing soft actuators and the challenges of sensing, actuation, and damage resistance in soft robotics.},
	number = {8},
	urldate = {2021-09-08},
	journal = {ADVANCED INTELLIGENT SYSTEMS},
	author = {Pan, Min and Yuan, Chenggang and Pickford, Tom and Tian, Jianhui and Ellingford, Christopher and Zhou, Ning and Bowen, Christopher and Wan, Chaoying},
	month = aug,
	year = {2021},
}

Soft robots and devices exploit highly deformable materials that are capable of changes in shape to allow conformable physical contact for controlled manipulation. While soft robots are resilient to mechanical impact, they are susceptible to mechanical damage, such as tears and punctures. The development of self-healing materials and actuators continues to attract increasing interest, in particular, with respect to integrating self-healing polymers to create bioinspired soft self-healing devices. Herein, a novel piezoelectric-driven self-healing leaf-motion mimic actuator is designed by combining a thermoplastic methyl thioglycolate-modified styrene-butadiene-styrene (MGSBS) elastomer with a piezoelectric macrofiber composite (MFC) for self-sensing applications. This article is the first demonstration of a self-sensing and self-healing actuator-sensor system, which is driven by a piezoelectric actuator and can mimic leaf motion. The leaf-motion actuator combines built-in dynamic sensing and room-temperature self-healing capabilities to restore macroscale cutting damage with an intrinsically high bandwidth of up to 10 kHz. The feasibility and potential of the new actuator for use in complex soft autonomous systems are demonstrated. These new results help to address the emerging influence of self-healing soft actuators and the challenges of sensing, actuation, and damage resistance in soft robotics.

@article{hickman_influence_2021,
	title = {Influence of the tetraalkoxysilane crosslinker on the properties of polysiloxane-based elastomers prepared by the {Lewis} acid-catalysed {Piers}-{Rubinsztajn} reaction},
	volume = {12},
	issn = {1759-9954},
	doi = {10.1039/d1py00872b},
	abstract = {We investigate the preparation of polysiloxane-based networks under solvent-free, ambient conditions using the Lewis acid catalysed Piers-Rubinsztajn (PR) reaction of hydride-terminated siloxanes with various tetrafunctional alkoxysilanes (tetraethoxysilane, tetrapropoxysilane, tetra-n-buxoxysilane, tetra-s-butoxysilane, tetra-s-butoxysilane, and tetrakis(2-ethylbutoxy)silane) as crosslinkers. We explore the effects of polysiloxane chain length and crosslinker alkyl group on the rheological performance of the elastomers. By analysing the reaction progress by grazing angle Fourier-transform infrared spectroscopy (FTIR) and determining the rheological properties of the resulting materials, we show that the use of linear or branched alkoxysilanes strongly influences the morphology and properties of these network polymers. We have shown the PR process can be tailored to reliably produce homogeneous, polysiloxane network materials. This work provides information on the relative rates of network formation under ambient conditions with an emphasis on the impact of crosslinker alkyl chain length. Our results show that electronics and sterics both play critical roles in influencing the rate of the curing reaction. Crucially, we newly demonstrate the benefit of a having tertiary carbon alpha to the SiO reaction centre, as is the case for the tetra-s-butoxysilane crosslinker, for delivering exceptionally rapid network cure and a concomitant enhancement in storage modulus of the resultant materials.},
	number = {34},
	urldate = {2021-08-28},
	journal = {POLYMER CHEMISTRY},
	author = {Hickman, Andrew M. and Chmel, Nikola and Cameron, Neil R. and Keddie, Daniel J. and Schiller, Tara L.},
	month = sep,
	year = {2021},
	pages = {4934--4941},
}

We investigate the preparation of polysiloxane-based networks under solvent-free, ambient conditions using the Lewis acid catalysed Piers-Rubinsztajn (PR) reaction of hydride-terminated siloxanes with various tetrafunctional alkoxysilanes (tetraethoxysilane, tetrapropoxysilane, tetra-n-buxoxysilane, tetra-s-butoxysilane, tetra-s-butoxysilane, and tetrakis(2-ethylbutoxy)silane) as crosslinkers. We explore the effects of polysiloxane chain length and crosslinker alkyl group on the rheological performance of the elastomers. By analysing the reaction progress by grazing angle Fourier-transform infrared spectroscopy (FTIR) and determining the rheological properties of the resulting materials, we show that the use of linear or branched alkoxysilanes strongly influences the morphology and properties of these network polymers. We have shown the PR process can be tailored to reliably produce homogeneous, polysiloxane network materials. This work provides information on the relative rates of network formation under ambient conditions with an emphasis on the impact of crosslinker alkyl chain length. Our results show that electronics and sterics both play critical roles in influencing the rate of the curing reaction. Crucially, we newly demonstrate the benefit of a having tertiary carbon alpha to the SiO reaction centre, as is the case for the tetra-s-butoxysilane crosslinker, for delivering exceptionally rapid network cure and a concomitant enhancement in storage modulus of the resultant materials.

@article{kerr_bistrithiocarbonate_2021,
	title = {Bis(trithiocarbonate) {Disulfides}: {From} {Chain} {Transfer} {Agent} {Precursors} to {Iniferter} {Control} {Agents} in {RAFT} {Polymerization}},
	volume = {54},
	issn = {0024-9297},
	doi = {10.1021/acs.macromol.1c00565},
	abstract = {While disulfide compounds have long been known to act as iniferters in radical polymerizations, the usage of bis(trithioacarbonates) directly in the RAFT process has been studied relatively little. Typically, these compounds are considered as precursors to other RAFT agents, either through organic synthesis or in situ generation during polymerization. Herein, we study the behavior of dodecyltrithiocarbonate disulfide in detail, using either thermal azo initiator or photoiniferter reaction conditions with a range of mononmers. We find that the iniferter product is mainly obtained, although side reactions lead to a mixture of end-group species. Control is highly dependent on the monomer family, with methacrylates yielding the narrowest dispersity polymers.},
	number = {14},
	urldate = {2021-08-08},
	journal = {MACROMOLECULES},
	author = {Kerr, Andrew and Moriceau, Guillaume and Przybyla, Magdalena A. and Smith, Timothy and Perrier, Sebastien},
	month = jul,
	year = {2021},
	pages = {6649--6661},
}

While disulfide compounds have long been known to act as iniferters in radical polymerizations, the usage of bis(trithioacarbonates) directly in the RAFT process has been studied relatively little. Typically, these compounds are considered as precursors to other RAFT agents, either through organic synthesis or in situ generation during polymerization. Herein, we study the behavior of dodecyltrithiocarbonate disulfide in detail, using either thermal azo initiator or photoiniferter reaction conditions with a range of mononmers. We find that the iniferter product is mainly obtained, although side reactions lead to a mixture of end-group species. Control is highly dependent on the monomer family, with methacrylates yielding the narrowest dispersity polymers.

@article{morgan_characterization_2021,
	title = {Characterization {Across} a {Dispersity}: {Polymer} {Mass} {Spectrometry} in the {Second} {Dimension}},
	volume = {32},
	issn = {1044-0305},
	doi = {10.1021/jasms.1c00106},
	abstract = {Due to the natural dispersity that is present in synthetic polymers, an added complexity is always present in the analysis of polymeric species. Tandem mass spectrometry analysis requires the isolation of individual precursors before a fragmentation event to allow the unambiguous characterization of these species and is not viable at certain levels of complexity due to achievable isolation widths. Two-dimensional mass spectrometry (2DMS) fragments ions and correlates fragments with their corresponding precursors without the need for isolation. In this study, 2DMS electron capture dissociation (ECD) fragmentation of a polyoxazoline and polyacrylamide species was carried out, resulting in the analysis of byproducts and individual polymer species without the use of chromatographic techniques. This study shows that 2DMS ECD is a powerful tool for the analysis of polyacrylamide and polyoxazoline species and offers a new dimension in the characterization of polymers.},
	number = {8},
	urldate = {2021-11-19},
	journal = {JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY},
	author = {Morgan, Tomos E. and Wootton, Christopher A. and Marzullo, Bryan and Paris, Johanna and Kerr, Andrew and Ellacott, Sean H. and van Agthoven, Maria A. and Barrow, Mark P. and Bristow, Anthony W. T. and Perrier, Sebastien and O'Connor, Peter B.},
	month = aug,
	year = {2021},
	pages = {2153--2161},
}

Due to the natural dispersity that is present in synthetic polymers, an added complexity is always present in the analysis of polymeric species. Tandem mass spectrometry analysis requires the isolation of individual precursors before a fragmentation event to allow the unambiguous characterization of these species and is not viable at certain levels of complexity due to achievable isolation widths. Two-dimensional mass spectrometry (2DMS) fragments ions and correlates fragments with their corresponding precursors without the need for isolation. In this study, 2DMS electron capture dissociation (ECD) fragmentation of a polyoxazoline and polyacrylamide species was carried out, resulting in the analysis of byproducts and individual polymer species without the use of chromatographic techniques. This study shows that 2DMS ECD is a powerful tool for the analysis of polyacrylamide and polyoxazoline species and offers a new dimension in the characterization of polymers.

@article{hand_application_2021,
	title = {Application of comprehensive {2D} chromatography in the anti-doping field: {Sample} identification and quantification},
	volume = {1178},
	issn = {1570-0232},
	doi = {10.1016/j.jchromb.2021.122584},
	abstract = {Anti-doping analysis requires an exceptional level of accuracy and precision given the stakes that are at play. Current methods rely on the application of chromatographic techniques linked with mass spectrometry to provide this. However, despite the effectiveness of these techniques in achieving good selectivity and specificity, some issues still exist. In order to reach the minimum required performance level as set by WADA, labs commonly use selective monitoring by quadrupole mass spectrometry. This can be potentially fooled through the use of masking agents or by moving the peaks, as often only a small portion of the spectrum is used for analysis. Further issues exist in the inability to detect new or modified compounds, or to reanalyse samples/spectra. One technique that could overcome these problems is that of comprehensive 2D chromatography. Here a second separation column is employed to generate greater separative power. Compared to conventional separation, GCxGC allows for a greater peak capacity (i.e., number of peaks that can be resolved within a given time) and greater separation of coeluting compounds, which makes the technique promising for the complex task required in anti-doping. When combined with Time of Flight Mass Spectrometry this technique demonstrates vast potential allowing for full mass range datasets to be obtained for retroactive analysis. Similarly, LCxLC provides improvements in resolving power compared to its 1D counterpart and can be used both online as part of the analysis or offline solely as a purification step. In this review we summarise the work in this field so far, how comprehensive chromatography has been applied to anti-doping studies, and discuss the future application for this technique.},
	urldate = {2021-08-08},
	journal = {JOURNAL OF CHROMATOGRAPHY B-ANALYTICAL TECHNOLOGIES IN THE BIOMEDICAL AND LIFE SCIENCES},
	author = {Hand, Rachel A. and Bassindale, Thomas and Turner, Nicholas and Morgan, Geraint},
	month = jul,
	year = {2021},
}

Anti-doping analysis requires an exceptional level of accuracy and precision given the stakes that are at play. Current methods rely on the application of chromatographic techniques linked with mass spectrometry to provide this. However, despite the effectiveness of these techniques in achieving good selectivity and specificity, some issues still exist. In order to reach the minimum required performance level as set by WADA, labs commonly use selective monitoring by quadrupole mass spectrometry. This can be potentially fooled through the use of masking agents or by moving the peaks, as often only a small portion of the spectrum is used for analysis. Further issues exist in the inability to detect new or modified compounds, or to reanalyse samples/spectra. One technique that could overcome these problems is that of comprehensive 2D chromatography. Here a second separation column is employed to generate greater separative power. Compared to conventional separation, GCxGC allows for a greater peak capacity (i.e., number of peaks that can be resolved within a given time) and greater separation of coeluting compounds, which makes the technique promising for the complex task required in anti-doping. When combined with Time of Flight Mass Spectrometry this technique demonstrates vast potential allowing for full mass range datasets to be obtained for retroactive analysis. Similarly, LCxLC provides improvements in resolving power compared to its 1D counterpart and can be used both online as part of the analysis or offline solely as a purification step. In this review we summarise the work in this field so far, how comprehensive chromatography has been applied to anti-doping studies, and discuss the future application for this technique.

@article{samantaray_design_2021,
	title = {Design and {Control} of {Compostability} in {Synthetic} {Biopolyesters}},
	volume = {9},
	issn = {2168-0485},
	doi = {10.1021/acssuschemeng.1c01424},
	abstract = {The aerobic composting and anaerobic digestion of plastics is a promising route to recovering the multidimensional value from biodegradable single-use plastics. At present, the collection, separation, and management of biodegradable plastic waste are extremely challenging, and the majority of these plastics still end up in landfills or incineration facilities. This is because not all biodegradable plastics can be treated using organic waste management options (composting). In addition, end-users at a domestic and industrial level are often unaware of the compostability potential of biodegradable plastics, which results in the mismanagement of these types of plastic. A greater understanding of the compostability of biodegradable plastics will generate the required knowledge base for interventions that support their market penetration, use, and proper management. In this review, we clarify the concepts of biodegradability and compostability in bioplastics, in particular commercial synthetic biopolyesters, which have increasing technical and economic importance, and discuss how macromolecular design, blending, and additives can be used to modify their compostability. Future trends on the uptake of compostable and biodegradable bioplastics are also discussed.},
	number = {28},
	urldate = {2021-07-30},
	journal = {ACS SUSTAINABLE CHEMISTRY \& ENGINEERING},
	author = {Samantaray, Paresh Kumar and Little, Alastair and Wemyss, Alan M. and Iacovidou, Eleni and Wan, Chaoying},
	month = jul,
	year = {2021},
	pages = {9151--9164},
}

The aerobic composting and anaerobic digestion of plastics is a promising route to recovering the multidimensional value from biodegradable single-use plastics. At present, the collection, separation, and management of biodegradable plastic waste are extremely challenging, and the majority of these plastics still end up in landfills or incineration facilities. This is because not all biodegradable plastics can be treated using organic waste management options (composting). In addition, end-users at a domestic and industrial level are often unaware of the compostability potential of biodegradable plastics, which results in the mismanagement of these types of plastic. A greater understanding of the compostability of biodegradable plastics will generate the required knowledge base for interventions that support their market penetration, use, and proper management. In this review, we clarify the concepts of biodegradability and compostability in bioplastics, in particular commercial synthetic biopolyesters, which have increasing technical and economic importance, and discuss how macromolecular design, blending, and additives can be used to modify their compostability. Future trends on the uptake of compostable and biodegradable bioplastics are also discussed.

@article{rho_situ_2021,
	title = {In situ monitoring of {PISA} morphologies},
	volume = {12},
	issn = {1759-9954},
	doi = {10.1039/d1py00239b},
	abstract = {Polymerization-induced self-assembly (PISA) is a facile method to obtain block copolymer aggregates with defined morphologies. However, the transitions between these morphologies have been difficult to monitor directly in real-time during the polymerization. Herein, we describe a straightforward and readily accessible in situ method to monitor the evolution of nanostructure via changes in internal hydrophobicity during the PISA process using a polymer-tethered pyrene fluorescent probe. We were able to correlate morphological transitions with changes of the pyrene emission and gain unprecedented insight into the evolution of core hydrophobicity during PISA.},
	number = {27},
	urldate = {2021-07-01},
	journal = {POLYMER CHEMISTRY},
	author = {Rho, Julia Y. and Scheutz, Georg M. and Hakkinen, Satu and Garrison, John B. and Song, Qiao and Yang, Jie and Richardson, Robert and Perrier, Sebastien and Sumerlin, Brent S.},
	month = jul,
	year = {2021},
	pages = {3947--3952},
}

Polymerization-induced self-assembly (PISA) is a facile method to obtain block copolymer aggregates with defined morphologies. However, the transitions between these morphologies have been difficult to monitor directly in real-time during the polymerization. Herein, we describe a straightforward and readily accessible in situ method to monitor the evolution of nanostructure via changes in internal hydrophobicity during the PISA process using a polymer-tethered pyrene fluorescent probe. We were able to correlate morphological transitions with changes of the pyrene emission and gain unprecedented insight into the evolution of core hydrophobicity during PISA.

@article{malina_feii_2021,
	title = {{FeII} {Metallohelices} {Stabilize} {DNA} {G}-{Quadruplexes} and {Downregulate} the {Expression} of {G}-{Quadruplex}-{Regulated} {Oncogenes}},
	volume = {27},
	issn = {0947-6539},
	doi = {10.1002/chem.202101388},
	abstract = {DNA G-quadruplexes (G4s) have been identified within the promoter regions of many proto-oncogenes. Thus, G4s represent attractive targets for cancer therapy, and the design and development of new drugs as G4 binders is a very active field of medicinal chemistry. Here, molecular biophysics and biology methods were employed to investigate the interaction of chiral metallohelices with a series of four DNA G4s (hTelo, c-myc, c-kit1, c-kit2) that are formed by the human telomeric sequence (hTelo) and in the promoter regions of c-MYC and c-KIT proto-oncogenes. We show that the investigated water-compatible, optically pure metallohelices, which are made by self-assembly of simple nonpeptidic organic components around Fe-II ions and exhibit bioactivity emulating the natural systems, bind with high affinity to G4 DNA and much lower affinity to duplex DNA. Notably, both enantiomers of a metallohelix containing a m-xylenyl bridge (5 b) were found to effectively inhibit primer elongation catalyzed by Taq DNA polymerase by stabilizing G4 structures formed in the template strands containing c-myc and c-kit2 G4-forming sequences. Moreover, both enantiomers of 5 b downregulated the expression of c-MYC and c-KIT oncogenes in human embryonic kidney cells at mRNA and protein levels. As metallohelices also bind alternative nucleic acid structures, they hold promise as potential multitargeted drugs.},
	number = {45},
	urldate = {2021-07-11},
	journal = {CHEMISTRY-A EUROPEAN JOURNAL},
	author = {Malina, Jaroslav and Kostrhunova, Hana and Scott, Peter and Brabec, Viktor},
	month = aug,
	year = {2021},
	pages = {11682--11692},
}

DNA G-quadruplexes (G4s) have been identified within the promoter regions of many proto-oncogenes. Thus, G4s represent attractive targets for cancer therapy, and the design and development of new drugs as G4 binders is a very active field of medicinal chemistry. Here, molecular biophysics and biology methods were employed to investigate the interaction of chiral metallohelices with a series of four DNA G4s (hTelo, c-myc, c-kit1, c-kit2) that are formed by the human telomeric sequence (hTelo) and in the promoter regions of c-MYC and c-KIT proto-oncogenes. We show that the investigated water-compatible, optically pure metallohelices, which are made by self-assembly of simple nonpeptidic organic components around Fe-II ions and exhibit bioactivity emulating the natural systems, bind with high affinity to G4 DNA and much lower affinity to duplex DNA. Notably, both enantiomers of a metallohelix containing a m-xylenyl bridge (5 b) were found to effectively inhibit primer elongation catalyzed by Taq DNA polymerase by stabilizing G4 structures formed in the template strands containing c-myc and c-kit2 G4-forming sequences. Moreover, both enantiomers of 5 b downregulated the expression of c-MYC and c-KIT oncogenes in human embryonic kidney cells at mRNA and protein levels. As metallohelices also bind alternative nucleic acid structures, they hold promise as potential multitargeted drugs.

@article{ekeocha_challenges_2021,
	title = {Challenges and {Opportunities} of {Self}-{Healing} {Polymers} and {Devices} for {Extreme} and {Hostile} {Environments}},
	volume = {33},
	issn = {0935-9648},
	doi = {10.1002/adma.202008052},
	abstract = {Engineering materials and devices can be damaged during their service life as a result of mechanical fatigue, punctures, electrical breakdown, and electrochemical corrosion. This damage can lead to unexpected failure during operation, which requires regular inspection, repair, and replacement of the products, resulting in additional energy consumption and cost. During operation in challenging, extreme, or harsh environments, such as those encountered in high or low temperature, nuclear, offshore, space, and deep mining environments, the robustness and stability of materials and devices are extremely important. Over recent decades, significant effort has been invested into improving the robustness and stability of materials through either structural design, the introduction of new chemistry, or improved manufacturing processes. Inspired by natural systems, the creation of self-healing materials has the potential to overcome these challenges and provide a route to achieve dynamic repair during service. Current research on self-healing polymers remains in its infancy, and self-healing behavior under harsh and extreme conditions is a particularly untapped area of research. Here, the self-healing mechanisms and performance of materials under a variety of harsh environments are discussed. An overview of polymer-based devices developed for a range of challenging environments is provided, along with areas for future research.},
	number = {33},
	urldate = {2021-07-15},
	journal = {ADVANCED MATERIALS},
	author = {Ekeocha, James and Ellingford, Christopher and Pan, Min and Wemyss, Alan M. and Bowen, Christopher and Wan, Chaoying},
	month = aug,
	year = {2021},
}

Engineering materials and devices can be damaged during their service life as a result of mechanical fatigue, punctures, electrical breakdown, and electrochemical corrosion. This damage can lead to unexpected failure during operation, which requires regular inspection, repair, and replacement of the products, resulting in additional energy consumption and cost. During operation in challenging, extreme, or harsh environments, such as those encountered in high or low temperature, nuclear, offshore, space, and deep mining environments, the robustness and stability of materials and devices are extremely important. Over recent decades, significant effort has been invested into improving the robustness and stability of materials through either structural design, the introduction of new chemistry, or improved manufacturing processes. Inspired by natural systems, the creation of self-healing materials has the potential to overcome these challenges and provide a route to achieve dynamic repair during service. Current research on self-healing polymers remains in its infancy, and self-healing behavior under harsh and extreme conditions is a particularly untapped area of research. Here, the self-healing mechanisms and performance of materials under a variety of harsh environments are discussed. An overview of polymer-based devices developed for a range of challenging environments is provided, along with areas for future research.

@article{cachelin_optical_2021,
	title = {Optical {UV} {Dosimeters} {Based} on {Photoracemization} of ({R})-(+)-1,1′-{Bi}(2-{Napthol}) ({BINOL}) within a {Chiral} {Nematic} {Liquid} {Crystalline} {Matrix}},
	volume = {6},
	issn = {2365-6549},
	doi = {10.1002/slct.202101229},
	abstract = {Accurate and low-cost wearable or portable monitors for personal solar ultraviolet (UV) exposure are of interest to reduce the risk of adverse UV effects such as eye diseases, sunburn and skin cancer. Here, a novel sensor involving the racemization of a chiral dopant within a nematic liquid crystalline matrix is described, and the suitability of these sensors to act as personal UV dosimeters is explored. It was shown that these sensors respond to UV light with a significant change in the position of the reflection band of the chiral nematic liquid crystal. The sensitivity of these sensors is shown to be 0.23 nm/mJcm(-2). This corresponds to a change of 80 nm over a dose equivalent to two hours of solar exposure.},
	number = {21},
	urldate = {2021-07-10},
	journal = {CHEMISTRYSELECT},
	author = {Cachelin, Pascal and Khandewal, Hitesh and Debije, Michael G. and Peijs, Ton and Bastiaansen, Cees W. M.},
	month = jun,
	year = {2021},
	pages = {5266--5270},
}

Accurate and low-cost wearable or portable monitors for personal solar ultraviolet (UV) exposure are of interest to reduce the risk of adverse UV effects such as eye diseases, sunburn and skin cancer. Here, a novel sensor involving the racemization of a chiral dopant within a nematic liquid crystalline matrix is described, and the suitability of these sensors to act as personal UV dosimeters is explored. It was shown that these sensors respond to UV light with a significant change in the position of the reflection band of the chiral nematic liquid crystal. The sensitivity of these sensors is shown to be 0.23 nm/mJcm(-2). This corresponds to a change of 80 nm over a dose equivalent to two hours of solar exposure.

@article{pancaro_polymeric_2021,
	title = {The polymeric glyco-linker controls the signal outputs for plasmonic gold nanorod biosensors due to biocorona formation},
	volume = {13},
	issn = {2040-3364},
	doi = {10.1039/d1nr01548f},
	abstract = {Gold nanorods (GNRs) are a promising platform for nanoplasmonic biosensing. The localised surface plasmon resonance (LSPR) peak of GNRs is located in the near-infrared optical window and is sensitive to local binding events, enabling label-free detection of biomarkers in complex biological fluids. A key challenge in the development of such sensors is achieving target affinity and selectivity, while both minimizing non-specific binding and maintaining colloidal stability. Herein, we reveal how GNRs decorated with galactosamine-terminated polymer ligands display significantly different binding responses in buffer compared to serum, due to biocorona formation, and how biocorona displacement due to lectin binding plays a key role in their optical responses. GNRs were coated with either poly(N-(2-hydroxypropyl)methacrylamide) (PHPMA) or poly(N-hydroxyethyl acrylamide) (PHEA) prepared via reversible addition-fragmentation chain-transfer (RAFT) polymerisation and end-functionalised with galactosamine (Gal) as the lectin-targeting unit. In buffer Gal-PHEA-coated GNRs aggregated upon soybean agglutinin (SBA) addition, whereas Gal-PHPMA-coated GNRs exhibited a red-shift of the LSPR spectrum without aggregation. In contrast, when incubated in serum Gal-PHPMA-coated nanorods showed no binding response, while Gal-PHEA GNRs exhibited a dose-dependent blue-shift of the LSPR peak, which is the opposite direction (red-shift) to what was observed in buffer. This differential behaviour was attributed to biocorona formation onto both polymer-coated GNRs, shown by differential centrifugal sedimentation and nanoparticle tracking analysis. Upon addition of SBA to the Gal-PHEA coated nanorods, signal was generated due to displacement of weakly-bound biocorona components by lectin binding. However, in the case of Gal-PHPMA which had a thicker corona, attributed to lower polymer grafting densities, addition of SBA did not lead to biocorona displacement and there was no signal output. These results show that plasmonic optical responses in complex biological media can be significantly affected by biocorona formation, and that biocorona formation itself does not prevent sensing so long as its exact nature (e.g. 'hard versus soft') is tuned.},
	number = {24},
	urldate = {2021-06-19},
	journal = {NANOSCALE},
	author = {Pancaro, Alessia and Szymonik, Michal and Georgiou, Panagiotis G. and Baker, Alexander N. and Walker, Marc and Adriaensens, Peter and Hendrix, Jelle and Gibson, I, Matthew and Nelissen, Inge},
	month = jun,
	year = {2021},
	pages = {10837--10848},
}

Gold nanorods (GNRs) are a promising platform for nanoplasmonic biosensing. The localised surface plasmon resonance (LSPR) peak of GNRs is located in the near-infrared optical window and is sensitive to local binding events, enabling label-free detection of biomarkers in complex biological fluids. A key challenge in the development of such sensors is achieving target affinity and selectivity, while both minimizing non-specific binding and maintaining colloidal stability. Herein, we reveal how GNRs decorated with galactosamine-terminated polymer ligands display significantly different binding responses in buffer compared to serum, due to biocorona formation, and how biocorona displacement due to lectin binding plays a key role in their optical responses. GNRs were coated with either poly(N-(2-hydroxypropyl)methacrylamide) (PHPMA) or poly(N-hydroxyethyl acrylamide) (PHEA) prepared via reversible addition-fragmentation chain-transfer (RAFT) polymerisation and end-functionalised with galactosamine (Gal) as the lectin-targeting unit. In buffer Gal-PHEA-coated GNRs aggregated upon soybean agglutinin (SBA) addition, whereas Gal-PHPMA-coated GNRs exhibited a red-shift of the LSPR spectrum without aggregation. In contrast, when incubated in serum Gal-PHPMA-coated nanorods showed no binding response, while Gal-PHEA GNRs exhibited a dose-dependent blue-shift of the LSPR peak, which is the opposite direction (red-shift) to what was observed in buffer. This differential behaviour was attributed to biocorona formation onto both polymer-coated GNRs, shown by differential centrifugal sedimentation and nanoparticle tracking analysis. Upon addition of SBA to the Gal-PHEA coated nanorods, signal was generated due to displacement of weakly-bound biocorona components by lectin binding. However, in the case of Gal-PHPMA which had a thicker corona, attributed to lower polymer grafting densities, addition of SBA did not lead to biocorona displacement and there was no signal output. These results show that plasmonic optical responses in complex biological media can be significantly affected by biocorona formation, and that biocorona formation itself does not prevent sensing so long as its exact nature (e.g. 'hard versus soft') is tuned.

@article{song_tubular_2021,
	title = {Tubular supramolecular alternating copolymers fabricated by cyclic peptide-polymer conjugates},
	volume = {12},
	issn = {2041-6520},
	doi = {10.1039/d1sc02389f},
	abstract = {Supramolecular copolymers are an emerging class of materials, which bring together different properties and functionalities of multiple components via noncovalent interactions. While it is widely acknowledged that the repeating unit sequence plays an essential role on the performance of these materials, mastering and tuning the supramolecular copolymer sequence is still an open challenge. To date, only statistical supramolecular copolymers have been reported using cyclic peptide-polymer conjugates as building blocks. To enrich the diversity of tubular supramolecular copolymers, we report here a strategy of controlling their sequences by introducing an extra complementary noncovalent interaction. Hence, two conjugates bearing one electron donor and one electron acceptor, respectively, are designed. The two conjugates can individually assemble into tubular supramolecular homopolymers driven by the multiple hydrogen bonding interactions between cyclic peptides. However, the complementary charge transfer interaction between the electron donor and acceptor makes each conjugate more favorable for complexing with its counterpart, resulting in an alternating sequence of the supramolecular copolymer. Following the same principle, more functional supramolecular alternating copolymers are expected to be designed and constructed via other complementary noncovalent interactions (electrostatic interactions, metal coordination interactions, and host-guest interactions, etc.).},
	number = {26},
	urldate = {2021-06-15},
	journal = {CHEMICAL SCIENCE},
	author = {Song, Qiao and Kerr, Andrew and Yang, Jie and Hall, Stephen C. L. and Perrier, Sebastien},
	month = jul,
	year = {2021},
	pages = {9096--9103},
}

Supramolecular copolymers are an emerging class of materials, which bring together different properties and functionalities of multiple components via noncovalent interactions. While it is widely acknowledged that the repeating unit sequence plays an essential role on the performance of these materials, mastering and tuning the supramolecular copolymer sequence is still an open challenge. To date, only statistical supramolecular copolymers have been reported using cyclic peptide-polymer conjugates as building blocks. To enrich the diversity of tubular supramolecular copolymers, we report here a strategy of controlling their sequences by introducing an extra complementary noncovalent interaction. Hence, two conjugates bearing one electron donor and one electron acceptor, respectively, are designed. The two conjugates can individually assemble into tubular supramolecular homopolymers driven by the multiple hydrogen bonding interactions between cyclic peptides. However, the complementary charge transfer interaction between the electron donor and acceptor makes each conjugate more favorable for complexing with its counterpart, resulting in an alternating sequence of the supramolecular copolymer. Following the same principle, more functional supramolecular alternating copolymers are expected to be designed and constructed via other complementary noncovalent interactions (electrostatic interactions, metal coordination interactions, and host-guest interactions, etc.).

@article{drain_solvent_2021,
	title = {Solvent {Dependency} in the {Synthesis} of {Multiblock} and {Cyclic} {Poly}(2-oxazoline)},
	volume = {54},
	issn = {0024-9297},
	doi = {10.1021/acs.macromol.1c00529},
	abstract = {Multiblock copolymers as well as cyclic polymers exhibit unique physical properties and are being utilized in various applications. However, the synthesis of such polymers is quite challenging because there is a delicate balance in achieving either structure. Here, we report a surprising solvent dependence on the cyclization and step-growth reactions of poly(2-alkyl 2-oxazoline)s. Additionally, other important parameters such as catalyst concentration, polymer concentration, and temperature were investigated, and their influences on the obtained ratio between step-growth and cyclization polymers are discussed. Step growth of a telechelic poly(2-ethyl 2-oxazoline) macromonomer yielded a multiblock polymer containing, on average, eight repeating units. Moreover, reaction conditions in order to favor cyclization over step-growth polymerization were optimized for poly(2-fatty acid-2-oxazoline). Finally, using the optimized conditions, an up to 80:20 cyclization/step-growth polymer mixture was obtained at a relatively high polymer concentration (50 mg/mL).},
	number = {12},
	urldate = {2021-07-22},
	journal = {MACROMOLECULES},
	author = {Drain, B. A. and Beyer, V. P. and Cattoz, B. and Becer, C. R.},
	month = jun,
	year = {2021},
	note = {Infineum UK Ltd},
	pages = {5549--5556},
}

Multiblock copolymers as well as cyclic polymers exhibit unique physical properties and are being utilized in various applications. However, the synthesis of such polymers is quite challenging because there is a delicate balance in achieving either structure. Here, we report a surprising solvent dependence on the cyclization and step-growth reactions of poly(2-alkyl 2-oxazoline)s. Additionally, other important parameters such as catalyst concentration, polymer concentration, and temperature were investigated, and their influences on the obtained ratio between step-growth and cyclization polymers are discussed. Step growth of a telechelic poly(2-ethyl 2-oxazoline) macromonomer yielded a multiblock polymer containing, on average, eight repeating units. Moreover, reaction conditions in order to favor cyclization over step-growth polymerization were optimized for poly(2-fatty acid-2-oxazoline). Finally, using the optimized conditions, an up to 80:20 cyclization/step-growth polymer mixture was obtained at a relatively high polymer concentration (50 mg/mL).

@article{concilio_oxazoline-methacrylate_2021,
	title = {Oxazoline-methacrylate graft-copolymers with upper critical solution temperature behaviour in {Yubase} oil},
	volume = {12},
	issn = {1759-9954},
	doi = {10.1039/d1py00534k},
	abstract = {Thermoresponsive behavior of polymers in aqueous solutions has been widely studied and utilized in various applications. However, the fundamental understanding on the use of oil soluble polymers in non-aqueous solutions is very limited. Herein, we report the synthesis of linear homo and copolymers as well as graft-copolymers based on 2-oxazoline monomers and the investigation of their solution behavior and thermal properties via turbidity measurements and thermal analyses (DSC and TGA). The homo and copolymers were synthetized via living cationic ring-opening polymerization (CROP) of 2-stearyl-2-oxazoline (SteOx) and 2-ethyl-2-oxazoline (EtOx) and their composition was varied in order to tune the thermoresponsive behavior in a commercially available base oil (Yubase-4). The graft-copolymers were obtained using the grafting-onto method. The backbone composed of a methacrylic acid and 2-ethylhexyl methacrylate copolymer was synthetized via reversible addition-fragmentation chain-transfer (RAFT) polymerization, while side chains consisting of SteOx-EtOx copolymers were obtained via CROP. Various polymerization parameters were evaluated in order to optimize the grafting efficiency and the solubility in oil of the synthetized graft-copolymers. It was seen that not only the overall hydrophobicity of the polymer chains but also the overall order of the system have significant effects on the upper critical solution temperature (UCST) in oil. Finally, a relationship between the crystallization temperature measured using DSC and the transition temperature (T-trans) values obtained from the turbidity measurements was compared.},
	number = {30},
	urldate = {2021-06-09},
	journal = {POLYMER CHEMISTRY},
	author = {Concilio, Matilde and Nguyen, Nga and Becer, C. Remzi},
	month = aug,
	year = {2021},
	note = {Infineum USA},
	pages = {4359--4371},
}

Thermoresponsive behavior of polymers in aqueous solutions has been widely studied and utilized in various applications. However, the fundamental understanding on the use of oil soluble polymers in non-aqueous solutions is very limited. Herein, we report the synthesis of linear homo and copolymers as well as graft-copolymers based on 2-oxazoline monomers and the investigation of their solution behavior and thermal properties via turbidity measurements and thermal analyses (DSC and TGA). The homo and copolymers were synthetized via living cationic ring-opening polymerization (CROP) of 2-stearyl-2-oxazoline (SteOx) and 2-ethyl-2-oxazoline (EtOx) and their composition was varied in order to tune the thermoresponsive behavior in a commercially available base oil (Yubase-4). The graft-copolymers were obtained using the grafting-onto method. The backbone composed of a methacrylic acid and 2-ethylhexyl methacrylate copolymer was synthetized via reversible addition-fragmentation chain-transfer (RAFT) polymerization, while side chains consisting of SteOx-EtOx copolymers were obtained via CROP. Various polymerization parameters were evaluated in order to optimize the grafting efficiency and the solubility in oil of the synthetized graft-copolymers. It was seen that not only the overall hydrophobicity of the polymer chains but also the overall order of the system have significant effects on the upper critical solution temperature (UCST) in oil. Finally, a relationship between the crystallization temperature measured using DSC and the transition temperature (T-trans) values obtained from the turbidity measurements was compared.

@article{marathianos_controlling_2021,
	title = {Controlling the {Particle} {Size} in {Surfactant}-{Free} {Latexes} from ω-{Propenyl} {Oligomers} {Obtained} through {Catalytic} {Chain} {Transfer} {Polymerization}},
	volume = {3},
	issn = {2637-6105},
	doi = {10.1021/acsapm.1c00366},
	abstract = {The surfactant-free emulsion polymerization of styrene, butyl methacrylate, and methyl methacrylate was conducted under starved-feed conditions in the presence of omega-propenyl poly(methacrylic acid) (pMAA) oligomers, obtained through catalytic chain transfer polymerization, as a stabilizer. A range of monomer to oligomer molar ratios were used, which resulted in stable latexes without any sign of coagulation for more than two years at ambient temperature. Moreover, the effect of substituting pMAA for a nonionic stabilizer (poly(glycerol monomethacrylate)) or a low molar mass ionic surfactant (sodium dodecyl sulfate) on the final properties of the latex was evaluated. Kinetic studies gave insight into the process through which the stabilization occurs, indicating that in the initial stages, monomeric radicals react with the oligomer to form amphiphilic copolymers. Subsequently, micelles formed from these copolymers swell with the additional monomer, which then polymerizes through a free-radical mechanism. Thermogravimetric analysis showed that the polymers have thermal stability up to 420 degrees C, while differential scanning calorimetry revealed copolymer compatibility only at low monomer to oligomer molar ratios. Finally, static and dynamic light scattering techniques and scanning electron microscopy were used for the determination of the particle size and particle size distributions and the development of a linear regression model to summarize the particle size characterization, according to which an increac in monomer to oligomer ratios by a factor of x is associated with a proportional increase in the particle volume.},
	number = {6},
	urldate = {2021-07-07},
	journal = {ACS APPLIED POLYMER MATERIALS},
	author = {Marathianos, Arkadios and Wemyss, Alan M. and Liarou, Evelina and Jones, Joseph R. and Shegiwal, Ataulla and Town, James S. and Lester, Daniel W. and Li, Youngguang and Haddleton, David M.},
	month = jun,
	year = {2021},
	pages = {3185--3196},
}

The surfactant-free emulsion polymerization of styrene, butyl methacrylate, and methyl methacrylate was conducted under starved-feed conditions in the presence of omega-propenyl poly(methacrylic acid) (pMAA) oligomers, obtained through catalytic chain transfer polymerization, as a stabilizer. A range of monomer to oligomer molar ratios were used, which resulted in stable latexes without any sign of coagulation for more than two years at ambient temperature. Moreover, the effect of substituting pMAA for a nonionic stabilizer (poly(glycerol monomethacrylate)) or a low molar mass ionic surfactant (sodium dodecyl sulfate) on the final properties of the latex was evaluated. Kinetic studies gave insight into the process through which the stabilization occurs, indicating that in the initial stages, monomeric radicals react with the oligomer to form amphiphilic copolymers. Subsequently, micelles formed from these copolymers swell with the additional monomer, which then polymerizes through a free-radical mechanism. Thermogravimetric analysis showed that the polymers have thermal stability up to 420 degrees C, while differential scanning calorimetry revealed copolymer compatibility only at low monomer to oligomer molar ratios. Finally, static and dynamic light scattering techniques and scanning electron microscopy were used for the determination of the particle size and particle size distributions and the development of a linear regression model to summarize the particle size characterization, according to which an increac in monomer to oligomer ratios by a factor of x is associated with a proportional increase in the particle volume.

@article{zhu_anchoring_2021,
	title = {An anchoring array assembly method for enhancing the electrical conductivity of composites of polypropylene and hybrid fillers},
	volume = {211},
	issn = {0266-3538},
	doi = {10.1016/j.compscitech.2021.108846},
	abstract = {Constructing an interconnected filler-filler network in a polymer matrix is essential for enhancing the electrical conductivity of polymer composites. This work describes an Anchoring Array Assembly method for distribution of copper particles (CP) and carbon fibers (CF) in a polypropylene (PP) matrix. Constrained by a predesigned array anchoring template, the CP distribution achieved a high packing density in the PP matrix during compression molding which is key for filling the gaps between CFs, as well as for forming an interconnected hybrid filler network. Using the fixed array anchoring design, the dispersion and flow behavior of the conductive fillers and the polymer matrix are critical. When the inclination angle between the groove of the anchor mold and the horizontal plane is greater than 11.5 degrees, the migration of CP in the molten PP in the anchor mold during the hot embossing process is restricted. The most conductive composites were obtained when the CPs were densely arranged in a triangular format. The conductive filler network was determined by the preset dense triangular "island-bridge" structure of the customized microarray mold. The conductivity of the composites prepared by the anchoring array assembly method (CF content 18 vol.\% and CP content 2 vol.\%) reached 137.70 S/m, 52 times higher than that prepared by traditional hot embossing methods with the same filler loading.},
	urldate = {2021-06-27},
	journal = {COMPOSITES SCIENCE AND TECHNOLOGY},
	author = {Zhu, Jiashu and Wan, Chaoying and Xu, Hong and Liu, Ying and Zhuang, Jian and Sun, Jingyao and Gao, Xiaolong and McNally, Tony and Huang, Yao and Wu, Daming},
	month = jul,
	year = {2021},
}

Constructing an interconnected filler-filler network in a polymer matrix is essential for enhancing the electrical conductivity of polymer composites. This work describes an Anchoring Array Assembly method for distribution of copper particles (CP) and carbon fibers (CF) in a polypropylene (PP) matrix. Constrained by a predesigned array anchoring template, the CP distribution achieved a high packing density in the PP matrix during compression molding which is key for filling the gaps between CFs, as well as for forming an interconnected hybrid filler network. Using the fixed array anchoring design, the dispersion and flow behavior of the conductive fillers and the polymer matrix are critical. When the inclination angle between the groove of the anchor mold and the horizontal plane is greater than 11.5 degrees, the migration of CP in the molten PP in the anchor mold during the hot embossing process is restricted. The most conductive composites were obtained when the CPs were densely arranged in a triangular format. The conductive filler network was determined by the preset dense triangular "island-bridge" structure of the customized microarray mold. The conductivity of the composites prepared by the anchoring array assembly method (CF content 18 vol.% and CP content 2 vol.%) reached 137.70 S/m, 52 times higher than that prepared by traditional hot embossing methods with the same filler loading.

@article{booth_thermoresponsive_2021,
	title = {Thermoresponsive icy road sign by light scattering and enhanced fluorescence},
	volume = {9},
	issn = {2050-7526},
	doi = {10.1039/d1tc01189h},
	abstract = {Prototypes of flexible, electricity-free, ice warning signs for roads and pavements have been developed. A temperature triggered response in the form of an upper critical solution temperature (UCST) type phase separation targeted near the freezing point of water manifests itself through light scattering as a clear-to-opaque transition. It is simultaneously amplified by an enhanced photoluminescence effect. The conceptual road sign application is a multi-lamellar flexible strip with an active layer of a polystyrene-based solution. The solvent is a plasticizer, here either dioctyl phthalate (DOP) or its alternative 1,2-cyclohexane dicarboxylic acid diisononyl ester (DINCH). A collection of styrene-based macromolecules were made by free radical (co)polymerization, varying molecular weight and monomer feed composition. UCST-type phase diagrams for the polymer solutions were constructed from cloud point data measured with a bespoke photographic set-up, in which up to 30 samples were analyzed simultaneously monitoring both light scattering, in the form of opacity measurements, and fluorescence. For the latter, the concept of restricted motion enhanced photoluminescence, often referred to as aggregation-induced emission (AIE), was used. Polystyrene labelled with tetraphenylethylene (TPE) was used for this. The contrast between 'ON' and 'OFF' states in the conceptual ice warning signs was optimized by tuning the polymer concentration and the active layer thickness. Our prototype signs show full reversibility over many temperature cycles. We believe the concept can be of wider use in electricity-free signs and labels.},
	number = {22},
	urldate = {2021-05-28},
	journal = {JOURNAL OF MATERIALS CHEMISTRY C},
	author = {Booth, Joshua R. and Young, Robert A. and Richards Gonzales, Andres N. and Meakin, Zachary J. and Preuss-Weber, Corinna M. and Jaggers, Ross W. and Bon, Stefan A. F.},
	month = jun,
	year = {2021},
	pages = {7174--7185},
}

Prototypes of flexible, electricity-free, ice warning signs for roads and pavements have been developed. A temperature triggered response in the form of an upper critical solution temperature (UCST) type phase separation targeted near the freezing point of water manifests itself through light scattering as a clear-to-opaque transition. It is simultaneously amplified by an enhanced photoluminescence effect. The conceptual road sign application is a multi-lamellar flexible strip with an active layer of a polystyrene-based solution. The solvent is a plasticizer, here either dioctyl phthalate (DOP) or its alternative 1,2-cyclohexane dicarboxylic acid diisononyl ester (DINCH). A collection of styrene-based macromolecules were made by free radical (co)polymerization, varying molecular weight and monomer feed composition. UCST-type phase diagrams for the polymer solutions were constructed from cloud point data measured with a bespoke photographic set-up, in which up to 30 samples were analyzed simultaneously monitoring both light scattering, in the form of opacity measurements, and fluorescence. For the latter, the concept of restricted motion enhanced photoluminescence, often referred to as aggregation-induced emission (AIE), was used. Polystyrene labelled with tetraphenylethylene (TPE) was used for this. The contrast between 'ON' and 'OFF' states in the conceptual ice warning signs was optimized by tuning the polymer concentration and the active layer thickness. Our prototype signs show full reversibility over many temperature cycles. We believe the concept can be of wider use in electricity-free signs and labels.

@article{constantinou_homo-_2021,
	title = {Homo- and co-polymerisation of di(propylene glycol) methyl ether methacrylate - a new monomer},
	volume = {12},
	issn = {1759-9954},
	doi = {10.1039/d1py00444a},
	abstract = {In this study, a new methacrylate monomer with two propylene glycol groups on the side chain, di(propylene glycol) methyl ether methacrylate (diPGMA), was synthesised via an esterification reaction. This new monomer was homo- and co-polymerised for the first time via group transfer polymerisation (GTP). Nine ABA triblock copolymers were synthesised via a "one-pot" GTP, with A and B blocks being based on the hydrophilic and the thermoresponsive oligo(ethylene glycol) methyl ether methacrylate, average M-n 300 g mol(-1) (OEGMA300), and the hydrophobic diPGMA, respectively. The molar mass (MM) and OEGMA300/diPGMA content was systematically varied and the effect of this on the self-assembly and thermoresponsive properties was investigated. All copolymers were shown to self-assemble into aggregates and the size of these aggregates increased with both the MM of the polymer and the polymer content in diPGMA. A thermoresponse was observed in aqueous media, with the cloud point (CP) decreasing as the hydrophobic content increases, and the MM decreases. In concentrated aqueous solutions, the polymer with the highest MM and highest diPGMA content formed gels, whose storage modulus increases as a function of the concentration. This study reports a promising alternative hydrophobic monomer to be used in the fabrication of thermogelling materials.},
	number = {24},
	urldate = {2021-05-28},
	journal = {POLYMER CHEMISTRY},
	author = {Constantinou, Anna P. and Patias, Georgios and Somuncuoglu, Birsen and Brock, Toby and Lester, Daniel W. and Haddleton, David M. and Georgiou, Theoni K.},
	month = jun,
	year = {2021},
	pages = {3522--+},
}

In this study, a new methacrylate monomer with two propylene glycol groups on the side chain, di(propylene glycol) methyl ether methacrylate (diPGMA), was synthesised via an esterification reaction. This new monomer was homo- and co-polymerised for the first time via group transfer polymerisation (GTP). Nine ABA triblock copolymers were synthesised via a "one-pot" GTP, with A and B blocks being based on the hydrophilic and the thermoresponsive oligo(ethylene glycol) methyl ether methacrylate, average M-n 300 g mol(-1) (OEGMA300), and the hydrophobic diPGMA, respectively. The molar mass (MM) and OEGMA300/diPGMA content was systematically varied and the effect of this on the self-assembly and thermoresponsive properties was investigated. All copolymers were shown to self-assemble into aggregates and the size of these aggregates increased with both the MM of the polymer and the polymer content in diPGMA. A thermoresponse was observed in aqueous media, with the cloud point (CP) decreasing as the hydrophobic content increases, and the MM decreases. In concentrated aqueous solutions, the polymer with the highest MM and highest diPGMA content formed gels, whose storage modulus increases as a function of the concentration. This study reports a promising alternative hydrophobic monomer to be used in the fabrication of thermogelling materials.

@article{georgiou_polymer_2021,
	title = {Polymer {Self}-{Assembly} {Induced} {Enhancement} of {Ice} {Recrystallization} {Inhibition}},
	volume = {143},
	issn = {0002-7863},
	doi = {10.1021/jacs.1c01963},
	abstract = {Ice binding proteins modulate ice nucleation/ growth and have huge (bio)technological potential. There are few synthetic materials that reproduce their function, and rational design is challenging due to the outstanding questions about the mechanisms of ice binding, including whether ice binding is essential to reproduce all their macroscopic properties. Here we report that nanoparticles obtained by polymerization-induced self-assembly (PISA) inhibit ice recrystallization (IRI) despite their constituent polymers having no apparent activity. Poly(ethylene glycol), poly(dimethylacrylamide), and poly(vinylpyrrolidone) coronas were all IRI-active when assembled into nanoparticles. Different core-forming blocks were also screened, revealing the core chemistry had no effect. These observations show ice binding domains are not essential for macroscopic IRI activity and suggest that the size, and crowding, of polymers may increase the IRI activity of "non-active" polymers. It was also discovered that poly(vinylpyrrolidone) particles had ice crystal shaping activity, indicating this polymer can engage ice crystal surfaces, even though on its own it does not show any appreciable ice recrystallization inhibition. Larger (vesicle) nanoparticles are shown to have higher ice recrystallization inhibition activity compared to smaller (sphere) particles, whereas ice nucleation activity was not found for any material. This shows that assembly into larger structures can increase IRI activity and that increasing the "size" of an IRI does not always lead to ice nucleation. This nanoparticle approach offers a platform toward ice-controlling soft materials and insight into how IRI activity scales with molecular size of additives.},
	number = {19},
	urldate = {2021-07-07},
	journal = {JOURNAL OF THE AMERICAN CHEMICAL SOCIETY},
	author = {Georgiou, Panagiotis G. and Marton, Huba L. and Baker, Alexander N. and Congdon, Thomas R. and Whale, Thomas F. and Gibson, I, Matthew},
	month = may,
	year = {2021},
	pages = {7449--7461},
}

Ice binding proteins modulate ice nucleation/ growth and have huge (bio)technological potential. There are few synthetic materials that reproduce their function, and rational design is challenging due to the outstanding questions about the mechanisms of ice binding, including whether ice binding is essential to reproduce all their macroscopic properties. Here we report that nanoparticles obtained by polymerization-induced self-assembly (PISA) inhibit ice recrystallization (IRI) despite their constituent polymers having no apparent activity. Poly(ethylene glycol), poly(dimethylacrylamide), and poly(vinylpyrrolidone) coronas were all IRI-active when assembled into nanoparticles. Different core-forming blocks were also screened, revealing the core chemistry had no effect. These observations show ice binding domains are not essential for macroscopic IRI activity and suggest that the size, and crowding, of polymers may increase the IRI activity of "non-active" polymers. It was also discovered that poly(vinylpyrrolidone) particles had ice crystal shaping activity, indicating this polymer can engage ice crystal surfaces, even though on its own it does not show any appreciable ice recrystallization inhibition. Larger (vesicle) nanoparticles are shown to have higher ice recrystallization inhibition activity compared to smaller (sphere) particles, whereas ice nucleation activity was not found for any material. This shows that assembly into larger structures can increase IRI activity and that increasing the "size" of an IRI does not always lead to ice nucleation. This nanoparticle approach offers a platform toward ice-controlling soft materials and insight into how IRI activity scales with molecular size of additives.

@article{li_cationic_2021,
	title = {Cationic {Glycopolymers} with {Aggregation}-{Induced} {Emission} for the {Killing}, {Imaging}, and {Detection} of {Bacteria}},
	volume = {22},
	issn = {1525-7797},
	doi = {10.1021/acs.biomac.1c00298},
	abstract = {Cationic glycopolymers with structures similar to those of typical poly(ionic liquids (PILs) were synthesized via the quaternization reaction of poly(4-vinyl pyridine) with halogen-functionalized D-mannose and tetraphenylethylene units. Such postpolymerization modification provided PILs with aggregation-induced emission effect as well as specific carbohydrate-protein recognition with lectins such as concanavalin A. The interactions between cationic glycopolymers and different microorganisms, including Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli, were used for the killing, imaging, and detection of bacteria. Besides, these sugar-containing PILs showed a relatively low hemolysis rate due to the presence of saccharide units, which may have potential application in the field of biomaterials.},
	number = {5},
	urldate = {2021-06-05},
	journal = {BIOMACROMOLECULES},
	author = {Li, Die and Chen, Jing and Hong, Mei and Wang, Yan and Haddleton, David M. and Li, Guang-Zhao and Zhang, Qiang},
	month = may,
	year = {2021},
	pages = {2224--2232},
}

Cationic glycopolymers with structures similar to those of typical poly(ionic liquids (PILs) were synthesized via the quaternization reaction of poly(4-vinyl pyridine) with halogen-functionalized D-mannose and tetraphenylethylene units. Such postpolymerization modification provided PILs with aggregation-induced emission effect as well as specific carbohydrate-protein recognition with lectins such as concanavalin A. The interactions between cationic glycopolymers and different microorganisms, including Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli, were used for the killing, imaging, and detection of bacteria. Besides, these sugar-containing PILs showed a relatively low hemolysis rate due to the presence of saccharide units, which may have potential application in the field of biomaterials.

@article{cespedes_enhanced_2021,
	title = {Enhanced properties of well-defined polymer networks prepared by a sequential thiol-{Michael} - radical thiol-ene ({STMRT}) strategy},
	volume = {151},
	issn = {0014-3057},
	doi = {10.1016/j.eurpolymj.2021.110440},
	abstract = {A sequential thiol-Michael - radical thiol-ene (STMRT) strategy was used to produce poly(ethylene glycol)-based model networks and enable establishment of a structure-property relationship from the network characteristics. Selective double thiol-Michael reactions on a series of poly(ethylene glycol) diacrylates (PEGDA), that differed in average chain length, with two molar equivalents of the trithiol trimethylolpropane tris(3-mercaptopropionate) (TMPTMP) yielded well-defined telechelic poly(ethylene glycol)-based tetrathiols. These tetrathiols were in turn used to produce model (co-)networks by photo-induced radical thiol-ene polymerization with either the same poly(ethylene glycol) diacrylates or with tri(ethyleneglycol) divinylether (TEGDVE). The properties of these networks were studied by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The STMRT-produced model networks possess storage moduli (E') up to 4-fold larger and glass transition temperatures (T-g) of up to 10 degrees C lower than conventionally produced counterparts. The STMRT strategy allows the properties of the model networks to be finely tuned by manipulation of crosslink density and average polymer chain length.},
	urldate = {2021-05-27},
	journal = {EUROPEAN POLYMER JOURNAL},
	author = {Cespedes, Sergio and Hand, Rachel A. and Chmel, Nikola and Moad, Graeme and Keddie, Daniel J. and Schiller, Tara L.},
	month = may,
	year = {2021},
}

A sequential thiol-Michael - radical thiol-ene (STMRT) strategy was used to produce poly(ethylene glycol)-based model networks and enable establishment of a structure-property relationship from the network characteristics. Selective double thiol-Michael reactions on a series of poly(ethylene glycol) diacrylates (PEGDA), that differed in average chain length, with two molar equivalents of the trithiol trimethylolpropane tris(3-mercaptopropionate) (TMPTMP) yielded well-defined telechelic poly(ethylene glycol)-based tetrathiols. These tetrathiols were in turn used to produce model (co-)networks by photo-induced radical thiol-ene polymerization with either the same poly(ethylene glycol) diacrylates or with tri(ethyleneglycol) divinylether (TEGDVE). The properties of these networks were studied by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The STMRT-produced model networks possess storage moduli (E') up to 4-fold larger and glass transition temperatures (T-g) of up to 10 degrees C lower than conventionally produced counterparts. The STMRT strategy allows the properties of the model networks to be finely tuned by manipulation of crosslink density and average polymer chain length.

@article{li_manganese-catalyzed_2021,
	title = {Manganese-{Catalyzed} {Batch} and {Continuous} {Flow} {Cationic} {RAFT} {Polymerization} {Induced} by {Visible} {Light}},
	volume = {10},
	issn = {2161-1653},
	doi = {10.1021/acsmacrolett.1c00180},
	abstract = {We present a robust manganese-catalyzed cationic reversible addition-fragmentation chain transfer (RAFT) polymerization induced by visible light. Well-defined poly(vinyl ether)s with controlled molecular weight and molecular weight distributions (MWDs) can be conveniently prepared at room temperature without monomer purification. The commercially available manganese carbonyl bromide is used as the photocatalyst for cationic RAFT polymerization. Moreover, this method has been further applied in both batch and continuous flow systems, providing a visible light induced flow cationic polymerization under mild conditions.},
	number = {5},
	urldate = {2021-06-05},
	journal = {ACS MACRO LETTERS},
	author = {Li, Jiajia and Kerr, Andrew and Song, Qiao and Yang, Jie and Hakkinen, Satu and Pan, Xiangqiang and Zhang, Zhengbiao and Zhu, Jian and Perrier, Sebastien},
	month = may,
	year = {2021},
	pages = {570--575},
}

We present a robust manganese-catalyzed cationic reversible addition-fragmentation chain transfer (RAFT) polymerization induced by visible light. Well-defined poly(vinyl ether)s with controlled molecular weight and molecular weight distributions (MWDs) can be conveniently prepared at room temperature without monomer purification. The commercially available manganese carbonyl bromide is used as the photocatalyst for cationic RAFT polymerization. Moreover, this method has been further applied in both batch and continuous flow systems, providing a visible light induced flow cationic polymerization under mild conditions.

@article{alqarni_synthetic_2021,
	title = {Synthetic {Routes} to {Single} {Chain} {Polymer} {Nanoparticles} ({SCNPs}): {Current} {Status} and {Perspectives}},
	volume = {42},
	issn = {1022-1336},
	doi = {10.1002/marc.202100035},
	abstract = {Recent advances in polymer science make it possible to create single chain polymer nanoparticles (SCNPs), which can mimic the folding of natural macromolecules, such as protein and nucleic acid, in terms of their native and functional state. Even though considerable progress has been done during the last years, the synthesis of relatively controlled SCNPs with a good folding accuracy is still challenging due to lack of appropriate chemical synthesis techniques. Different types of SCNPs are developed with enhanced properties and used for various applications, e.g., delivery systems, imaging agents, and nanomedicine. As it is believed that SCNPs are so crucial to elucidate single chain technology, in this review, recent developments in SCNPs are discussed comprehensively according to their synthetic approaches to keep readers updated on this important research field. First, selective point folding methods are classified and highlighted, and then repeat unit folding routes are discussed with exciting examples.},
	number = {11},
	urldate = {2021-04-29},
	journal = {MACROMOLECULAR RAPID COMMUNICATIONS},
	author = {Alqarni, Meshari A. M. and Waldron, Christopher and Yilmaz, Gokhan and Becer, C. Remzi},
	month = jun,
	year = {2021},
}

Recent advances in polymer science make it possible to create single chain polymer nanoparticles (SCNPs), which can mimic the folding of natural macromolecules, such as protein and nucleic acid, in terms of their native and functional state. Even though considerable progress has been done during the last years, the synthesis of relatively controlled SCNPs with a good folding accuracy is still challenging due to lack of appropriate chemical synthesis techniques. Different types of SCNPs are developed with enhanced properties and used for various applications, e.g., delivery systems, imaging agents, and nanomedicine. As it is believed that SCNPs are so crucial to elucidate single chain technology, in this review, recent developments in SCNPs are discussed comprehensively according to their synthetic approaches to keep readers updated on this important research field. First, selective point folding methods are classified and highlighted, and then repeat unit folding routes are discussed with exciting examples.

@article{zhao_plug-and-play_2021,
	title = {Plug-and-play aqueous electrochemical atom transfer radical polymerization†},
	volume = {57},
	issn = {1359-7345},
	doi = {10.1039/d1cc01312b},
	abstract = {A simplified 'plug-and-play' approach to aqueous electrochemical atom transfer radical polymerization (eATRP) has been developed. Well-controlled polymerization of PEGA(480) (D-m = 1.17-1.31) is reported under potentiostatic (3-electrodes, undivided cell) and galvanostatic (2-electrodes, 6-steps) conditions.},
	number = {32},
	urldate = {2021-03-27},
	journal = {CHEMICAL COMMUNICATIONS},
	author = {Zhao, Boyu and Mohammed, Mahir and A. Jones, Bryn and Wilson, Paul},
	month = apr,
	year = {2021},
	pages = {3897--3900},
}

A simplified 'plug-and-play' approach to aqueous electrochemical atom transfer radical polymerization (eATRP) has been developed. Well-controlled polymerization of PEGA(480) (D-m = 1.17-1.31) is reported under potentiostatic (3-electrodes, undivided cell) and galvanostatic (2-electrodes, 6-steps) conditions.

@article{bhatti_photo-actuation_2021,
	title = {Photo-{Actuation} {Stress} of {Ultra}-{Drawn}, {Chain}-{Extended} {Polyethylene}},
	volume = {3},
	issn = {2637-6105},
	doi = {10.1021/acsapm.1c00268},
	abstract = {The influence of solid-state drawing on the photo-actuation stress of oriented semi-crystalline polymers is explored experimentally and theoretically. Photo-responsive and ultra-drawn linear polyethylenes (PEs) containing a commercial benzotriazole dye (BZT) are studied as a model material. In accordance with previous studies, it is found that the actuation stress as a function of draw ratio exhibits an optimum and that the stress first increases and then decreases again slightly. A semi-empirical model is presented that describes the photo-actuation stress as a function of the draw ratio, Young's modulus, thermal expansion coefficient, and temperature difference between the illuminated and non-illuminated state. The Young's modulus and thermal expansion coefficient versus draw ratio curves are described using models based on the pseudo-affine deformation scheme in combination with a two-phase structural model in which highly oriented elements are connected in series with a disordered phase. Rather surprisingly, it is found that the model predicts that the photo-actuation stress is virtually independent of the draw ratio and the degree of chain orientation and extension. An excellent agreement is observed between model predictions and experimental results if the actuation stress is corrected for temperature effects related to the conversion of light into heat. The structure-property relationships derived here provide guidelines for the design of light-driven artificial muscle systems based on ultra-drawn polymers. For instance, it is predicted that ultra-drawn polyamides and polyesters are potentially excellent candidates for producing photo-actuators provided that suitable additives are used and this despite their low maximum attainable draw ratio, Young's modulus and strength.},
	number = {4},
	urldate = {2021-05-28},
	journal = {ACS APPLIED POLYMER MATERIALS},
	author = {Bhatti, Muhammad Rehan Asghar and Bilotti, Emiliano and Peijs, Ton and Bastiaansen, Cees W. M.},
	month = apr,
	year = {2021},
	note = {Univ Engn \& Technol Lahore},
	pages = {2211--2217},
}

The influence of solid-state drawing on the photo-actuation stress of oriented semi-crystalline polymers is explored experimentally and theoretically. Photo-responsive and ultra-drawn linear polyethylenes (PEs) containing a commercial benzotriazole dye (BZT) are studied as a model material. In accordance with previous studies, it is found that the actuation stress as a function of draw ratio exhibits an optimum and that the stress first increases and then decreases again slightly. A semi-empirical model is presented that describes the photo-actuation stress as a function of the draw ratio, Young's modulus, thermal expansion coefficient, and temperature difference between the illuminated and non-illuminated state. The Young's modulus and thermal expansion coefficient versus draw ratio curves are described using models based on the pseudo-affine deformation scheme in combination with a two-phase structural model in which highly oriented elements are connected in series with a disordered phase. Rather surprisingly, it is found that the model predicts that the photo-actuation stress is virtually independent of the draw ratio and the degree of chain orientation and extension. An excellent agreement is observed between model predictions and experimental results if the actuation stress is corrected for temperature effects related to the conversion of light into heat. The structure-property relationships derived here provide guidelines for the design of light-driven artificial muscle systems based on ultra-drawn polymers. For instance, it is predicted that ultra-drawn polyamides and polyesters are potentially excellent candidates for producing photo-actuators provided that suitable additives are used and this despite their low maximum attainable draw ratio, Young's modulus and strength.

@article{basturk_fabrication_2021,
	title = {Fabrication and characterization of composites of a perovskite and polymers with high dielectric permittivity},
	volume = {135},
	issn = {0025-5408},
	doi = {10.1016/j.materresbull.2020.111126},
	abstract = {Composites of strontium titanate (SrTiO3) at loadings up to 50 vol.\% with polar poly(butylene terephthalate) (PBT) and non-polar linear low density polyethylene (LLDPE) were prepared to investigate their dielectric responses in the wireless frequency range. The SrTiO3 particles were uniformly dispersed in the polymers at low loadings, but were more bead-like and agglomerated at higher SrTiO3 loadings. The SrTiO3 has a strong nucleating effect on both polymers, increasing the crystallization temperature and reducing the crystallinity of both polymers. Dielectric properties of composites were measured between 2.45-5 GHz. Dielectric permittivity (epsilon') of composites at 2.45 GHz increased with increasing SrTiO3 content. epsilon' increased by a factor of 5 for PBT, from 3.7 for unfilled PBT to 16.5 and by a factor of similar to 8.5 for unfilled LLDPE, from 2.3 to 19.7 for maximum SrTiO3 loading. The composites had similar dissipation factor values as the unfilled polymers. The Lichtenecker model was in good agreement with the experimental data.},
	urldate = {2021-01-07},
	journal = {MATERIALS RESEARCH BULLETIN},
	author = {Basturk, S. Bahar and Dancer, Claire E. J. and McNally, Tony},
	month = mar,
	year = {2021},
}

Composites of strontium titanate (SrTiO3) at loadings up to 50 vol.% with polar poly(butylene terephthalate) (PBT) and non-polar linear low density polyethylene (LLDPE) were prepared to investigate their dielectric responses in the wireless frequency range. The SrTiO3 particles were uniformly dispersed in the polymers at low loadings, but were more bead-like and agglomerated at higher SrTiO3 loadings. The SrTiO3 has a strong nucleating effect on both polymers, increasing the crystallization temperature and reducing the crystallinity of both polymers. Dielectric properties of composites were measured between 2.45-5 GHz. Dielectric permittivity (epsilon') of composites at 2.45 GHz increased with increasing SrTiO3 content. epsilon' increased by a factor of 5 for PBT, from 3.7 for unfilled PBT to 16.5 and by a factor of similar to 8.5 for unfilled LLDPE, from 2.3 to 19.7 for maximum SrTiO3 loading. The composites had similar dissipation factor values as the unfilled polymers. The Lichtenecker model was in good agreement with the experimental data.

@article{jacucci_anisotropic_2021,
	title = {Anisotropic silica colloids for light scattering},
	volume = {9},
	issn = {2050-7526},
	doi = {10.1039/d1tc00072a},
	abstract = {Scattering enhancers are a class of nanomaterials used in every colored or white material surrounding us: from paints and inks to food and cosmetics to packaging and paper. Such hiding pigments usually consist of non-absorbing, high refractive index nanoparticles, for example spherically shaped titanium dioxide nanopowders. However use of TiO2 carries a high environmental burden. To offset the carbon footprint and health concerns inherent with the use of titanium dioxide, one could approach the challenge of scattering optimization by modifying the morphology of the scattering elements rather than their refractive index. Here, inspired by the bright anisotropic scattering system found in nature, we demonstrate that anisotropic sphero-cylindrical particles can outperform the scattering efficiency of their isotropic counterparts - obtaining an excellent scattering performances across the visible electromagnetic spectrum. We developed a class of micron-sized scattering enhancers composed only of silica. We show that these cylindrical colloids are easily assembled into scattering supracolloidal balls, a new class of pigment microspheres which can be used in formulations for ultrabright coatings.},
	number = {8},
	urldate = {2021-04-16},
	journal = {JOURNAL OF MATERIALS CHEMISTRY C},
	author = {Jacucci, Gianni and Longbottom, Brooke W. and Parkins, Christopher C. and Bon, Stefan A. F. and Vignolini, Silvia},
	month = feb,
	year = {2021},
	pages = {2695--2700},
}

Scattering enhancers are a class of nanomaterials used in every colored or white material surrounding us: from paints and inks to food and cosmetics to packaging and paper. Such hiding pigments usually consist of non-absorbing, high refractive index nanoparticles, for example spherically shaped titanium dioxide nanopowders. However use of TiO2 carries a high environmental burden. To offset the carbon footprint and health concerns inherent with the use of titanium dioxide, one could approach the challenge of scattering optimization by modifying the morphology of the scattering elements rather than their refractive index. Here, inspired by the bright anisotropic scattering system found in nature, we demonstrate that anisotropic sphero-cylindrical particles can outperform the scattering efficiency of their isotropic counterparts - obtaining an excellent scattering performances across the visible electromagnetic spectrum. We developed a class of micron-sized scattering enhancers composed only of silica. We show that these cylindrical colloids are easily assembled into scattering supracolloidal balls, a new class of pigment microspheres which can be used in formulations for ultrabright coatings.

@article{wemyss_dynamic_2021,
	title = {Dynamic {Polymer} {Networks}: {A} {New} {Avenue} towards {Sustainable} and {Advanced} {Soft} {Machines}},
	volume = {60},
	issn = {1433-7851},
	doi = {10.1002/anie.202013254},
	abstract = {While the fascinating field of soft machines has grown rapidly over the last two decades, the materials they are constructed from have remained largely unchanged during this time. Parallel activities have led to significant advances in the field of dynamic polymer networks, leading to the design of three-dimensionally cross-linked polymeric materials that are able to adapt and transform through stimuli-induced bond exchange. Recent work has begun to merge these two fields of research by incorporating the stimuli-responsive properties of dynamic polymer networks into soft machine components. These include dielectric elastomers, stretchable electrodes, nanogenerators, and energy storage devices. In this Minireview, we outline recent progress made in this emerging research area and discuss future directions for the field.},
	number = {25},
	urldate = {2021-03-04},
	journal = {ANGEWANDTE CHEMIE-INTERNATIONAL EDITION},
	author = {Wemyss, Alan M. and Ellingford, Christopher and Morishita, Yoshihiro and Bowen, Chris and Wan, Chaoying},
	month = jun,
	year = {2021},
	pages = {13725--13736},
}

While the fascinating field of soft machines has grown rapidly over the last two decades, the materials they are constructed from have remained largely unchanged during this time. Parallel activities have led to significant advances in the field of dynamic polymer networks, leading to the design of three-dimensionally cross-linked polymeric materials that are able to adapt and transform through stimuli-induced bond exchange. Recent work has begun to merge these two fields of research by incorporating the stimuli-responsive properties of dynamic polymer networks into soft machine components. These include dielectric elastomers, stretchable electrodes, nanogenerators, and energy storage devices. In this Minireview, we outline recent progress made in this emerging research area and discuss future directions for the field.

@article{song_metallohelices_2021,
	title = {Metallohelices emulate the properties of short cationic α-helical peptides},
	volume = {12},
	issn = {2041-6520},
	doi = {10.1039/d0sc06412b},
	abstract = {Naturally occurring peptides in many living systems perform antimicrobial and anticancer host defence roles, but their potential for clinical application is limited by low metabolic stability and relatively high costs of goods. Self-assembled helical metal complexes provide an attractive synthetic platform for non-peptidic architectures that can emulate some of the properties of short cationic alpha-helical peptides, with tuneable charge, shape, size and amphipathicity. Correspondingly there is a growing body of evidence demonstrating that these supramolecular architectures exhibit bioactivity that emulates that of the natural systems. We review that evidence in the context of synthetic advances in the area, driven by the potential for biomedical applications. We note some design considerations for new biologically-relevant metallohelices, and give our outlook on the future of these compounds as therapeutic peptidomimetics.},
	number = {5},
	urldate = {2021-03-05},
	journal = {CHEMICAL SCIENCE},
	author = {Song, Hualong and Postings, Miles and Scott, Peter and Rogers, Nicola J.},
	month = feb,
	year = {2021},
	pages = {1620--1631},
}

Naturally occurring peptides in many living systems perform antimicrobial and anticancer host defence roles, but their potential for clinical application is limited by low metabolic stability and relatively high costs of goods. Self-assembled helical metal complexes provide an attractive synthetic platform for non-peptidic architectures that can emulate some of the properties of short cationic alpha-helical peptides, with tuneable charge, shape, size and amphipathicity. Correspondingly there is a growing body of evidence demonstrating that these supramolecular architectures exhibit bioactivity that emulates that of the natural systems. We review that evidence in the context of synthetic advances in the area, driven by the potential for biomedical applications. We note some design considerations for new biologically-relevant metallohelices, and give our outlook on the future of these compounds as therapeutic peptidomimetics.

@article{abdouni_self-assembled_2021,
	title = {Self-{Assembled} {Multi}- and {Single}-{Chain} {Glyconanoparticles} and {Their} {Lectin} {Recognition}},
	volume = {22},
	issn = {1525-7797},
	doi = {10.1021/acs.biomac.0c01486},
	abstract = {In this work, we describe the physicochemical characterization of amphiphilic glycopolymers synthesized via copper(0)-mediated reversible-deactivation radical polymerization (Cu-RDRP). Depending on the chemical composition of the polymer, these glycopolymers are able to form multi-chain or single-chain polymeric nanoparticles. The folding of these polymers is first of all driven by the amphiphilicity of the glycopolymers and furthermore by the supramolecular formation of helical supramolecular stacks of benzene-1,3,5-tricarboxamides (BTAs) stabilized by threefold hydrogen bonding. The obtained polymeric nanoparticles were subsequently evaluated for their lectin-binding affinity toward a series of mannose- and galactose-binding lectins via surface plasmon resonance. We found that addition of 2-ethylhexyl acrylate to the polymer composition results in compact particles, which translates to a reduction in binding affinity, whereas with the addition of BTAs, the relation between the nature of the particle and the binding ability system becomes more unpredictable.},
	number = {2},
	urldate = {2021-03-21},
	journal = {BIOMACROMOLECULES},
	author = {Abdouni, Yamin and ter Huume, Gijs M. and Yilmaz, Gokhan and Monaco, Alessandra and Redondo-Gomez, Carlos and Meijer, E. W. and Palmans, Anja R. A. and Becer, C. Remzi},
	month = feb,
	year = {2021},
	pages = {661--670},
}

In this work, we describe the physicochemical characterization of amphiphilic glycopolymers synthesized via copper(0)-mediated reversible-deactivation radical polymerization (Cu-RDRP). Depending on the chemical composition of the polymer, these glycopolymers are able to form multi-chain or single-chain polymeric nanoparticles. The folding of these polymers is first of all driven by the amphiphilicity of the glycopolymers and furthermore by the supramolecular formation of helical supramolecular stacks of benzene-1,3,5-tricarboxamides (BTAs) stabilized by threefold hydrogen bonding. The obtained polymeric nanoparticles were subsequently evaluated for their lectin-binding affinity toward a series of mannose- and galactose-binding lectins via surface plasmon resonance. We found that addition of 2-ethylhexyl acrylate to the polymer composition results in compact particles, which translates to a reduction in binding affinity, whereas with the addition of BTAs, the relation between the nature of the particle and the binding ability system becomes more unpredictable.

@article{chen_cooperative_2021,
	title = {Cooperative {Effects} of {Cellulose} {Nanocrystals} and {Sepiolite} {When} {Combined} on {Ionic} {Liquid} {Plasticised} {Chitosan} {Materials}},
	volume = {13},
	issn = {2073-4360},
	doi = {10.3390/polym13040571},
	abstract = {Cellulose nanocrystals (CNCs) and/or sepiolite (SPT) were thermomechanically mixed with un-plasticised chitosan and chitosan/carboxymethyl cellulose (CMC) blends plasticised with 1-ethyl-3-methylimidazolium acetate ([C(2)mim][OAc]). Examination of the morphology of these materials indicates that SPT aggregates were reduced when CNCs or [C(2)mim][OAc] were present. Inclusion of CNCs and/or SPT had a greater effect on material properties when the matrices were un-plasticised. Addition of SPT or CNCs altered the crystalline structure of the un-plasticised chitosan matrix. Moreover, a combination of SPT and CNCs was more effective at suppressing re-crystallisation. Nonetheless, the mechanical properties and surface hydrophobicity were more related to CNC/SPT-biopolymer interactions. The un-plasticised bionanocomposites generally showed increased relaxation temperatures, enhanced tensile strength, and reduced surface wettability. For the [C(2)mim][OAc] plasticised matrices, the ionic liquid (IL) dominates the interactions with the biopolymers such that the effect of the nanofillers is diminished. However, for the [C(2)mim][OAc] plasticised chitosan/CMC matrix, CNCs and SPT acted synergistically suppressing re-crystallisation but resulting in increased tensile strength.},
	number = {4},
	urldate = {2021-03-17},
	journal = {POLYMERS},
	author = {Chen, Pei and Xie, Fengwei and Tang, Fengzai and McNally, Tony},
	month = feb,
	year = {2021},
}

Cellulose nanocrystals (CNCs) and/or sepiolite (SPT) were thermomechanically mixed with un-plasticised chitosan and chitosan/carboxymethyl cellulose (CMC) blends plasticised with 1-ethyl-3-methylimidazolium acetate ([C(2)mim][OAc]). Examination of the morphology of these materials indicates that SPT aggregates were reduced when CNCs or [C(2)mim][OAc] were present. Inclusion of CNCs and/or SPT had a greater effect on material properties when the matrices were un-plasticised. Addition of SPT or CNCs altered the crystalline structure of the un-plasticised chitosan matrix. Moreover, a combination of SPT and CNCs was more effective at suppressing re-crystallisation. Nonetheless, the mechanical properties and surface hydrophobicity were more related to CNC/SPT-biopolymer interactions. The un-plasticised bionanocomposites generally showed increased relaxation temperatures, enhanced tensile strength, and reduced surface wettability. For the [C(2)mim][OAc] plasticised matrices, the ionic liquid (IL) dominates the interactions with the biopolymers such that the effect of the nanofillers is diminished. However, for the [C(2)mim][OAc] plasticised chitosan/CMC matrix, CNCs and SPT acted synergistically suppressing re-crystallisation but resulting in increased tensile strength.

@article{ellacott_comparative_2021,
	title = {Comparative {Study} of the {Cellular} {Uptake} and {Intracellular} {Behavior} of a {Library} of {Cyclic} {Peptide}-{Polymer} {Nanotubes} with {Different} {Self}-{Assembling} {Properties}},
	volume = {22},
	issn = {1525-7797},
	doi = {10.1021/acs.biomac.0c01512},
	abstract = {Particle shape has been described as a key factor in improving cell internalization and biodistribution among the different properties investigated for drug-delivery systems. In particular, tubular structures have been identified as promising candidates for improving drug delivery. Here, we investigate the influence of different design elements of cyclic peptide-polymer nanotubes (CPNTs) on cellular uptake including the nature and length of the polymer and the cyclic peptide building block. By varying the composition of these cyclic peptide-polymer conjugates, a library of CPNTs of lengths varying from a few to over a 150 nm were synthesized and characterized using scattering techniques (small-angle neutron scattering and static light scattering). In vitro studies with fluorescently labeled CPNTs have shown that nanotubes comprised of a single polymer arm with a size between 8 and 16 nm were the most efficiently taken up by three different mammalian cell lines. A mechanistic study on multicellular tumor spheroids has confirmed the ability of these compounds to penetrate to their core. Variations in the proportion of paracellular and transcellular uptake with the self-assembling potential insights about the behavior of CPNTs in cellular systems.},
	number = {2},
	urldate = {2021-03-21},
	journal = {BIOMACROMOLECULES},
	author = {Ellacott, Sean H. and Sanchez-Cano, Carlos and Mansfield, Edward D. H. and Rho, Julia Y. and Song, Ji-Inn and Peltier, Raoul and Perrier, Sebastien},
	month = feb,
	year = {2021},
	pages = {710--722},
}

Particle shape has been described as a key factor in improving cell internalization and biodistribution among the different properties investigated for drug-delivery systems. In particular, tubular structures have been identified as promising candidates for improving drug delivery. Here, we investigate the influence of different design elements of cyclic peptide-polymer nanotubes (CPNTs) on cellular uptake including the nature and length of the polymer and the cyclic peptide building block. By varying the composition of these cyclic peptide-polymer conjugates, a library of CPNTs of lengths varying from a few to over a 150 nm were synthesized and characterized using scattering techniques (small-angle neutron scattering and static light scattering). In vitro studies with fluorescently labeled CPNTs have shown that nanotubes comprised of a single polymer arm with a size between 8 and 16 nm were the most efficiently taken up by three different mammalian cell lines. A mechanistic study on multicellular tumor spheroids has confirmed the ability of these compounds to penetrate to their core. Variations in the proportion of paracellular and transcellular uptake with the self-assembling potential insights about the behavior of CPNTs in cellular systems.

@article{kodura_light-fueled_2021,
	title = {Light-fueled dynamic covalent crosslinking of single polymer chains in non-equilibrium states},
	volume = {12},
	issn = {2041-6520},
	doi = {10.1039/d0sc05818a},
	abstract = {While polymer synthesis proceeds predominantly towards the thermodynamic minimum, living systems operate on the reverse principle - consuming fuel to maintain a non-equilibrium state. Herein, we report the controlled formation of 3D macromolecular architectures based on light-fueled covalent non-equilibrium chemistry. In the presence of green light (525 nm) and a bivalent triazolinedione (TAD) crosslinker, naphthalene-containing polymers can be folded into single chain nanoparticles (SCNPs). At ambient temperature, the cycloaddition product of TAD with naphthalene reverts and the SCNP unfolds into its linear parent polymer. The reported SCNP is the first example of a reversible light triggered folding of single polymer chains and can readily be repeated for several cycles. The folded state of the SCNP can either be preserved through a constant supply of light fuel, kinetic trapping or through a chemical modification that makes the folded state thermodynamically favored. Whereas small molecule bivalent TAD/naphthalene cycloaddition products largely degraded after 3 days in solution, even in the presence of fuel, the SCNP entities were found to remain intact, thereby indicating the light-fueled stabilization of the SCNP to be an inherent feature of the confined macromolecular environment.},
	number = {4},
	urldate = {2021-03-14},
	journal = {CHEMICAL SCIENCE},
	author = {Kodura, Daniel and Houck, Hannes A. and Bloesser, Fabian R. and Goldmann, Anja S. and Du Prez, Filip E. and Frisch, Hendrik and Barner-Kowollik, Christopher},
	month = jan,
	year = {2021},
	pages = {1302--1310},
}

While polymer synthesis proceeds predominantly towards the thermodynamic minimum, living systems operate on the reverse principle - consuming fuel to maintain a non-equilibrium state. Herein, we report the controlled formation of 3D macromolecular architectures based on light-fueled covalent non-equilibrium chemistry. In the presence of green light (525 nm) and a bivalent triazolinedione (TAD) crosslinker, naphthalene-containing polymers can be folded into single chain nanoparticles (SCNPs). At ambient temperature, the cycloaddition product of TAD with naphthalene reverts and the SCNP unfolds into its linear parent polymer. The reported SCNP is the first example of a reversible light triggered folding of single polymer chains and can readily be repeated for several cycles. The folded state of the SCNP can either be preserved through a constant supply of light fuel, kinetic trapping or through a chemical modification that makes the folded state thermodynamically favored. Whereas small molecule bivalent TAD/naphthalene cycloaddition products largely degraded after 3 days in solution, even in the presence of fuel, the SCNP entities were found to remain intact, thereby indicating the light-fueled stabilization of the SCNP to be an inherent feature of the confined macromolecular environment.

@article{basturk_dielectric_2021,
	title = {Dielectric performance of composites of {BaTiO3} and polymers for capacitor applications under microwave frequency},
	volume = {138},
	issn = {0021-8995},
	doi = {10.1002/app.50521},
	abstract = {Composites of nano-sized barium titanate (BaTiO3) with volume fractions up to 0.5 and poly(butylene terephthalate) (PBT) or linear low-density polyethylene (LLDPE) were made via extrusion. Scanning electron microscopy demonstrated that BaTiO3 is well dispersed in the polymer matrices. The crystalline content (DSC) and thermal stability (TGA) of both polymers decreased with increasing BaTiO3 loading. Dielectric properties of the composites were measured using a vector network analyzer. Both dielectric permittivity and tangent loss increased with increasing BaTiO3 content. At 2.45 GHz, the dielectric permittivity for 48 vol\% BaTiO3-filled LLDPE and 43 vol\% BaTiO3-filled PBT was 25 and 21.2, respectively. There was a good fit between the Lichtenecker model and experimental data obtained up to a certain value, with the permittivity variations being dependent on volume fraction. The improved dielectric performance achieved on inclusion of BaTiO3 confirms both composite systems as potential candidates for microwave frequency capacitor applications.},
	number = {22},
	urldate = {2021-02-10},
	journal = {JOURNAL OF APPLIED POLYMER SCIENCE},
	author = {Basturk, S. Bahar and Dancer, Claire E. J. and McNally, Tony},
	month = jun,
	year = {2021},
}

Composites of nano-sized barium titanate (BaTiO3) with volume fractions up to 0.5 and poly(butylene terephthalate) (PBT) or linear low-density polyethylene (LLDPE) were made via extrusion. Scanning electron microscopy demonstrated that BaTiO3 is well dispersed in the polymer matrices. The crystalline content (DSC) and thermal stability (TGA) of both polymers decreased with increasing BaTiO3 loading. Dielectric properties of the composites were measured using a vector network analyzer. Both dielectric permittivity and tangent loss increased with increasing BaTiO3 content. At 2.45 GHz, the dielectric permittivity for 48 vol% BaTiO3-filled LLDPE and 43 vol% BaTiO3-filled PBT was 25 and 21.2, respectively. There was a good fit between the Lichtenecker model and experimental data obtained up to a certain value, with the permittivity variations being dependent on volume fraction. The improved dielectric performance achieved on inclusion of BaTiO3 confirms both composite systems as potential candidates for microwave frequency capacitor applications.

@article{khan_raft_2021,
	title = {{RAFT} {Emulsion} {Polymerization} for ({Multi})block {Copolymer} {Synthesis}: {Overcoming} the {Constraints} of {Monomer} {Order}},
	volume = {54},
	issn = {0024-9297},
	doi = {10.1021/acs.macromol.0c02415},
	abstract = {Synthesis of (multi)block copolymers using reversible addition-fragmentation chain transfer (RAFT) polymerization generally suffers from the limitation that the order of the blocks must be considered. Herein, syntheses of block copolymers by RAFT polymerization using trithiocarbonate RAFT species are conducted as solution, miniemulsion, and emulsion polymerizations to demonstrate that the issue of monomer order for styrene and butyl methacrylate can be largely overcome in emulsion polymerization under carefully chosen conditions. The presence of monomer droplets in emulsion polymerization-in addition to polymer particles that constitute the locus of polymerization-leads to a reduction in the ratio of RAFT end groups to monomer at the locus of polymerization. Consequently, fragmentation of the RAFT adduct radical in the "backward" ("wrong") direction is associated with fewer monomer additions, thus minimizing the impact of this undesired kinetic event. It is demonstrated that RAFT emulsion polymerization can be exploited to prepare an alternating pentablock copolymer composed of methacrylates (with 10 mol \% styrene) and styrene without consideration of monomer order, thereby significantly broadening the scope of RAFT polymerization for multiblock copolymer synthesis.},
	number = {2},
	urldate = {2021-03-02},
	journal = {MACROMOLECULES},
	author = {Khan, Murtaza and Guimaraes, Thiago R. and Choong, Kenneth and Moad, Graeme and Perrier, Sebastien and Zetterlund, Per B.},
	month = jan,
	year = {2021},
	pages = {736--746},
}

Synthesis of (multi)block copolymers using reversible addition-fragmentation chain transfer (RAFT) polymerization generally suffers from the limitation that the order of the blocks must be considered. Herein, syntheses of block copolymers by RAFT polymerization using trithiocarbonate RAFT species are conducted as solution, miniemulsion, and emulsion polymerizations to demonstrate that the issue of monomer order for styrene and butyl methacrylate can be largely overcome in emulsion polymerization under carefully chosen conditions. The presence of monomer droplets in emulsion polymerization-in addition to polymer particles that constitute the locus of polymerization-leads to a reduction in the ratio of RAFT end groups to monomer at the locus of polymerization. Consequently, fragmentation of the RAFT adduct radical in the "backward" ("wrong") direction is associated with fewer monomer additions, thus minimizing the impact of this undesired kinetic event. It is demonstrated that RAFT emulsion polymerization can be exploited to prepare an alternating pentablock copolymer composed of methacrylates (with 10 mol % styrene) and styrene without consideration of monomer order, thereby significantly broadening the scope of RAFT polymerization for multiblock copolymer synthesis.

@article{rho_100th_2021,
	title = {100th {Anniversary} of {Macromolecular} {Science} {Viewpoint}: {User}'s {Guide} to {Supramolecular} {Peptide}-{Polymer} {Conjugates}},
	volume = {10},
	issn = {2161-1653},
	doi = {10.1021/acsmacrolett.0c00734},
	abstract = {This Viewpoint highlights the design principles and development of peptide-based supramolecular polymers. Here we delve deep into the practicalities of synthesizing and characterizing these macromolecular structures and provide a thorough overview of the benefits and challenges that come with these systems. This Viewpoint emphasizes to beginners and experts alike the importance of understanding the fundamental behavior and self-assembly processes when designing these complex and dynamic functional materials.},
	number = {2},
	urldate = {2021-03-14},
	journal = {ACS MACRO LETTERS},
	author = {Rho, Julia Y. and Perrier, Sebastien},
	month = feb,
	year = {2021},
	pages = {258--271},
}

This Viewpoint highlights the design principles and development of peptide-based supramolecular polymers. Here we delve deep into the practicalities of synthesizing and characterizing these macromolecular structures and provide a thorough overview of the benefits and challenges that come with these systems. This Viewpoint emphasizes to beginners and experts alike the importance of understanding the fundamental behavior and self-assembly processes when designing these complex and dynamic functional materials.

@article{zhang_understanding_2021,
	title = {Understanding {H2O2}-{Induced} {Thermo}-{Oxidative} {Reclamation} of {Vulcanized} {Styrene} {Butadiene} {Rubber} at {Low} {Temperatures}},
	volume = {9},
	issn = {2168-0485},
	doi = {10.1021/acssuschemeng.0c08867},
	abstract = {Recombination reactions often occur in the process of chemical, thermal, or mechanical degradation of vulcanized styrene butadiene rubber (SBR), which hinders the recycling efficiency of waste tire rubbers. In this work, we developed an effective method to transform solid vulcanized SBR into reclaimed rubber with 100\% sol fraction through a hydrogen peroxide (H2O2)-induced thermo-oxidative reclamation process at 100 degrees C with the assistance of soybean oil. The structural evolution of the vulcanized SBR and the role of H2O2 and soybean oil in the reclaiming process were investigated by sol-gel analysis, gel permeation chromatography (GPC), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), and C-13 nuclear magnetic resonance (C-13 NMR) spectroscopy. The results showed that vulcanized SBR underwent severe oxidative scission, the sol of the reclaimed samples increased from 20.4 wt \% up to 100 wt \% with a decreased molecular weight to 1.378 x 10(4) g/mol. Multiple functional groups such as carboxyl, hydroxyl, and ether groups were generated in the polymer chains as confirmed by C-13 NMR and FTIR spectroscopy. Moreover, the reaction pathway of the oxidative reclamation was quantified by density functional theory (DFT) calculations, suggesting that hydroxyl radicals were generated from a homolytic cleavage reaction of H2O2 with SBR by hydrogen abstraction and accelerated the rate-determining step of the SBR oxidation. The apparent activation energy (E-a) of the initial stage of the oxidative reclamation decreased from 223 to 160 kJ/mol according to the model-free kinetics results.},
	number = {5},
	urldate = {2021-03-10},
	journal = {ACS SUSTAINABLE CHEMISTRY \& ENGINEERING},
	author = {Zhang, Zhen and Li, Jiayi and Wan, Chaoying and Zhang, Yuxin and Wang, Shifeng},
	month = feb,
	year = {2021},
	pages = {2378--2387},
}

Recombination reactions often occur in the process of chemical, thermal, or mechanical degradation of vulcanized styrene butadiene rubber (SBR), which hinders the recycling efficiency of waste tire rubbers. In this work, we developed an effective method to transform solid vulcanized SBR into reclaimed rubber with 100% sol fraction through a hydrogen peroxide (H2O2)-induced thermo-oxidative reclamation process at 100 degrees C with the assistance of soybean oil. The structural evolution of the vulcanized SBR and the role of H2O2 and soybean oil in the reclaiming process were investigated by sol-gel analysis, gel permeation chromatography (GPC), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), and C-13 nuclear magnetic resonance (C-13 NMR) spectroscopy. The results showed that vulcanized SBR underwent severe oxidative scission, the sol of the reclaimed samples increased from 20.4 wt % up to 100 wt % with a decreased molecular weight to 1.378 x 10(4) g/mol. Multiple functional groups such as carboxyl, hydroxyl, and ether groups were generated in the polymer chains as confirmed by C-13 NMR and FTIR spectroscopy. Moreover, the reaction pathway of the oxidative reclamation was quantified by density functional theory (DFT) calculations, suggesting that hydroxyl radicals were generated from a homolytic cleavage reaction of H2O2 with SBR by hydrogen abstraction and accelerated the rate-determining step of the SBR oxidation. The apparent activation energy (E-a) of the initial stage of the oxidative reclamation decreased from 223 to 160 kJ/mol according to the model-free kinetics results.

@article{wilson-whitford_textured_2021,
	title = {Textured {Microcapsules} through {Crystallization}},
	volume = {13},
	issn = {1944-8244},
	doi = {10.1021/acsami.0c22378},
	abstract = {This work demonstrates the fabrication of surface-textured microcapsules formed from emulsion droplets, which are stabilized by an interlocking mesh of needle-like crystals. Crystals of the small-organic-compound decane-1,10-bis(cyclohexyl carbamate) are formed within the geometric confinement of the droplets, through precipitation from a binary-solvent-dispersed phase. This binary mixture consists of a volatile solvent and nonvolatile carrier oil. Crystallization is facilitated upon supersaturation due to evaporation of the volatile solvent. Microcapsule diameter can be easily tuned using microfluidics. This approach also proves to be scalable when using conventional mixers, yielding spikey microcapsules with diameters in the range of 10-50 mu m. It is highlighted that the capsule shape can be molded and arrested by jamming using recrystallization in geometric confinement. Moreover, it is shown that these textured microcapsules show a promising enhanced deposition onto a range of fabric fibers.},
	number = {4},
	urldate = {2021-03-14},
	journal = {ACS APPLIED MATERIALS \& INTERFACES},
	author = {Wilson-Whitford, Samuel R. and Jaggers, Ross W. and Longbottom, Brooke W. and Donald, Matt K. and Clarkson, Guy J. and Bon, Stefan A. F.},
	month = feb,
	year = {2021},
	pages = {5887--5894},
}

This work demonstrates the fabrication of surface-textured microcapsules formed from emulsion droplets, which are stabilized by an interlocking mesh of needle-like crystals. Crystals of the small-organic-compound decane-1,10-bis(cyclohexyl carbamate) are formed within the geometric confinement of the droplets, through precipitation from a binary-solvent-dispersed phase. This binary mixture consists of a volatile solvent and nonvolatile carrier oil. Crystallization is facilitated upon supersaturation due to evaporation of the volatile solvent. Microcapsule diameter can be easily tuned using microfluidics. This approach also proves to be scalable when using conventional mixers, yielding spikey microcapsules with diameters in the range of 10-50 mu m. It is highlighted that the capsule shape can be molded and arrested by jamming using recrystallization in geometric confinement. Moreover, it is shown that these textured microcapsules show a promising enhanced deposition onto a range of fabric fibers.

@article{efstathiou_self-healing_2021,
	title = {Self-healing and mechanical performance of dynamic glycol chitosan hydrogel nanocomposites},
	volume = {9},
	issn = {2050-750X},
	doi = {10.1039/d0tb02390f},
	abstract = {The application of functional self-healing and mechanically robust hydrogels in bioengineering, drug delivery, soft robotics, etc., is continuously growing. However, fabricating hydrogels that simultaneously possess good mechanical and self-healing properties remains a challenge. Developing robust hydrogel formulations for the encapsulation and release of hydrophobic substances is a major challenge especially in some pharmaceutical treatments where the many of drugs show incompatibility with the hydrophilic hydrogel matrices. Schiff base hydrogels have been developed using a benzaldehyde multifunctional amphiphilic polyacrylamide crosslinker in conjunction with glycol chitosan. The polymeric crosslinker was synthesized by a two-step reaction using aqueous Cu-RDRP to give an ABA telechelic copolymer of N,N-dimethyl acrylamide (DMAc) and N-hydroxyethyl acrylamide (HEAm) from a bifunctional PEG. The polymer was then modified by post functionalization leading to a multifunctional benzaldehyde crosslinker that was shown to be capable of self-assembly into aggregates in aqueous media serving as a possible candidate for the entrapment of hydrophobic substances. Aqueous solutions of the crosslinker spontaneously formed hydrogels when mixed with glycol chitosan due to the in situ formation of imine bonds. Hydrogels were characterized while additional comparisons were made with a commonly used bifunctional PEG crosslinker. The effect of introducing partially reduced graphene oxide (GO) nanosheets was also examined and led to enhancements in both mechanical properties (2.0 fold increase in modulus and 1.4 fold increase in strain) and self-healing efficiencies ({\textgreater}99\% from 60\% by rheology) relative to the pristine polymer hydrogels.},
	number = {3},
	urldate = {2021-03-02},
	journal = {JOURNAL OF MATERIALS CHEMISTRY B},
	author = {Efstathiou, Spyridon and Wemyss, Alan M. and Patias, Georgios and Al-Shok, Lucas and Grypioti, Maria and Coursari, Despina and Ma, Congkai and Atkins, Christophe J. and Shegiwal, Ataulla and Wan, Chaoying and Haddleton, David M.},
	month = jan,
	year = {2021},
	pages = {809--823},
}

The application of functional self-healing and mechanically robust hydrogels in bioengineering, drug delivery, soft robotics, etc., is continuously growing. However, fabricating hydrogels that simultaneously possess good mechanical and self-healing properties remains a challenge. Developing robust hydrogel formulations for the encapsulation and release of hydrophobic substances is a major challenge especially in some pharmaceutical treatments where the many of drugs show incompatibility with the hydrophilic hydrogel matrices. Schiff base hydrogels have been developed using a benzaldehyde multifunctional amphiphilic polyacrylamide crosslinker in conjunction with glycol chitosan. The polymeric crosslinker was synthesized by a two-step reaction using aqueous Cu-RDRP to give an ABA telechelic copolymer of N,N-dimethyl acrylamide (DMAc) and N-hydroxyethyl acrylamide (HEAm) from a bifunctional PEG. The polymer was then modified by post functionalization leading to a multifunctional benzaldehyde crosslinker that was shown to be capable of self-assembly into aggregates in aqueous media serving as a possible candidate for the entrapment of hydrophobic substances. Aqueous solutions of the crosslinker spontaneously formed hydrogels when mixed with glycol chitosan due to the in situ formation of imine bonds. Hydrogels were characterized while additional comparisons were made with a commonly used bifunctional PEG crosslinker. The effect of introducing partially reduced graphene oxide (GO) nanosheets was also examined and led to enhancements in both mechanical properties (2.0 fold increase in modulus and 1.4 fold increase in strain) and self-healing efficiencies (\textgreater99% from 60% by rheology) relative to the pristine polymer hydrogels.

@article{richards_introducing_2021,
	title = {Introducing affinity and selectivity into galectin-targeting nanoparticles with fluorinated glycan ligands},
	volume = {12},
	issn = {2041-6520},
	doi = {10.1039/d0sc05360k},
	abstract = {Galectins are potential biomarkers and therapeutic targets. However, galectins display broad affinity towards beta-galactosides meaning glycan-based (nano)biosensors lack the required selectivity and affinity. Using a polymer-stabilized nanoparticle biosensing platform, we herein demonstrate that the specificity of immobilised lacto-N-biose towards galectins can be 'turned on/off' by using site-specific glycan fluorination and in some cases reversal of specificity can be achieved. The panel of fluoro-glycans were obtained by a chemoenzymatic approach, exploiting BiGalK and BiGalHexNAcP enzymes from Bifidobacterium infantis which are shown to tolerate fluorinated glycans, introducing structural diversity which would be very laborious by chemical methods alone. These results demonstrate that integrating non-natural, fluorinated glycans into nanomaterials can encode unprecedented selectivity with potential applications in biosensing.},
	number = {3},
	urldate = {2021-03-05},
	journal = {CHEMICAL SCIENCE},
	author = {Richards, Sarah-Jane and Keenan, Tessa and Vendeville, Jean-Baptiste and Wheatley, David E. and Chidwick, Harriet and Budhadev, Darshita and Council, Claire E. and Webster, Claire S. and Ledru, Helene and Baker, Alexander N. and Walker, Marc and Galan, M. Carmen and Linclau, Bruno and Fascione, Martin A. and Gibson, Matthew I.},
	month = jan,
	year = {2021},
	pages = {905--910},
}

Galectins are potential biomarkers and therapeutic targets. However, galectins display broad affinity towards beta-galactosides meaning glycan-based (nano)biosensors lack the required selectivity and affinity. Using a polymer-stabilized nanoparticle biosensing platform, we herein demonstrate that the specificity of immobilised lacto-N-biose towards galectins can be 'turned on/off' by using site-specific glycan fluorination and in some cases reversal of specificity can be achieved. The panel of fluoro-glycans were obtained by a chemoenzymatic approach, exploiting BiGalK and BiGalHexNAcP enzymes from Bifidobacterium infantis which are shown to tolerate fluorinated glycans, introducing structural diversity which would be very laborious by chemical methods alone. These results demonstrate that integrating non-natural, fluorinated glycans into nanomaterials can encode unprecedented selectivity with potential applications in biosensing.

@article{schmitt_bright_2021,
	title = {The bright and the dark side of the sphere: light-stabilized microparticles},
	volume = {12},
	issn = {1759-9954},
	doi = {10.1039/d0py01456g},
	abstract = {Visible light-triggered reversible triazolinedione (TAD) chemistry was already reported in the 1970s but it has only recently been introduced into the field of materials science, and as such remains relatively unexplored. Here, we exploit the reversible naphthalene-TAD Diels-Alder couple to crosslink pre-synthesized polymers in a precipitation-like polymerization to form narrow disperse microparticles. The approach does not require additives such as stabilizers or initiators and proceeds to deliver particles under relatively mild conditions in less than 1 h. While the crosslinked particles maintain their shape upon continuous irradiation with green light, the particles can be readily degraded in the dark at ambient temperature through a spontaneous cycloreversion process. In addition, the formation and degradation rate can be tuned by employing shorter or longer prepolymers, with particles synthesized from larger polymers degrading slower compared to their shorter polymer counterparts. The particle formation, light-stabilization and degradation were characterized in-depth by scanning electron microscopy (SEM) and online static light scattering experiments. In particular the particles' tuneable intrinsic degradation behaviour could hold key potential, for instance, in long term drug or fertilizer delivery systems.},
	number = {3},
	urldate = {2021-03-10},
	journal = {POLYMER CHEMISTRY},
	author = {Schmitt, Christian W. and Walden, Sarah L. and Delafresnaye, Laura and Houck, Hannes A. and Barner, Leonie and Barner-Kowollik, Christopher},
	month = jan,
	year = {2021},
	pages = {449--457},
}

Visible light-triggered reversible triazolinedione (TAD) chemistry was already reported in the 1970s but it has only recently been introduced into the field of materials science, and as such remains relatively unexplored. Here, we exploit the reversible naphthalene-TAD Diels-Alder couple to crosslink pre-synthesized polymers in a precipitation-like polymerization to form narrow disperse microparticles. The approach does not require additives such as stabilizers or initiators and proceeds to deliver particles under relatively mild conditions in less than 1 h. While the crosslinked particles maintain their shape upon continuous irradiation with green light, the particles can be readily degraded in the dark at ambient temperature through a spontaneous cycloreversion process. In addition, the formation and degradation rate can be tuned by employing shorter or longer prepolymers, with particles synthesized from larger polymers degrading slower compared to their shorter polymer counterparts. The particle formation, light-stabilization and degradation were characterized in-depth by scanning electron microscopy (SEM) and online static light scattering experiments. In particular the particles' tuneable intrinsic degradation behaviour could hold key potential, for instance, in long term drug or fertilizer delivery systems.

@article{baker_sars-cov-2_2021,
	title = {The {SARS}-{COV}-2 {Spike} {Protein} {Binds} {Sialic} {Acids}, and {Enables} {Rapid} {Detection} in a {Lateral} {Flow} {Point} of {Care} {Diagnostic} {Device} (vol 6, pg 2046, 2020)},
	volume = {7},
	issn = {2374-7943},
	doi = {10.1021/acscentsci.1c00027},
	number = {2},
	urldate = {2021-04-04},
	journal = {ACS CENTRAL SCIENCE},
	author = {Baker, Alexander and Richards, Sarah-Jane and Congdon, Thomas and Hasan, Muhammad and Guy, Collette and Zwetsloot, Alexander and Gallo, Angelo and Lewandowski, Jozef and Stansfeld, Phillip and Straube, Anne and Walker, Marc and Chessa, Simona and Pergolizzi, Giulia and Dedola, Simone and Field, Robert and Gibson, Matthew},
	month = feb,
	year = {2021},
	pages = {379--380},
}

@article{song_efficient_2021,
	title = {Efficient {Artificial} {Light}-{Harvesting} {System} {Based} on {Supramolecular} {Peptide} {Nanotubes} in {Water}},
	volume = {143},
	issn = {0002-7863},
	doi = {10.1021/jacs.0c11060},
	abstract = {Artificial light-harvesting systems in aqueous media which mimic nature are of significant importance; however, they are often restrained by the solubility and the undesired aggregation-caused quenching effect of the hydrophobic chromophores. Here, we report a generalized strategy toward the construction of efficient artificial light-harvesting systems based on supramolecular peptide nanotubes in water. By molecularly aligning the hydrophobic chromophores along the nanotubes in a slipped manner, an artificial light-harvesting system with a two-step sequential Forster resonance energy transfer process is successfully fabricated, showing an energy transfer efficiency up to 95\% and a remarkably high fluorescence quantum yield of 30\%, along with high stability. Furthermore, the spectral emission could be continuously tuned from blue through green to orange, as well as outputted as a white light continuum with a fluorescence quantum yield of 29.9\%. Our findings provide a versatile approach of designing efficient artificial light-harvesting systems and constructing highly emissive organic materials in aqueous media.},
	number = {1},
	urldate = {2021-03-05},
	journal = {JOURNAL OF THE AMERICAN CHEMICAL SOCIETY},
	author = {Song, Qiao and Goia, Sofia and Yang, Jie and Hall, Stephen C. L. and Staniforth, Michael and Stavros, Vasilios G. and Perrier, Sebastien},
	month = jan,
	year = {2021},
	pages = {382--389},
}

Artificial light-harvesting systems in aqueous media which mimic nature are of significant importance; however, they are often restrained by the solubility and the undesired aggregation-caused quenching effect of the hydrophobic chromophores. Here, we report a generalized strategy toward the construction of efficient artificial light-harvesting systems based on supramolecular peptide nanotubes in water. By molecularly aligning the hydrophobic chromophores along the nanotubes in a slipped manner, an artificial light-harvesting system with a two-step sequential Forster resonance energy transfer process is successfully fabricated, showing an energy transfer efficiency up to 95% and a remarkably high fluorescence quantum yield of 30%, along with high stability. Furthermore, the spectral emission could be continuously tuned from blue through green to orange, as well as outputted as a white light continuum with a fluorescence quantum yield of 29.9%. Our findings provide a versatile approach of designing efficient artificial light-harvesting systems and constructing highly emissive organic materials in aqueous media.

@article{armes_introduction_2021,
	title = {Introduction to polymerisation-induced self assembly},
	volume = {12},
	issn = {1759-9954},
	doi = {10.1039/d0py90190c},
	abstract = {Steve Armes, Sebastien Perrier and Per Zetterlund introduce the Polymer Chemistry themed collection on polymerisation-induced self assembly.},
	number = {1},
	urldate = {2021-01-25},
	journal = {POLYMER CHEMISTRY},
	author = {Armes, Steven P. and Perrier, Sebastien and Zetterlund, Per B.},
	month = jan,
	year = {2021},
	pages = {8--11},
}

Steve Armes, Sebastien Perrier and Per Zetterlund introduce the Polymer Chemistry themed collection on polymerisation-induced self assembly.

@article{guimaraes_polymerization-induced_2021,
	title = {Polymerization-induced self-assembly via {RAFT} in emulsion: effect of {Z}-group on the nucleation step},
	volume = {12},
	issn = {1759-9954},
	doi = {10.1039/d0py01311k},
	abstract = {Polymerization-induced self-assembly (PISA) has emerged as one of the most powerful and widely employed techniques for preparation of block copolymer and polymeric nanoparticles in dispersed systems. Its success relies on a rapid, easily scalable and straightforward process, associated with the ability to readily control nanoparticle morphology. In the present work, we have investigated the effect of the Z-group of RAFT agents ZC(=S)-SR on the nucleation step of aqueous RAFT PISA performed in environmentally friendly emulsion polymerization. Seven different poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA) macroRAFTs were synthesized using RAFT agents containing Z-groups of different hydrophilicity. Slow polymerizations and incomplete chain extension reactions were observed for systems with the most hydrophilic Z-group, while the more hydrophobic Z groups led to higher polymerization rates and very successful chain extensions. A mechanism based on Z-group induced RAFT exit is proposed to rationalize this surprising behaviour, providing important information on the mechanistic understanding and optimization of PISA in emulsion.},
	number = {1},
	urldate = {2021-01-25},
	journal = {POLYMER CHEMISTRY},
	author = {Guimaraes, Thiago R. and Bong, Y. Loong and Thompson, Steven W. and Moad, Graeme and Perrier, Sebastien and Zetterlund, Per B.},
	month = jan,
	year = {2021},
	pages = {122--133},
}

Polymerization-induced self-assembly (PISA) has emerged as one of the most powerful and widely employed techniques for preparation of block copolymer and polymeric nanoparticles in dispersed systems. Its success relies on a rapid, easily scalable and straightforward process, associated with the ability to readily control nanoparticle morphology. In the present work, we have investigated the effect of the Z-group of RAFT agents ZC(=S)-SR on the nucleation step of aqueous RAFT PISA performed in environmentally friendly emulsion polymerization. Seven different poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA) macroRAFTs were synthesized using RAFT agents containing Z-groups of different hydrophilicity. Slow polymerizations and incomplete chain extension reactions were observed for systems with the most hydrophilic Z-group, while the more hydrophobic Z groups led to higher polymerization rates and very successful chain extensions. A mechanism based on Z-group induced RAFT exit is proposed to rationalize this surprising behaviour, providing important information on the mechanistic understanding and optimization of PISA in emulsion.

@article{tobin_synthesis_2021,
	title = {Synthesis and self-assembly of corona-functionalised polymeric arsenical nanoparticles},
	volume = {144},
	issn = {0014-3057},
	doi = {10.1016/j.eurpolymj.2020.110235},
	abstract = {Polymeric arsenicals are emerging as an interesting platform for functional and (re)active materials in the field of polymer and (bio)materials science. Through exploiting the diverse and distinct reactivity of organic arsenicals in As(V), As(III) and As(I) oxidation states efficient methods for bioconjugation as well as hydrogel and nanoparticles formation have been reported. Here we expand on this body of work by reporting the synthesis of new amphiphilic block copolymeric arsenicals with a target composition of P((DMAm100-x-co AsAmx)-b-DAAm(100)) (P1, X = 0; P2, X = 5; P3, X = 20) which form nanoparticles (NP1-NP3; D-h = 49-71 nm) upon self-assembly in water. The mole fraction of the AsAm monomer appears to have an effect on the particle morphology and stability, with stability decreasing as a function of the AsAm mole fraction in the corona. The reactivity of the AsAm (As(V)) group has been exploited to modify the corona functionality via direct reduction (NPRed) and sequential reduction and thiol substitution (NPGSH). The resulting As(III)-functionalised nanoparticles (NPRed) exhibited concentration-dependent toxicity against human prostate adenocarcinoma epithelia cell (PC-3) alluding to future development of these particles for mono- or combination therapy within appropriate nanoparticle formulations.},
	urldate = {2021-02-09},
	journal = {EUROPEAN POLYMER JOURNAL},
	author = {Tobin, Hayden and Liarou, Evelina and Song, Ji-Inn and Magiakos, Alexandros and Wilson, Paul},
	month = feb,
	year = {2021},
}

Polymeric arsenicals are emerging as an interesting platform for functional and (re)active materials in the field of polymer and (bio)materials science. Through exploiting the diverse and distinct reactivity of organic arsenicals in As(V), As(III) and As(I) oxidation states efficient methods for bioconjugation as well as hydrogel and nanoparticles formation have been reported. Here we expand on this body of work by reporting the synthesis of new amphiphilic block copolymeric arsenicals with a target composition of P((DMAm100-x-co AsAmx)-b-DAAm(100)) (P1, X = 0; P2, X = 5; P3, X = 20) which form nanoparticles (NP1-NP3; D-h = 49-71 nm) upon self-assembly in water. The mole fraction of the AsAm monomer appears to have an effect on the particle morphology and stability, with stability decreasing as a function of the AsAm mole fraction in the corona. The reactivity of the AsAm (As(V)) group has been exploited to modify the corona functionality via direct reduction (NPRed) and sequential reduction and thiol substitution (NPGSH). The resulting As(III)-functionalised nanoparticles (NPRed) exhibited concentration-dependent toxicity against human prostate adenocarcinoma epithelia cell (PC-3) alluding to future development of these particles for mono- or combination therapy within appropriate nanoparticle formulations.

@article{goutianos_low_2021,
	title = {On the low reinforcing efficiency of carbon nanotubes in high-performance polymer fibres},
	volume = {7},
	issn = {2055-0324},
	doi = {10.1080/20550324.2021.1917815},
	abstract = {Driven by the exceptionally high mechanical properties of carbon nanotubes (CNTs), over the years an extensive research effort has been devoted to the reinforcement of high-performance polymer fibres with CNTs. However, to date, improvements in the strength of these fibres have been rather modest even for relatively high CNT contents. After a brief review of CNT reinforced polymer fibres, here, analytical and numerical finite element models will be used to show that these experimental findings are to be expected based on the intrinsic mechanical properties of these polymer fibres and CNTs, their aspect ratio and interfacial characteristics. Results show that for realistic CNT contents and aspect ratios, the extraordinary strength of CNTs cannot be easily fully exploited in high-performance polymer fibres like Dyneema (R) or Kevlar (R). Even if CNTs are perfectly aligned, bonded and dispersed, the low intrinsic shear strength of these highly anisotropic polymer fibres limits effective stress transfer and nanotube reinforcement.},
	number = {1},
	urldate = {2021-06-01},
	journal = {NANOCOMPOSITES},
	author = {Goutianos, Stergios and Peijs, Ton},
	month = jan,
	year = {2021},
	pages = {53--69},
}

Driven by the exceptionally high mechanical properties of carbon nanotubes (CNTs), over the years an extensive research effort has been devoted to the reinforcement of high-performance polymer fibres with CNTs. However, to date, improvements in the strength of these fibres have been rather modest even for relatively high CNT contents. After a brief review of CNT reinforced polymer fibres, here, analytical and numerical finite element models will be used to show that these experimental findings are to be expected based on the intrinsic mechanical properties of these polymer fibres and CNTs, their aspect ratio and interfacial characteristics. Results show that for realistic CNT contents and aspect ratios, the extraordinary strength of CNTs cannot be easily fully exploited in high-performance polymer fibres like Dyneema (R) or Kevlar (R). Even if CNTs are perfectly aligned, bonded and dispersed, the low intrinsic shear strength of these highly anisotropic polymer fibres limits effective stress transfer and nanotube reinforcement.

@article{sultanova_microscale_2021,
	title = {Microscale diffusion-mechanics model for a polymer-based solid-state battery cathode},
	volume = {186},
	issn = {0927-0256},
	doi = {10.1016/j.commatsci.2020.109990},
	abstract = {A non-linear microscale diffusion-mechanics model combining mass transport and linear momentum balance equations, with elasto-viscoplastic polymer constitutive law and interfacial traction-separation law is proposed to provide a new insight into the effects of viscoplasticity and interfacial damage on the in situ diffusive -mechanical behaviour of a polymer-based cathode for a solid-state battery (SSB). Diffusion and mechanics are coupled through two mechanisms: (1) active particle (AP) volumetric change dependence on Li concentration, and (2) interfacial flux dependence on mechanical opening. The model is resolved for a simple cathode microstructure using an axisymmetric unit cell concept, and integrated with the non-linear finite-element solver ABAQUS with the help of its user subroutines (UMAT and UINTER). Finite-element simulations reveal that plastic deformations of the polymer due to volumetric changes of the AP reduce the value of the interfacial opening displacement, which is desirable for maintaining interfacial flux. The results also demonstrate that slower battery charging rates may lead to a softer polymer response, and thus a smaller interfacial gap. Moreover, a comparison between the linear elastic and current elasto-viscoplastic models for the polymer electrolyte shows that even 5\% volumetric shrinkage of the AP leads to an overprediction of the interfacial opening with the linear elastic material law, which limits its validity in modelling polymer-based SSBs.},
	urldate = {2021-01-05},
	journal = {COMPUTATIONAL MATERIALS SCIENCE},
	author = {Sultanova, Leyla and Figiel, Lukasz},
	month = jan,
	year = {2021},
}

A non-linear microscale diffusion-mechanics model combining mass transport and linear momentum balance equations, with elasto-viscoplastic polymer constitutive law and interfacial traction-separation law is proposed to provide a new insight into the effects of viscoplasticity and interfacial damage on the in situ diffusive -mechanical behaviour of a polymer-based cathode for a solid-state battery (SSB). Diffusion and mechanics are coupled through two mechanisms: (1) active particle (AP) volumetric change dependence on Li concentration, and (2) interfacial flux dependence on mechanical opening. The model is resolved for a simple cathode microstructure using an axisymmetric unit cell concept, and integrated with the non-linear finite-element solver ABAQUS with the help of its user subroutines (UMAT and UINTER). Finite-element simulations reveal that plastic deformations of the polymer due to volumetric changes of the AP reduce the value of the interfacial opening displacement, which is desirable for maintaining interfacial flux. The results also demonstrate that slower battery charging rates may lead to a softer polymer response, and thus a smaller interfacial gap. Moreover, a comparison between the linear elastic and current elasto-viscoplastic models for the polymer electrolyte shows that even 5% volumetric shrinkage of the AP leads to an overprediction of the interfacial opening with the linear elastic material law, which limits its validity in modelling polymer-based SSBs.

@article{zhang_nanoengineered_2021,
	title = {Nanoengineered electrospun fibers and their biomedical applications: a review},
	volume = {7},
	issn = {2055-0324},
	doi = {10.1080/20550324.2020.1857121},
	abstract = {Electrospun fibers have received significant interests for various application areas such as filtration, composites and biomedical products due to their large surface area, good continuity, high porosity and many other unique properties. In bio-related applications, electrospun fibers have been used for in-situ drug delivery, tissue engineering scaffolds and wound dressing. In more recent years, there has been a drive toward novel electrospun fibers with added functionalities. Nanoengineering of electrospun fibers has introduced many of such novel properties. Through this review, researchers are provided with a state of the art overview of nanoenhanced electrospun fibers with added functionalities. Examples of some nanoengineered fibers include; surface functionalization, multi-component fibers, porous nanofibers, the creation of surface nano-topographies, and the incorporation of nanoparticles to create hierarchical fibrous structures for tailoring of physicochemical properties with a special focus on biomedical applications.},
	number = {1},
	urldate = {2021-02-03},
	journal = {NANOCOMPOSITES},
	author = {Zhang, Xi and Shi, Xuetao and Gautrot, Julien E. and Peijs, Ton},
	month = jan,
	year = {2021},
	pages = {1--34},
}

Electrospun fibers have received significant interests for various application areas such as filtration, composites and biomedical products due to their large surface area, good continuity, high porosity and many other unique properties. In bio-related applications, electrospun fibers have been used for in-situ drug delivery, tissue engineering scaffolds and wound dressing. In more recent years, there has been a drive toward novel electrospun fibers with added functionalities. Nanoengineering of electrospun fibers has introduced many of such novel properties. Through this review, researchers are provided with a state of the art overview of nanoenhanced electrospun fibers with added functionalities. Examples of some nanoengineered fibers include; surface functionalization, multi-component fibers, porous nanofibers, the creation of surface nano-topographies, and the incorporation of nanoparticles to create hierarchical fibrous structures for tailoring of physicochemical properties with a special focus on biomedical applications.

@article{beyer_thiol-bromo_2021,
	title = {Thiol-{Bromo} {Click} {Reaction} for {One}-{Pot} {Synthesis} of {Star}-{Shaped} {Polymers}},
	volume = {42},
	issn = {1022-1336},
	doi = {10.1002/marc.202000519},
	abstract = {Star-shaped polymers have unique physical properties and they are sought after materials in industry. However, the ease of synthesis is essential for translation of these materials into large-scale applications. Herein, a highly efficient synthetic method to prepare star-shaped polymers by combination of Cu-mediated reversible deactivation radical polymerization (Cu-RDRP) and thiol-bromo click reaction is described. Well-defined linear and block polymers with a very high bromine chain end fidelity are obtained via Cu-RDRP and subsequently react with multi-functional thiol compounds. High coupling efficiencies of larger than 90\% are obtained owing to the quick and efficient reaction between thiols and alkyl bromides. Moreover, the arms of the obtained star-shaped polymers are linked via thioether bonds to the core, making them susceptible for oxidative degradation.},
	number = {2},
	urldate = {2020-12-01},
	journal = {MACROMOLECULAR RAPID COMMUNICATIONS},
	author = {Beyer, Valentin Peter and Cattoz, Beatrice and Becer, Caglar Remzi},
	month = jan,
	year = {2021},
	note = {Infineum UK Ltd},
}

Star-shaped polymers have unique physical properties and they are sought after materials in industry. However, the ease of synthesis is essential for translation of these materials into large-scale applications. Herein, a highly efficient synthetic method to prepare star-shaped polymers by combination of Cu-mediated reversible deactivation radical polymerization (Cu-RDRP) and thiol-bromo click reaction is described. Well-defined linear and block polymers with a very high bromine chain end fidelity are obtained via Cu-RDRP and subsequently react with multi-functional thiol compounds. High coupling efficiencies of larger than 90% are obtained owing to the quick and efficient reaction between thiols and alkyl bromides. Moreover, the arms of the obtained star-shaped polymers are linked via thioether bonds to the core, making them susceptible for oxidative degradation.

@article{chen_understanding_2021,
	title = {Understanding the effects of montmorillonite and sepiolite on the properties of solution-cast chitosan and chitosan/silk peptide composite films},
	volume = {70},
	issn = {0959-8103},
	doi = {10.1002/pi.6103},
	abstract = {Blending with another biopolymer or nanomaterial can be an effective route to modify or tailor the properties of chitosan materials. In this work, we compared the effects of two nanoclays, montmorillonite (MMT) and sepiolite (SPT), on the properties of chitosan and chitosan/silk peptide (SP) films. While the solution-cast chitosan/SP films showed no phase separation on a micron length scale, some degree of molecular-level heterogeneity or incompatibility was evident. MMT nanoplatelets were delaminated in the chitosan-alone matrix, resulting in enhanced mechanical properties and hydrophobicity. In comparison, inclusion of SPT nanoneedles was less effective at altering the properties of the chitosan matrix. In the chitosan/SP system, the MMT was poorly dispersed, suggesting the two biopolymers interfere with how each interacts with the nanoclay. Nonetheless, in this case, MMT disrupted biopolymer chain interactions, leading to reduced mechanical properties and increased surface hydrophilicity. In contrast, SPT was found to enhance the mechanical properties of the chitosan/SP matrix, certainly associated with it being better dispersed. Thus, this work shows the efficacy of MMT and SPT as a route to altering the structure and properties of chitosan-based biopolymer matrices.},
	number = {5},
	urldate = {2020-09-22},
	journal = {POLYMER INTERNATIONAL},
	author = {Chen, Pei and Xie, Fengwei and McNally, Tony},
	month = may,
	year = {2021},
	pages = {527--535},
}

Blending with another biopolymer or nanomaterial can be an effective route to modify or tailor the properties of chitosan materials. In this work, we compared the effects of two nanoclays, montmorillonite (MMT) and sepiolite (SPT), on the properties of chitosan and chitosan/silk peptide (SP) films. While the solution-cast chitosan/SP films showed no phase separation on a micron length scale, some degree of molecular-level heterogeneity or incompatibility was evident. MMT nanoplatelets were delaminated in the chitosan-alone matrix, resulting in enhanced mechanical properties and hydrophobicity. In comparison, inclusion of SPT nanoneedles was less effective at altering the properties of the chitosan matrix. In the chitosan/SP system, the MMT was poorly dispersed, suggesting the two biopolymers interfere with how each interacts with the nanoclay. Nonetheless, in this case, MMT disrupted biopolymer chain interactions, leading to reduced mechanical properties and increased surface hydrophilicity. In contrast, SPT was found to enhance the mechanical properties of the chitosan/SP matrix, certainly associated with it being better dispersed. Thus, this work shows the efficacy of MMT and SPT as a route to altering the structure and properties of chitosan-based biopolymer matrices.

@article{jenkins_investigation_2020,
	title = {Investigation into {Durable} {Polymers} with {Enhanced} {Toughness} and {Elasticity} for {Application} in {Flexible} {Li}-{Ion} {Batteries}},
	volume = {3},
	issn = {2574-0962},
	doi = {10.1021/acsaem.0c02442},
	abstract = {Next-generation wearable devices compel the development of lithium-ion batteries (LIBs) that can afford mechanical flexibility while remaining safe and stable energy sources. In conventional battery designs the electrode coatings are susceptible to fracture and disintegration when exposed to cyclic flexure. This results in capacity loss, resistance increases, and severely limits their cycle life. Polyurethane (PU) has been investigated as a battery binder but without research into the variety of chemistries available, and how they affect performance. This research investigates three different PU chemistries, each composed of a different polyol backbone-polyester, polyether and polycaprolactone. These are compared with PVDF, the most commonly used rigid binder in industry. The combination of electrochemical and mechanical characterization identified the importance of PU binder chemistry, particularly when the binder's interaction with the electrolyte was considered. Both the polyester and polycaprolactone PU chemistries swelled significantly when placed in an electrolyte, compromising their conductive networks and mechanical advantages. In contrast, polyether PU was found to be a suitable binder for flexible batteries as it has strong adhesion and retains its properties even after swelling in the electrolyte. These findings present a promising polymer choice to facilitate the development of advanced and durable electrodes for flexible energy storage systems.},
	number = {12},
	urldate = {2021-03-02},
	journal = {ACS APPLIED ENERGY MATERIALS},
	author = {Jenkins, Craig A. and Coles, Stuart R. and Loveridge, Melanie J.},
	month = dec,
	year = {2020},
	pages = {12494--12505},
}

Next-generation wearable devices compel the development of lithium-ion batteries (LIBs) that can afford mechanical flexibility while remaining safe and stable energy sources. In conventional battery designs the electrode coatings are susceptible to fracture and disintegration when exposed to cyclic flexure. This results in capacity loss, resistance increases, and severely limits their cycle life. Polyurethane (PU) has been investigated as a battery binder but without research into the variety of chemistries available, and how they affect performance. This research investigates three different PU chemistries, each composed of a different polyol backbone-polyester, polyether and polycaprolactone. These are compared with PVDF, the most commonly used rigid binder in industry. The combination of electrochemical and mechanical characterization identified the importance of PU binder chemistry, particularly when the binder's interaction with the electrolyte was considered. Both the polyester and polycaprolactone PU chemistries swelled significantly when placed in an electrolyte, compromising their conductive networks and mechanical advantages. In contrast, polyether PU was found to be a suitable binder for flexible batteries as it has strong adhesion and retains its properties even after swelling in the electrolyte. These findings present a promising polymer choice to facilitate the development of advanced and durable electrodes for flexible energy storage systems.

@article{przybyla_natural_2020,
	title = {Natural cyclodextrins and their derivatives for polymer synthesis},
	volume = {11},
	issn = {1759-9954},
	doi = {10.1039/d0py01464h},
	abstract = {Cyclodextrins (CDs) are a family of cyclic oligosaccharides with a hydrophilic exterior surface and a nonpolar cavity interior, therefore, CDs can form inclusion complexes through noncovalent interactions with a broad range of hydrophobic guests. CD derivatives and CD-based polymers find important uses in different fields such as pharmacy, cosmetics, biomedicine, textiles, and food domain due to their unique properties during the past decade. Hence, in this review, functionalised CDs and CD-based polymers are classified and discussed according to their synthetic approaches comprehensively to help polymer chemists for the development of new CD-based materials for different types of applications.},
	number = {48},
	urldate = {2021-01-12},
	journal = {POLYMER CHEMISTRY},
	author = {Przybyla, Magdalena A. and Yilmaz, Gokhan and Becer, C. Remzi},
	month = dec,
	year = {2020},
	pages = {7582--7602},
}

Cyclodextrins (CDs) are a family of cyclic oligosaccharides with a hydrophilic exterior surface and a nonpolar cavity interior, therefore, CDs can form inclusion complexes through noncovalent interactions with a broad range of hydrophobic guests. CD derivatives and CD-based polymers find important uses in different fields such as pharmacy, cosmetics, biomedicine, textiles, and food domain due to their unique properties during the past decade. Hence, in this review, functionalised CDs and CD-based polymers are classified and discussed according to their synthetic approaches comprehensively to help polymer chemists for the development of new CD-based materials for different types of applications.

@article{lefley_macromolecular_2020,
	title = {Macromolecular design and preparation of polymersomes},
	volume = {11},
	issn = {1759-9954},
	doi = {10.1039/d0py01247e},
	abstract = {From drug delivery to nanoreactors and protocells, polymersomes have gained considerable interest from researchers due to their novel applications. However, one of the main challenges is the selection of the most appropriate synthetic route. It is crucial to consider factors such as desired application, functionalisation, and environment of the polymersome when designing a synthetic route. This review will explore the current scope of polymersome synthesis and preparation methods, and will conclude by highlighting the most recent reports on polymersome related systems such as virus-like nanoparticles. From the choice of monomers, to polymerisation techniques, and to preparation methods used, we aim for this review to be utilised as a tutorial guide for the synthesis of a range of polymersomes, each with varying characteristics and applications.},
	number = {45},
	urldate = {2020-12-09},
	journal = {POLYMER CHEMISTRY},
	author = {Lefley, James and Waldron, Christopher and Becer, C. Remzi},
	month = dec,
	year = {2020},
	pages = {7124--7136},
}

From drug delivery to nanoreactors and protocells, polymersomes have gained considerable interest from researchers due to their novel applications. However, one of the main challenges is the selection of the most appropriate synthetic route. It is crucial to consider factors such as desired application, functionalisation, and environment of the polymersome when designing a synthetic route. This review will explore the current scope of polymersome synthesis and preparation methods, and will conclude by highlighting the most recent reports on polymersome related systems such as virus-like nanoparticles. From the choice of monomers, to polymerisation techniques, and to preparation methods used, we aim for this review to be utilised as a tutorial guide for the synthesis of a range of polymersomes, each with varying characteristics and applications.

@article{liu_effect_2020,
	title = {The effect of conductive network on positive temperature coefficient behaviour in conductive polymer composites},
	volume = {139},
	issn = {1359-835X},
	doi = {10.1016/j.compositesa.2020.106074},
	abstract = {Flexible and controllable self-regulating heating devices with positive temperature coefficient (PTC) behaviour are potentially excellent candidates in applications like healthcare, soft robotics, artificial skin and wearable electronics. Although extensive studies have been carried out in this field to understand the mechanism of PTC effect, rather limited conclusions have been reached. Many controversies remain on the dominating factors that influence the PTC performance of composites, hence limiting their design and broader applications. Herein, we propose a systematic study to explore the PTC phenomenon and the underlying mechanism, from a conductive network viewpoint, taking account of both conductive fillers and polymer matrices. Three representative conductive fillers with distinct dimensions and shapes (0D silver coated glass spheres, 1D carbon nanotubes and 2D graphene nanoplatelets), in combination with three different polymer matrices (high density polyethylene, thermoplastic polyurethane and polycarbonate) were selected to elucidate the effect of the "robustness" of different conductive networks on PTC behaviour in conductive polymer composites (CPCs). The desired conductive network can be obtained by selecting preferentially larger filler size, lower filler aspect ratio and/or selective distribution of filler (e.g. in the amorphous region of semi-crystalline polymers). The highest PTC intensity was observed around the "critical" percolation threshold, in correspondence of networks with the lowest number of inter-particle contacts. This study can serve as a guideline in the selection of the most appropriate conductive filler and polymer matrix for various self-regulating heating requirements and final applications.},
	urldate = {2020-11-10},
	journal = {COMPOSITES PART A-APPLIED SCIENCE AND MANUFACTURING},
	author = {Liu, Yi and Asare, Eric and Porwal, Harshit and Barbieri, Ettore and Goutianos, Stergios and Evans, Jamie and Newton, Mark and Busfield, James J. C. and Peijs, Ton and Zhang, Han and Bilotti, Emiliano},
	month = dec,
	year = {2020},
	note = {LMK Thermosafe Ltd},
}

Flexible and controllable self-regulating heating devices with positive temperature coefficient (PTC) behaviour are potentially excellent candidates in applications like healthcare, soft robotics, artificial skin and wearable electronics. Although extensive studies have been carried out in this field to understand the mechanism of PTC effect, rather limited conclusions have been reached. Many controversies remain on the dominating factors that influence the PTC performance of composites, hence limiting their design and broader applications. Herein, we propose a systematic study to explore the PTC phenomenon and the underlying mechanism, from a conductive network viewpoint, taking account of both conductive fillers and polymer matrices. Three representative conductive fillers with distinct dimensions and shapes (0D silver coated glass spheres, 1D carbon nanotubes and 2D graphene nanoplatelets), in combination with three different polymer matrices (high density polyethylene, thermoplastic polyurethane and polycarbonate) were selected to elucidate the effect of the "robustness" of different conductive networks on PTC behaviour in conductive polymer composites (CPCs). The desired conductive network can be obtained by selecting preferentially larger filler size, lower filler aspect ratio and/or selective distribution of filler (e.g. in the amorphous region of semi-crystalline polymers). The highest PTC intensity was observed around the "critical" percolation threshold, in correspondence of networks with the lowest number of inter-particle contacts. This study can serve as a guideline in the selection of the most appropriate conductive filler and polymer matrix for various self-regulating heating requirements and final applications.

@article{rodriguez_effect_2020,
	title = {Effect of chromium doping on high temperature tribological properties of silicon-doped diamond-like carbon films},
	volume = {152},
	issn = {0301-679X},
	doi = {10.1016/j.triboint.2020.106546},
	abstract = {Amorphous carbon films were deposited by means of closed-field unbalanced magnetron sputtering (CFUBMS). The silicon content was fixed at 1.3 at. \%, while the chromium content was increased by modification of the current applied to the chromium magnetrons, with two doping levels, 0.3 and 2.7 at. \%. Both, hardness and thermal stability were found to decrease as result of increasing chromium. Ball-on-disk tests revealed friction coefficients of 0.06 at room temperature with similar specific wear rate in all films (similar to 4 x 10(-13) m(3) N-1 m(-1)). Increasing annealing temperatures were found to reduce the coefficient of friction compared to room temperature values, while increasing the specific wear rate for all films.},
	urldate = {2021-02-22},
	journal = {TRIBOLOGY INTERNATIONAL},
	author = {Rodriguez, Bruno J. and Schiller, Tara L. and Proprentner, Daniela and Walker, Marc and Low, C. T. John and Shollock, Barbara and Sun, Hailin and Navabpour, Parnia},
	month = dec,
	year = {2020},
	note = {Teer Coatings Ltd},
}

Amorphous carbon films were deposited by means of closed-field unbalanced magnetron sputtering (CFUBMS). The silicon content was fixed at 1.3 at. %, while the chromium content was increased by modification of the current applied to the chromium magnetrons, with two doping levels, 0.3 and 2.7 at. %. Both, hardness and thermal stability were found to decrease as result of increasing chromium. Ball-on-disk tests revealed friction coefficients of 0.06 at room temperature with similar specific wear rate in all films (similar to 4 x 10(-13) m(3) N-1 m(-1)). Increasing annealing temperatures were found to reduce the coefficient of friction compared to room temperature values, while increasing the specific wear rate for all films.

@article{nathan_life_2020,
	title = {Life {Cycle} {Assessment} and {Judgement}},
	volume = {14},
	issn = {1871-4757},
	doi = {10.1007/s11569-020-00376-2},
	abstract = {It has become a standard for researchers carrying out biotechnology projects to do a life cycle assessment (LCA). This is a process for assessing the environmental impact of a technology, product or policy. Doing so is no simple matter, and in the last decades, a rich set of methodologies has developed around LCA. However, the proper methods and meanings of the process remain contested. Preceding the development of the international standard that now governs LCA, there was a lively debate in the academic community about the inclusion of 'values' within the process. We revisit this debate and reconsider the way forward for LCA. We set out ways in which those outside of science can provide input into LCAs by informing the value assumptions at stake. At the same time, we will emphasize that the role of those within the scientific community need not (and sometimes, will inevitably not) involve value-free inquiry. We carry out this exploration through a case study of a particular technology project that sought ways to produce industrial and consumer products from algal oils.},
	number = {3},
	urldate = {2020-12-09},
	journal = {NANOETHICS},
	author = {Nathan, Christopher and Coles, Stuart},
	month = dec,
	year = {2020},
	pages = {271--283},
}

It has become a standard for researchers carrying out biotechnology projects to do a life cycle assessment (LCA). This is a process for assessing the environmental impact of a technology, product or policy. Doing so is no simple matter, and in the last decades, a rich set of methodologies has developed around LCA. However, the proper methods and meanings of the process remain contested. Preceding the development of the international standard that now governs LCA, there was a lively debate in the academic community about the inclusion of 'values' within the process. We revisit this debate and reconsider the way forward for LCA. We set out ways in which those outside of science can provide input into LCAs by informing the value assumptions at stake. At the same time, we will emphasize that the role of those within the scientific community need not (and sometimes, will inevitably not) involve value-free inquiry. We carry out this exploration through a case study of a particular technology project that sought ways to produce industrial and consumer products from algal oils.

@article{baker_sars-cov-2_2020,
	title = {The {SARS}-{COV}-2 {Spike} {Protein} {Binds} {Sialic} {Acids} and {Enables} {Rapid} {Detection} in a {Lateral} {Flow} {Point} of {Care} {Diagnostic} {Device}},
	volume = {6},
	issn = {2374-7943},
	doi = {10.1021/acscentsci.0c00855},
	abstract = {There is an urgent need to understand the behavior of of the novel coronavirus (SARS-COV-2), which is the causative agent of COVID-19, and to develop point-of-care diagnostics. Here, a glyconanoparticle platform is used to discover that N-acetyl neuraminic acid has affinity toward the SARS-COV-2 spike glycoprotein, demonstrating its glycan-binding function. Optimization of the particle size and coating enabled detection of the spike glycoprotein in lateral flow and showed selectivity over the SARS-COV-1 spike protein. Using a virus-like particle and a pseudotyped lentivirus model, paper-based lateral flow detection was demonstrated in under 30 min, showing the potential of this system as a low-cost detection platform.},
	number = {11},
	urldate = {2020-11-25},
	journal = {ACS CENTRAL SCIENCE},
	author = {Baker, Alexander N. and Richards, Sarah-Jane and Guy, Collette S. and Congdon, Thomas R. and Hasan, Muhammad and Zwetsloot, Alexander J. and Gallo, Angelo and Lewandowski, Jozef R. and Stansfeld, Phillip J. and Straube, Anne and Walker, Marc and Chessa, Simona and Pergolizzi, Giulia and Dedola, Simone and Field, Robert A. and Gibson, I, Matthew},
	month = nov,
	year = {2020},
	note = {Iceni Diagnost Ltd},
	pages = {2046--2052},
}

There is an urgent need to understand the behavior of of the novel coronavirus (SARS-COV-2), which is the causative agent of COVID-19, and to develop point-of-care diagnostics. Here, a glyconanoparticle platform is used to discover that N-acetyl neuraminic acid has affinity toward the SARS-COV-2 spike glycoprotein, demonstrating its glycan-binding function. Optimization of the particle size and coating enabled detection of the spike glycoprotein in lateral flow and showed selectivity over the SARS-COV-1 spike protein. Using a virus-like particle and a pseudotyped lentivirus model, paper-based lateral flow detection was demonstrated in under 30 min, showing the potential of this system as a low-cost detection platform.

@article{hrabina_cationic_2020,
	title = {Cationic {FeII} {Triplex}-{Forming} {Metallohelices} as {DNA} {Bulge} {Binders}},
	volume = {26},
	issn = {0947-6539},
	doi = {10.1002/chem.202004060},
	abstract = {Bulges are essential structural elements in nucleic acids. The detection and targeting of bulged DNA sequences are highly important. Small molecules capable of targeting DNA bulges have attracted considerable attention because they cannot only be used as reagents for bulge recognition, but also as potential therapeutic drugs. Herein, the interactions of DNA duplexes, containing bulges of various sizes and base compositions, with a series of Fe-II triplex-forming metallohelices are reported. The results obtained, with the aid of molecular biophysics methods, show that the investigated metallohelices prefer to bind to bulged DNA, rather than double-stranded DNA, and that their binding affinities towards bulges differ among individual metallohelices. Moreover, their binding affinities towards bulges strongly depend on the bulge size and the base composition of the bulge loop. The investigated metallohelices can enter eukaryotic cells and accumulate in the cell nucleus, allowing them to interact with nucleic acids. Hence, it is reasonable to suggest that the interaction of metallohelices with nucleic acid bulges might contribute to the mechanism of their biological activity.},
	number = {69},
	urldate = {2020-11-30},
	journal = {CHEMISTRY-A EUROPEAN JOURNAL},
	author = {Hrabina, Ondrej and Malina, Jaroslav and Scott, Peter and Brabec, Viktor},
	month = dec,
	year = {2020},
	pages = {16554--16562},
}

Bulges are essential structural elements in nucleic acids. The detection and targeting of bulged DNA sequences are highly important. Small molecules capable of targeting DNA bulges have attracted considerable attention because they cannot only be used as reagents for bulge recognition, but also as potential therapeutic drugs. Herein, the interactions of DNA duplexes, containing bulges of various sizes and base compositions, with a series of Fe-II triplex-forming metallohelices are reported. The results obtained, with the aid of molecular biophysics methods, show that the investigated metallohelices prefer to bind to bulged DNA, rather than double-stranded DNA, and that their binding affinities towards bulges differ among individual metallohelices. Moreover, their binding affinities towards bulges strongly depend on the bulge size and the base composition of the bulge loop. The investigated metallohelices can enter eukaryotic cells and accumulate in the cell nucleus, allowing them to interact with nucleic acids. Hence, it is reasonable to suggest that the interaction of metallohelices with nucleic acid bulges might contribute to the mechanism of their biological activity.

@article{kim_-caprolactone-derived_2020,
	title = {An ε-caprolactone-derived 2-oxazoline inimer for the synthesis of graft copolymers},
	volume = {11},
	issn = {1759-9954},
	doi = {10.1039/d0py01092h},
	abstract = {An inimer approach is presented here for the formation of bottlebrush copolymers consisting of a poly(2-oxazoline) backbone and acrylate branches. A hydroxyl group containing 2-oxazoline (2-n-pentanol-2-oxazoline) was synthesized from epsilon-caprolactone, which is a sustainable starting material. 2-n-Pentanol-2-oxazoline was then further functionalized with a bromoisobutyrate group, which was used to initiate a Cu(0)-mediated reversible-deactivation radical polymerisation (RDRP) of acrylates. This compound is termed an "inimer" because it contains both a monomer (2-oxazoline) and an initiator (the RDRP initiator in this study). Herein, we report the use of an inimer to form 2-oxazoline-based polymer backbones through cationic ring opening polymerisation, and further polymerisation via the Cu(0)-mediated RDRP of acrylates was achieved by initiating from the RDRP-initiator sites embedded within the poly(2-oxazoline) backbone. Furthermore, statistical copolymers of 2-ethyl 2-oxazoline and the inimer were also formed leading to statistically distributed radical initiating sites, which were then used to form graft copolymers of varying densities.},
	number = {42},
	urldate = {2020-11-17},
	journal = {POLYMER CHEMISTRY},
	author = {Kim, Jungyeon and Waldron, Christopher and Cattoz, Beatrice and Becer, C. Remzi},
	month = nov,
	year = {2020},
	note = {Infineum UK Ltd},
	pages = {6847--6852},
}

An inimer approach is presented here for the formation of bottlebrush copolymers consisting of a poly(2-oxazoline) backbone and acrylate branches. A hydroxyl group containing 2-oxazoline (2-n-pentanol-2-oxazoline) was synthesized from epsilon-caprolactone, which is a sustainable starting material. 2-n-Pentanol-2-oxazoline was then further functionalized with a bromoisobutyrate group, which was used to initiate a Cu(0)-mediated reversible-deactivation radical polymerisation (RDRP) of acrylates. This compound is termed an "inimer" because it contains both a monomer (2-oxazoline) and an initiator (the RDRP initiator in this study). Herein, we report the use of an inimer to form 2-oxazoline-based polymer backbones through cationic ring opening polymerisation, and further polymerisation via the Cu(0)-mediated RDRP of acrylates was achieved by initiating from the RDRP-initiator sites embedded within the poly(2-oxazoline) backbone. Furthermore, statistical copolymers of 2-ethyl 2-oxazoline and the inimer were also formed leading to statistically distributed radical initiating sites, which were then used to form graft copolymers of varying densities.

@article{goutianos_self-reinforced_2020,
	title = {Self-{Reinforced} {Polypropylene} {Composites} based on {Discontinuous} {Tapes}-{An} {Experimental} and {Numerical} {Study} of the {Influence} of {Tape} {Length}},
	volume = {27},
	issn = {0929-189X},
	doi = {10.1007/s10443-020-09838-y},
	abstract = {The creation of highly oriented, coextruded polypropylene (PP) tapes allows the production of recyclable self-reinforced polypropylene (SRPP) or all-PP composites, with a large temperature processing window and high volume reinforcement content (similar to 90\%). The objective of this research is to assess the performance potential of SRPP composites based on discontinuous or short tapes. For this, the critical tape length for effective mechanical reinforcement of aligned discontinuous PP tapes was determined, while the stress transfer from PP matrix to PP tape was investigated in single tape model composites in combination with an optical strain mapping technique. Mechanical behaviour of both single tape as well as aligned tape model composites was evaluated using finite element analysis (FEA) and used to predict the properties of randomly oriented short tape composites. These discontinuous tape SRPP composites may be of interest from a manufacturing as well as recycling point of view. In terms of manufacturing, such systems are of interest as they may show improved formability during stamping or compression moulding operations while from a recycling point of view it would allow the re-use of production waste like cuttings of fabrics or tapes.},
	number = {6},
	urldate = {2020-11-17},
	journal = {APPLIED COMPOSITE MATERIALS},
	author = {Goutianos, Stergios and Cabrera, Norbert O. and Alcock, Ben and Reynolds, Neil and Peijs, Ton},
	month = dec,
	year = {2020},
	pages = {767--793},
}

The creation of highly oriented, coextruded polypropylene (PP) tapes allows the production of recyclable self-reinforced polypropylene (SRPP) or all-PP composites, with a large temperature processing window and high volume reinforcement content (similar to 90%). The objective of this research is to assess the performance potential of SRPP composites based on discontinuous or short tapes. For this, the critical tape length for effective mechanical reinforcement of aligned discontinuous PP tapes was determined, while the stress transfer from PP matrix to PP tape was investigated in single tape model composites in combination with an optical strain mapping technique. Mechanical behaviour of both single tape as well as aligned tape model composites was evaluated using finite element analysis (FEA) and used to predict the properties of randomly oriented short tape composites. These discontinuous tape SRPP composites may be of interest from a manufacturing as well as recycling point of view. In terms of manufacturing, such systems are of interest as they may show improved formability during stamping or compression moulding operations while from a recycling point of view it would allow the re-use of production waste like cuttings of fabrics or tapes.

@article{chen_introducing_2020,
	title = {Introducing {Porosity} in {Colloidal} {Biocoatings} to {Increase} {Bacterial} {Viability}},
	volume = {21},
	issn = {1525-7797},
	doi = {10.1021/acs.biomac.0c00649},
	abstract = {A biocoating confines nongrowing, metabolically active bacteria within a synthetic colloidal polymer (i.e., latex) film. Bacteria encapsulated inside biocoatings can perform useful functions, such as a biocatalyst in wastewater treatment. A biocoating needs to have a high permeability to allow a high rate of mass transfer for rehydration and the transport of both nutrients and metabolic products. It therefore requires an interconnected porous structure. Tuning the porosity architecture is a challenge. Here, we exploited rigid tubular nanodays (halloysite) and nontoxic latex particles (with a relatively high glass transition temperature) as the colloidal "building blocks" to tailor the porosity inside biocoatings containing Escherichia coli bacteria as a model organism. Electron microscope images revealed inefficient packing of the rigid nanotubes and proved the existence of nanovoids along the halloysite/polymer interfaces. Single-cell observations using confocal laser scanning microscopy provided evidence for metabolic activity of the E. coli within the biocoatings through the expression of a yellow fluorescent protein. A custom-built apparatus was used to measure the permeability of a fluorescein sodium salt in the biocoatings. Whereas there was no measurable permeability in a coating made from only latex particles, the permeability coefficient of the composite biocoatings increased with increasing halloysite content up to a value of 1 X 10(-4) m h(-1). The effects of this increase in permeability was demonstrated through a specially developed resazurin reduction assay. Bacteria encapsulated in halloysite composite biocoatings had statistically significant higher metabolic activities in comparison to bacteria encapsulated in a nonoptimized coating made from latex particles alone.},
	number = {11},
	urldate = {2021-01-15},
	journal = {BIOMACROMOLECULES},
	author = {Chen, Yuxiu and Krings, Simone and Booth, Joshua R. and Bon, Stefan A. F. and Hingley-Wilson, Suzanne and Keddie, Joseph L.},
	month = nov,
	year = {2020},
	pages = {4545--4558},
}

A biocoating confines nongrowing, metabolically active bacteria within a synthetic colloidal polymer (i.e., latex) film. Bacteria encapsulated inside biocoatings can perform useful functions, such as a biocatalyst in wastewater treatment. A biocoating needs to have a high permeability to allow a high rate of mass transfer for rehydration and the transport of both nutrients and metabolic products. It therefore requires an interconnected porous structure. Tuning the porosity architecture is a challenge. Here, we exploited rigid tubular nanodays (halloysite) and nontoxic latex particles (with a relatively high glass transition temperature) as the colloidal "building blocks" to tailor the porosity inside biocoatings containing Escherichia coli bacteria as a model organism. Electron microscope images revealed inefficient packing of the rigid nanotubes and proved the existence of nanovoids along the halloysite/polymer interfaces. Single-cell observations using confocal laser scanning microscopy provided evidence for metabolic activity of the E. coli within the biocoatings through the expression of a yellow fluorescent protein. A custom-built apparatus was used to measure the permeability of a fluorescein sodium salt in the biocoatings. Whereas there was no measurable permeability in a coating made from only latex particles, the permeability coefficient of the composite biocoatings increased with increasing halloysite content up to a value of 1 X 10(-4) m h(-1). The effects of this increase in permeability was demonstrated through a specially developed resazurin reduction assay. Bacteria encapsulated in halloysite composite biocoatings had statistically significant higher metabolic activities in comparison to bacteria encapsulated in a nonoptimized coating made from latex particles alone.

@article{eriksson_influence_2020,
	title = {Influence of the {Solidification} {Process} on the {Mechanical} {Properties} of {Solid}-{State} {Drawn} {PCL}/{Sepiolite} {Nanocomposite} {Tapes}},
	volume = {8},
	issn = {2079-6439},
	doi = {10.3390/fib8110070},
	abstract = {In this research, poly(epsilon-caprolactone) (PCL) was melt-mixed with sepiolite nanoclays in a twin-screw extruder. In a subsequent step, the extruded films were drawn in the solid state to highly oriented nanocomposite films or tapes. A twin-screw extruder equipped with a Sultzer mixer for improved mixing in combination with a bench top drawing unit was used to prepare oriented nanocomposite tapes of different sepiolite loading and draw ratios. In order to study the influence of the solidification step on the drawability of the materials, different cooling procedures were applied prior to drawing. Optical microscopy images showed that slow or fast solidification using different chill rolls settings (open or closed) for the cast films resulted in different morphological conditions for subsequent drawing. The addition of sepiolite nanofillers led to nucleation and faster crystallization kinetics and oriented tapes which deformed by homogenous deformation rather than necking. The addition of sepiolite significantly improved the mechanical properties of both undrawn and drawn PCL tapes and Young's modulus (1.5 GPa) and tensile strength (360 MPa) for composites based on 4 wt\% sepiolite were among the highest ever reported for PCL nanocomposites. Interestingly, samples cooled with open chill rolls (slow crystallization) showed the highest modulus while solidification with closed rolls (fast crystallization) showed the highest tensile strength after drawing.},
	number = {11},
	urldate = {2020-12-10},
	journal = {FIBERS},
	author = {Eriksson, Maria and Goossens, Han and Peijs, Ton},
	month = nov,
	year = {2020},
}

In this research, poly(epsilon-caprolactone) (PCL) was melt-mixed with sepiolite nanoclays in a twin-screw extruder. In a subsequent step, the extruded films were drawn in the solid state to highly oriented nanocomposite films or tapes. A twin-screw extruder equipped with a Sultzer mixer for improved mixing in combination with a bench top drawing unit was used to prepare oriented nanocomposite tapes of different sepiolite loading and draw ratios. In order to study the influence of the solidification step on the drawability of the materials, different cooling procedures were applied prior to drawing. Optical microscopy images showed that slow or fast solidification using different chill rolls settings (open or closed) for the cast films resulted in different morphological conditions for subsequent drawing. The addition of sepiolite nanofillers led to nucleation and faster crystallization kinetics and oriented tapes which deformed by homogenous deformation rather than necking. The addition of sepiolite significantly improved the mechanical properties of both undrawn and drawn PCL tapes and Young's modulus (1.5 GPa) and tensile strength (360 MPa) for composites based on 4 wt% sepiolite were among the highest ever reported for PCL nanocomposites. Interestingly, samples cooled with open chill rolls (slow crystallization) showed the highest modulus while solidification with closed rolls (fast crystallization) showed the highest tensile strength after drawing.

@article{king_exploring_2020,
	title = {Exploring precision polymers to fine-tune magnetic resonance imaging properties of iron oxide nanoparticles},
	volume = {579},
	issn = {0021-9797},
	doi = {10.1016/j.jcis.2020.06.036},
	abstract = {The use of bio-polymers as stabilising agents for iron oxide-based negative magnetic resonance imaging (MRI) contrast agents has become popular in recent years, however the wide polydispersity of biologically-derived and commercially available polymers limits the ability to produce truly tuneable and reproducible behaviour, a major challenge in this area. In this work, stable colloids of iron oxide nanoparticles were prepared utilising precision-engineered bio-polymer mimics, poly(2-acrylamido-2-methylpropane sodium sulfonate) (P(AMPS)) polymers, with controlled narrow polydispersity molecular weights, as templating stabilisers. In addition to producing magnetic colloids with excellent MRI contrast capabilities (r(2) values reaching 434.2 mM(-1) s(-1) at 25 degrees C and 23 MHz, several times higher than similar commercial analogues), variable field relaxometry provided unexpected important insights into the dynamic environment of the hydrated materials, and hence their exceptional MRI behaviour. Thanks to the polymer's templating backbone and flexible conformation in aqueous suspension, nanocomposites appear to behave as "multi-core" clustered species, enhancing interparticle interactions whilst retaining water diffusion, boosting relaxation properties at low frequency. This clustering behaviour, evidenced by small-angle X-ray scattering, and strong relaxometric response, was fine-tuned using the well-defined molecular weight polymer species with precise iron to polymer ratios. By also showing negligible haemo- lytic activity, these nanocomposites exhibit considerable potential for MRI diagnostics. Crown Copyright (C) 2020 Published by Elsevier Inc. All rights reserved.},
	urldate = {2020-12-08},
	journal = {JOURNAL OF COLLOID AND INTERFACE SCIENCE},
	author = {King, Aaron M. and Bray, Caroline and Hall, Stephen C. L. and Bear, Joseph C. and Bogart, Lara K. and Perrier, Sebastien and Davies, Gemma-Louise},
	month = nov,
	year = {2020},
	pages = {401--411},
}

The use of bio-polymers as stabilising agents for iron oxide-based negative magnetic resonance imaging (MRI) contrast agents has become popular in recent years, however the wide polydispersity of biologically-derived and commercially available polymers limits the ability to produce truly tuneable and reproducible behaviour, a major challenge in this area. In this work, stable colloids of iron oxide nanoparticles were prepared utilising precision-engineered bio-polymer mimics, poly(2-acrylamido-2-methylpropane sodium sulfonate) (P(AMPS)) polymers, with controlled narrow polydispersity molecular weights, as templating stabilisers. In addition to producing magnetic colloids with excellent MRI contrast capabilities (r(2) values reaching 434.2 mM(-1) s(-1) at 25 degrees C and 23 MHz, several times higher than similar commercial analogues), variable field relaxometry provided unexpected important insights into the dynamic environment of the hydrated materials, and hence their exceptional MRI behaviour. Thanks to the polymer's templating backbone and flexible conformation in aqueous suspension, nanocomposites appear to behave as "multi-core" clustered species, enhancing interparticle interactions whilst retaining water diffusion, boosting relaxation properties at low frequency. This clustering behaviour, evidenced by small-angle X-ray scattering, and strong relaxometric response, was fine-tuned using the well-defined molecular weight polymer species with precise iron to polymer ratios. By also showing negligible haemo- lytic activity, these nanocomposites exhibit considerable potential for MRI diagnostics. Crown Copyright (C) 2020 Published by Elsevier Inc. All rights reserved.

@article{lee_particle_2020,
	title = {On {Particle} {Size} {Distributions} in {Catalytic} {Chain} {Transfer} {Emulsion} {Polymerization}: {Chain}-{Extension} and the {Use} of {Derived} {Macromonomers} as {Reactive} {Surfactants} in {Emulsion} {Polymerization}},
	volume = {21},
	issn = {1525-7797},
	doi = {10.1021/acs.biomac.0c00766},
	abstract = {Catalytic chain transfer emulsion polymerization (CCTP) and subsequent chain extension via reversible addition- fragmentation chain transfer (RAFT) were used to synthesize amphiphilic macromonomers (MM), in the form of polymer latexes. The macromonomers consisted of two blocks whose first was a random copolymer of methacrylic acid and methyl methacrylate, at 35:65 mol:mol, while the second block was n-butyl methacrylate P[(MAA-co-MMA)-block-PBMA]. The block copolymer colloids were disintegrated and micellized upon addition of ammonia. The resulting nanosized polymer dispersions were used as reactive surfactants in the emulsion polymerization of n-butyl methacrylate. For this, a dual stage slow-fast monomer feed profile was used. The final polymer latexes were in the sub-100 nm range for the partide diameter at 30\% w/w total polymer content. The emphasis of the work is to discuss and find an explanation for the observed particle size distributions in the three consecutive emulsion polymerization steps. The particle size distribution of the co-unsaturated macromonomer latex synthesized by CCTP emulsion polymerization was found to be much broader than expected. This discrepancy is attributed to an extended particle nucleation period. The chain extension step in the macromonomer latex preparation showed considerable secondary nucleation. The presence of water-soluble macromonomer species from the CCTP emulsion polymerization step assured that control of chain growth persisted. The use of the amphiphilic macromonomers as reactive surfactants in the form of a nanosized aggregate seed dispersion showed that the average particle diameter could be tuned and that the molecular weight distributions could be regulated, when monomer starved conditions were used in the emulsion polymerizations.},
	number = {11},
	urldate = {2021-01-15},
	journal = {BIOMACROMOLECULES},
	author = {Lee, Wai Hin and Booth, Joshua R. and Bon, Stefan A. F.},
	month = nov,
	year = {2020},
	pages = {4599--4614},
}

Catalytic chain transfer emulsion polymerization (CCTP) and subsequent chain extension via reversible addition- fragmentation chain transfer (RAFT) were used to synthesize amphiphilic macromonomers (MM), in the form of polymer latexes. The macromonomers consisted of two blocks whose first was a random copolymer of methacrylic acid and methyl methacrylate, at 35:65 mol:mol, while the second block was n-butyl methacrylate P[(MAA-co-MMA)-block-PBMA]. The block copolymer colloids were disintegrated and micellized upon addition of ammonia. The resulting nanosized polymer dispersions were used as reactive surfactants in the emulsion polymerization of n-butyl methacrylate. For this, a dual stage slow-fast monomer feed profile was used. The final polymer latexes were in the sub-100 nm range for the partide diameter at 30% w/w total polymer content. The emphasis of the work is to discuss and find an explanation for the observed particle size distributions in the three consecutive emulsion polymerization steps. The particle size distribution of the co-unsaturated macromonomer latex synthesized by CCTP emulsion polymerization was found to be much broader than expected. This discrepancy is attributed to an extended particle nucleation period. The chain extension step in the macromonomer latex preparation showed considerable secondary nucleation. The presence of water-soluble macromonomer species from the CCTP emulsion polymerization step assured that control of chain growth persisted. The use of the amphiphilic macromonomers as reactive surfactants in the form of a nanosized aggregate seed dispersion showed that the average particle diameter could be tuned and that the molecular weight distributions could be regulated, when monomer starved conditions were used in the emulsion polymerizations.

@article{wilson_interlayer_2020,
	title = {Interlayer {Hybridization} of {Virgin} {Carbon}, {Recycled} {Carbon} and {Natural} {Fiber} {Laminates}},
	volume = {13},
	issn = {1996-1944},
	doi = {10.3390/ma13214955},
	abstract = {To meet sustainability objectives in the transport sector, natural fiber (NF) and recycled carbon fiber (RCF) have been developed, although they have been typically limited to low to medium performance components. This work has considered the effect of interlayer hybridization of woven NF and non-woven RCF with woven virgin carbon fibers (VCF) on the mechanical and damping performance of hybrid laminates, produced using double bag vacuum infusion (DBVI). The mean damping ratio of the pure laminates showed a trend of NF{\textgreater}RCF{\textgreater}VCF, which was inversely proportional to their modulus. The tensile, flexural and damping properties of hybrid laminates were dominated by the outermost ply. The VCF-RCF and VCF-NF hybrid laminates showed a comparatively greater mean damping ratio. The results of this work demonstrate a method for the uptake of alternative materials with a minimal impact on the mechanical properties and improved damping performance.},
	number = {21},
	urldate = {2020-11-30},
	journal = {MATERIALS},
	author = {Wilson, Peter R. and Ratner, Alon and Stocker, Gary and Syred, Frank and Kirwan, Kerry and Coles, Stuart R.},
	month = nov,
	year = {2020},
	note = {Bruel \& Kjaer Global Engn Serv},
}

To meet sustainability objectives in the transport sector, natural fiber (NF) and recycled carbon fiber (RCF) have been developed, although they have been typically limited to low to medium performance components. This work has considered the effect of interlayer hybridization of woven NF and non-woven RCF with woven virgin carbon fibers (VCF) on the mechanical and damping performance of hybrid laminates, produced using double bag vacuum infusion (DBVI). The mean damping ratio of the pure laminates showed a trend of NF\textgreaterRCF\textgreaterVCF, which was inversely proportional to their modulus. The tensile, flexural and damping properties of hybrid laminates were dominated by the outermost ply. The VCF-RCF and VCF-NF hybrid laminates showed a comparatively greater mean damping ratio. The results of this work demonstrate a method for the uptake of alternative materials with a minimal impact on the mechanical properties and improved damping performance.

@article{patel_post-impact_2020,
	title = {Post-impact damage tolerance of natural fibre-reinforced sheet moulding compound},
	volume = {29},
	issn = {0963-6935},
	doi = {10.1177/2633366X20967935},
	abstract = {Natural fibre composites are of interest for a wide range of semi-structural applications in the building, construction and automotive sector. For a number of these applications, the evaluation of performance degradation after impact is of some relevance. The present work focused on the influence of fibre volume fraction and fibre surface treatment on the residual load-bearing capability of hemp fibre-reinforced sheet moulding compound (H-SMC) after non-penetrating impacts. Post-impact flexural strength and stiffness of H-SMC decreased linearly with increasing impact energy. At higher impact energy levels, the residual flexural strength of H-SMC improved with increasing fibre volume fraction. However, for the same amount of absorbed energy, the residual strength or damage tolerance capability of glass fibre-reinforced sheet moulding compound was about twice that of H-SMC. Composites based on surface treated hemp fibres showed a slight improvement in residual flexural strength, particularly for systems based on hemp fibres treated with a combined alkaline and silane surface treatment. Surface treated systems showed improved levels of adhesion and increased levels of energy absorption through potential mechanisms such as debonding, pull-out or fibre fibrillation.},
	urldate = {2020-12-01},
	journal = {ADVANCED COMPOSITES LETTERS},
	author = {Patel, Harish K. and Peijs, Ton},
	month = oct,
	year = {2020},
}

Natural fibre composites are of interest for a wide range of semi-structural applications in the building, construction and automotive sector. For a number of these applications, the evaluation of performance degradation after impact is of some relevance. The present work focused on the influence of fibre volume fraction and fibre surface treatment on the residual load-bearing capability of hemp fibre-reinforced sheet moulding compound (H-SMC) after non-penetrating impacts. Post-impact flexural strength and stiffness of H-SMC decreased linearly with increasing impact energy. At higher impact energy levels, the residual flexural strength of H-SMC improved with increasing fibre volume fraction. However, for the same amount of absorbed energy, the residual strength or damage tolerance capability of glass fibre-reinforced sheet moulding compound was about twice that of H-SMC. Composites based on surface treated hemp fibres showed a slight improvement in residual flexural strength, particularly for systems based on hemp fibres treated with a combined alkaline and silane surface treatment. Surface treated systems showed improved levels of adhesion and increased levels of energy absorption through potential mechanisms such as debonding, pull-out or fibre fibrillation.

@article{bhatti_photo-thermal_2020,
	title = {Photo-thermal actuation of ultra-drawn high-density polyethylene},
	volume = {207},
	issn = {0032-3861},
	doi = {10.1016/j.polymer.2020.122897},
	abstract = {In this work, the photo-actuation of melt-processed ultra-drawn films based on high-density polyethylene (HDPE), incorporating a light-responsive additive (2-(2H-benzotriazol-2-yl)-4,6-ditertpentylphenol, BZT), is presented. These oriented films exhibits a fast ({\textless}1 s) and reversible photo-thermal response upon exposure to ultra-violet (UV) light with a maximum actuation stress of -20 MPa at a strain of 0.1\%. Actuation is triggered by light, which is absorbed by the BZT and transferred into heat. The generated heat, in combination with the intrinsic high stiffness (similar to 30 GPa) and negative thermal expansion of these oriented polymer films, induces entropy driven contraction of the macromolecular chains and thus when constrained an actuation stress. The above described set of properties, in combination with the facile, low cost and industrially scalable processing of these actuators makes them suitable for a wide range of potential applications, such as light driven robotics, control devices and functional textiles.},
	urldate = {2020-11-03},
	journal = {POLYMER},
	author = {Bhatti, Muhammad Rehan Asghar and Bilotti, Emiliano and Zhang, Han and Bastiaansen, Cees W. M. and Peijs, Ton},
	month = oct,
	year = {2020},
	note = {Univ Engn \& Technol Lahore},
}

In this work, the photo-actuation of melt-processed ultra-drawn films based on high-density polyethylene (HDPE), incorporating a light-responsive additive (2-(2H-benzotriazol-2-yl)-4,6-ditertpentylphenol, BZT), is presented. These oriented films exhibits a fast (\textless1 s) and reversible photo-thermal response upon exposure to ultra-violet (UV) light with a maximum actuation stress of -20 MPa at a strain of 0.1%. Actuation is triggered by light, which is absorbed by the BZT and transferred into heat. The generated heat, in combination with the intrinsic high stiffness (similar to 30 GPa) and negative thermal expansion of these oriented polymer films, induces entropy driven contraction of the macromolecular chains and thus when constrained an actuation stress. The above described set of properties, in combination with the facile, low cost and industrially scalable processing of these actuators makes them suitable for a wide range of potential applications, such as light driven robotics, control devices and functional textiles.

@article{zhang_self-healing_2020,
	title = {Self-{Healing} of {Materials} under {High} {Electrical} {Stress}},
	volume = {3},
	issn = {2590-2393},
	doi = {10.1016/j.matt.2020.07.020},
	abstract = {There is an increasing demand for materials and electronic devices to operate under conditions of high electrical or mechanical stress, or a combination of both. Applications include high-voltage insulation, capacitors, batteries, actuation, and energy harvesting. Since the application of a high electric field, current, or mechanical stress can introduce damage, there is a growing need to improve damage tolerance or provide a degree of self-healing to recover properties and functionality. This Perspective provides an overview of the current research directions in self-healing under conditions of high electric and mechanical stress. Damage and recovery mechanisms are initially outlined, which includes healing and damage tolerance by electrical clearing, dielectric breakdown, and electrical treeing. Modeling and simulation processes to better understand the mechanisms are also discussed. The exploitation of such healing processes in specific applications are then described, which include power transmission cables, storage capacitors, battery systems, actuators, and energy harvesters. Areas for future research directions are identified.},
	number = {4},
	urldate = {2020-12-04},
	journal = {MATTER},
	author = {Zhang, Yan and Khanbareh, Hamideh and Roscow, James and Pan, Min and Bowen, Chris and Wan, Chaoying},
	month = oct,
	year = {2020},
	pages = {989--1008},
}

There is an increasing demand for materials and electronic devices to operate under conditions of high electrical or mechanical stress, or a combination of both. Applications include high-voltage insulation, capacitors, batteries, actuation, and energy harvesting. Since the application of a high electric field, current, or mechanical stress can introduce damage, there is a growing need to improve damage tolerance or provide a degree of self-healing to recover properties and functionality. This Perspective provides an overview of the current research directions in self-healing under conditions of high electric and mechanical stress. Damage and recovery mechanisms are initially outlined, which includes healing and damage tolerance by electrical clearing, dielectric breakdown, and electrical treeing. Modeling and simulation processes to better understand the mechanisms are also discussed. The exploitation of such healing processes in specific applications are then described, which include power transmission cables, storage capacitors, battery systems, actuators, and energy harvesters. Areas for future research directions are identified.

@article{morgan_electron_2020,
	title = {Electron {Capture} {Dissociation} of {Trithiocarbonate}-{Terminated} {Acrylamide} {Homo}- and {Copolymers}: {A} {Terminus}-{Directed} {Mechanism}?},
	volume = {92},
	issn = {0003-2700},
	doi = {10.1021/acs.analchem.0c01224},
	abstract = {The structure and sequence elucidation of complex homo- and copolymers is key for further understanding polymers, polymer synthesis, and polymer interactions in biological processes. In this contribution, poly(dimethylacrylamide) homo- and dimethylacrylamide/4-acryloylmorpholine block copolymers were synthesized and analyzed by electron capture dissociation (ECD) and Fourier transform ion cyclotron resonance (FT-ICR) tandem mass spectrometry. Double-resonance experiments were carried out, providing a better understanding of the fragmentation process. A novel radical dissociation process is presented, and electron capture caused a specific cleavage at the terminal butyl-trithiocarbonate group, which initiated a free radical dissociation process.},
	number = {19},
	urldate = {2020-11-20},
	journal = {ANALYTICAL CHEMISTRY},
	author = {Morgan, Tomos E. and Kerr, Andrew and Wootton, Christopher A. and Barrow, Mark P. and Bristow, Anthony W. T. and Perrier, Sebastien and O'Connor, Peter B.},
	month = oct,
	year = {2020},
	pages = {12852--12859},
}

The structure and sequence elucidation of complex homo- and copolymers is key for further understanding polymers, polymer synthesis, and polymer interactions in biological processes. In this contribution, poly(dimethylacrylamide) homo- and dimethylacrylamide/4-acryloylmorpholine block copolymers were synthesized and analyzed by electron capture dissociation (ECD) and Fourier transform ion cyclotron resonance (FT-ICR) tandem mass spectrometry. Double-resonance experiments were carried out, providing a better understanding of the fragmentation process. A novel radical dissociation process is presented, and electron capture caused a specific cleavage at the terminal butyl-trithiocarbonate group, which initiated a free radical dissociation process.

@article{laezza_protecting_2020,
	title = {Protecting {Group} {Free} {Synthesis} of {Glyconanoparticles} {Using} {Amino}-{Oxy}-{Terminated} {Polymer} {Ligands}},
	volume = {31},
	issn = {1043-1802},
	doi = {10.1021/acs.bioconjchem.0c00465},
	abstract = {Glycomaterials display enhanced binding affinity to carbohydrate-binding proteins due to the nonlinear enhancement associated with the cluster glycoside effect. Gold nanoparticles bearing glycans have attracted significant interest in particular. This is due to their versatility, their highly tunable gold cores (size and shape), and their application in biosensors and diagnostic tools. However, conjugating glycans onto these materials can be challenging, necessitating either multiple protecting group manipulations or the use of only simple glycans. This results in limited structural diversity compared to glycoarrays which can include hundreds of glycans. Here we report a method to generate glyconanoparticles from unprotected glycans by conjugation to polymer tethers bearing terminal amino-oxy groups, which are then immobilized onto gold nanoparticles. Using an isotope-labeled glycan, the efficiency of this reaction was probed in detail to confirm conjugation, with 25\% of end-groups being functionalized, predominantly in the ring-closed form. Facile post-glycosylation purification is achieved by simple centrifugation/washing cycles to remove excess glycan and polymer. This streamlined synthetic approach may be particularly useful for the preparation of glyconanoparticle libraries using automation, to identify hits to be taken forward using more conventional synthetic methods. Exemplar lectin-binding studies were undertaken to confirm the availability of the glycans for binding and show this is a powerful tool for rapid assessment of multivalent glycan binding.},
	number = {10},
	urldate = {2020-12-18},
	journal = {BIOCONJUGATE CHEMISTRY},
	author = {Laezza, Antonio and Georgiou, Panagiotis G. and Richards, Sarah-Jane and Baker, Alexander N. and Walker, Marc and Gibson, I, Matthew},
	month = oct,
	year = {2020},
	pages = {2392--2403},
}

Glycomaterials display enhanced binding affinity to carbohydrate-binding proteins due to the nonlinear enhancement associated with the cluster glycoside effect. Gold nanoparticles bearing glycans have attracted significant interest in particular. This is due to their versatility, their highly tunable gold cores (size and shape), and their application in biosensors and diagnostic tools. However, conjugating glycans onto these materials can be challenging, necessitating either multiple protecting group manipulations or the use of only simple glycans. This results in limited structural diversity compared to glycoarrays which can include hundreds of glycans. Here we report a method to generate glyconanoparticles from unprotected glycans by conjugation to polymer tethers bearing terminal amino-oxy groups, which are then immobilized onto gold nanoparticles. Using an isotope-labeled glycan, the efficiency of this reaction was probed in detail to confirm conjugation, with 25% of end-groups being functionalized, predominantly in the ring-closed form. Facile post-glycosylation purification is achieved by simple centrifugation/washing cycles to remove excess glycan and polymer. This streamlined synthetic approach may be particularly useful for the preparation of glyconanoparticle libraries using automation, to identify hits to be taken forward using more conventional synthetic methods. Exemplar lectin-binding studies were undertaken to confirm the availability of the glycans for binding and show this is a powerful tool for rapid assessment of multivalent glycan binding.

@article{zhao_fluorinated_2020,
	title = {Fluorinated {Polymers} via {Para}-{Fluoro}-{Thiol} and {Thiol}-{Bromo} {Click} {Step} {Growth} {Polymerization}},
	volume = {41},
	issn = {1022-1336},
	doi = {10.1002/marc.202000409},
	abstract = {Click reactions are utilized widely to modify chain ends and side groups of polymers while click polymerizations based on step-growth polymerization of bifunctional monomers have recently attracted increased attention of polymer chemists. Herein, the combination of two highly efficient click reactions, namely para-fluoro-thiol click and thiol-bromo substitution reactions, is demonstrated to form fluorinated polymers with tuned hydrophobicity owing to the nature of the dithiol linker compound. The key compound in this study is 2,3,4,5,6-pentafluoro benzyl bromide that provides the combination of thiol click reactions. The thiols used here are 4,4-thiobisbenzenthiol, 2,2'-(ethylenedioxy) diethanethiol, and 1,2-ethanedithiol that allow tuning of the properties of obtained polymers. The step-growth click reaction conditions are optimized by screening the effect of reaction temperature, base, solvent, and stochiometric ratio of the compounds. Thermal properties and hydrophobicity of synthesized polymers are determined via water contact angle, thermogravimetric analysis and differential scanning calorimetry measurements, showing thermal stability up to 300 degrees C, glass transition temperatures ranging from -25 to 82 degrees C and water contact angles ranging from 55 to 90 degrees C.},
	number = {22},
	urldate = {2020-10-12},
	journal = {MACROMOLECULAR RAPID COMMUNICATIONS},
	author = {Zhao, Tieshuai and Beyer, Valentin P. and Becer, Caglar Remzi},
	month = nov,
	year = {2020},
}

Click reactions are utilized widely to modify chain ends and side groups of polymers while click polymerizations based on step-growth polymerization of bifunctional monomers have recently attracted increased attention of polymer chemists. Herein, the combination of two highly efficient click reactions, namely para-fluoro-thiol click and thiol-bromo substitution reactions, is demonstrated to form fluorinated polymers with tuned hydrophobicity owing to the nature of the dithiol linker compound. The key compound in this study is 2,3,4,5,6-pentafluoro benzyl bromide that provides the combination of thiol click reactions. The thiols used here are 4,4-thiobisbenzenthiol, 2,2'-(ethylenedioxy) diethanethiol, and 1,2-ethanedithiol that allow tuning of the properties of obtained polymers. The step-growth click reaction conditions are optimized by screening the effect of reaction temperature, base, solvent, and stochiometric ratio of the compounds. Thermal properties and hydrophobicity of synthesized polymers are determined via water contact angle, thermogravimetric analysis and differential scanning calorimetry measurements, showing thermal stability up to 300 degrees C, glass transition temperatures ranging from -25 to 82 degrees C and water contact angles ranging from 55 to 90 degrees C.

@article{richardson_low-dispersity_2020,
	title = {Low-{Dispersity} {Polymers} in {Ab} {Initio} {Emulsion} {Polymerization}: {Improved} {MacroRAFT} {Agent} {Performance} in {Heterogeneous} {Media}},
	volume = {53},
	issn = {0024-9297},
	doi = {10.1021/acs.macromol.0c01311},
	abstract = {We demonstrate that the in-built monomer-feeding mechanism in an emulsion polymerization can be used to dramatically increase control (providing low molar mass dispersity (D) {\textless}= 1.15) over polymerizations mediated by reversible addition-fragmentation chain transfer (RAFT) agents with relatively low transfer constants (C-tr). An amphiphilic RAFT agent [RSC(= S)Z], based on a hydrophilic methacrylic R-group [(C) over dot(CH3)(2)CO2-PEG] and a hydrophobic Z group with C-tr approximate to 2, was used to mediate the polymerization of a range of methacrylate monomers under both heterogeneous and homogeneous conditions. Consistent with the low C-tr, batch miniemulsion or solution polymerizations did not provide polymers with low D. The issue of a low C-tr is overcome in an emulsion polymerization when the [monomer]/[RAFT agent] ratio at the locus of polymerization is substantially lower than the overall ratio, due to the presence of a discrete monomer droplet phase. The proposed mechanism is supported by a theoretical model. As a demonstration of the increased level of control achievable, the system has been exploited to generate methacrylate multiblock copolymers.},
	number = {18},
	urldate = {2020-10-19},
	journal = {MACROMOLECULES},
	author = {Richardson, Robert A. E. and Guimaraes, Thiago R. and Khan, Murtaza and Moad, Graeme and Zetterlund, Per B. and Perrier, Sebastien},
	month = sep,
	year = {2020},
	pages = {7672--7683},
}

We demonstrate that the in-built monomer-feeding mechanism in an emulsion polymerization can be used to dramatically increase control (providing low molar mass dispersity (D) \textless= 1.15) over polymerizations mediated by reversible addition-fragmentation chain transfer (RAFT) agents with relatively low transfer constants (C-tr). An amphiphilic RAFT agent [RSC(= S)Z], based on a hydrophilic methacrylic R-group [(C) over dot(CH3)(2)CO2-PEG] and a hydrophobic Z group with C-tr approximate to 2, was used to mediate the polymerization of a range of methacrylate monomers under both heterogeneous and homogeneous conditions. Consistent with the low C-tr, batch miniemulsion or solution polymerizations did not provide polymers with low D. The issue of a low C-tr is overcome in an emulsion polymerization when the [monomer]/[RAFT agent] ratio at the locus of polymerization is substantially lower than the overall ratio, due to the presence of a discrete monomer droplet phase. The proposed mechanism is supported by a theoretical model. As a demonstration of the increased level of control achievable, the system has been exploited to generate methacrylate multiblock copolymers.

@article{chen_structure_2020,
	title = {Structure and properties of thermomechanically processed silk peptide and nanoclay filled chitosan},
	volume = {6},
	issn = {2055-0324},
	doi = {10.1080/20550324.2020.1820796},
	abstract = {While chitosan has great potential for biomedical and wider application due to its appealing characteristics such as biocompatibility and inherent antimicrobial activity, its properties usually need to be further tailored for specific uses. In this study, the effect of inclusion of silk peptide (SP) and nanoclays (montmorillonite, MMT and sepiolite, SPT) on the properties of thermomechanically processed chitosan were examined. Blending SP with chitosan led to a material with greater elasticity and surface wettability. For the chitosan matrix, addition of either MMT or SPT resulted in increased mechanical properties with MMT being more effective, likely due to its 2D layered structure. For the chitosan/SP matrix, while inclusion of MMT caused increased mechanical properties and thermal stability, SPT was more effective than MMT at reducing surface hydrophilicity and SPT fully counteracted the increased surface hydrophilicity caused by SP. Thus, this work shows the different effects of MMT and SPT on chitosan-based materials and provides insights into achieving balanced properties.inclusion of[GRAPHICS].},
	number = {3},
	urldate = {2020-10-06},
	journal = {NANOCOMPOSITES},
	author = {Chen, Pei and Xie, Fengwei and Tang, Fengzai and McNally, Tony},
	year = {2020},
	pages = {125--136},
}

While chitosan has great potential for biomedical and wider application due to its appealing characteristics such as biocompatibility and inherent antimicrobial activity, its properties usually need to be further tailored for specific uses. In this study, the effect of inclusion of silk peptide (SP) and nanoclays (montmorillonite, MMT and sepiolite, SPT) on the properties of thermomechanically processed chitosan were examined. Blending SP with chitosan led to a material with greater elasticity and surface wettability. For the chitosan matrix, addition of either MMT or SPT resulted in increased mechanical properties with MMT being more effective, likely due to its 2D layered structure. For the chitosan/SP matrix, while inclusion of MMT caused increased mechanical properties and thermal stability, SPT was more effective than MMT at reducing surface hydrophilicity and SPT fully counteracted the increased surface hydrophilicity caused by SP. Thus, this work shows the different effects of MMT and SPT on chitosan-based materials and provides insights into achieving balanced properties.inclusion of[GRAPHICS].

@article{zhang_aqueous_2020,
	title = {Aqueous copper-mediated reversible deactivation radical polymerization ({RDRP}) utilizing polyetheramine derived initiators},
	volume = {11},
	issn = {1759-9954},
	doi = {10.1039/d0py00555j},
	abstract = {Copper-mediated reversible deactivation radical polymeriation (Cu-RDRP) in aqueous media has been employed to synthesize temperature-responsive block copolymers, utilizing both hydrophobic and hydrophilic amide functional macroinitiators derived from polyetheramines (Jeffamines (TM)). Thein situand rapid diproportionation of Cu(i)Br/Me6TREN in water is exploited for the efficient homopolymerization ofN-isopropyl acrylamide (NIPAM) and dimethyl acrylamide (DMA), at near full conversions ({\textgreater}99\%), with low dispersity (D{\textless} 1.18) and with a range of molar masses. The Jeffamine (TM)-derived macroinitiators were used for both the synthesis of homopolymer and for one-pot chain extensions and block copolymerizations (i.e.Jeffamine (TM)-PNIPAM-b-PDMA). The obtained polymers exhibit controlled thermoresponsive aggregation behaviour which varies depending on the hydrophilicity/hydrophobicity of the macroinitiators and the composition of the block copolymers. Thermal analysis and dynamic light scattering (DLS) give an insight into the effect of these macroinitiators on the thermoresponsive aggregation behaviour of the synthesized polymers.},
	number = {34},
	urldate = {2020-09-15},
	journal = {POLYMER CHEMISTRY},
	author = {Zhang, Jirui and Liarou, Evelina and Town, James and Li, Yongguang and Wemyss, Alan M. and Haddleton, David M.},
	month = sep,
	year = {2020},
	pages = {5534--5541},
}

Copper-mediated reversible deactivation radical polymeriation (Cu-RDRP) in aqueous media has been employed to synthesize temperature-responsive block copolymers, utilizing both hydrophobic and hydrophilic amide functional macroinitiators derived from polyetheramines (Jeffamines (TM)). Thein situand rapid diproportionation of Cu(i)Br/Me6TREN in water is exploited for the efficient homopolymerization ofN-isopropyl acrylamide (NIPAM) and dimethyl acrylamide (DMA), at near full conversions (\textgreater99%), with low dispersity (D\textless 1.18) and with a range of molar masses. The Jeffamine (TM)-derived macroinitiators were used for both the synthesis of homopolymer and for one-pot chain extensions and block copolymerizations (i.e.Jeffamine (TM)-PNIPAM-b-PDMA). The obtained polymers exhibit controlled thermoresponsive aggregation behaviour which varies depending on the hydrophilicity/hydrophobicity of the macroinitiators and the composition of the block copolymers. Thermal analysis and dynamic light scattering (DLS) give an insight into the effect of these macroinitiators on the thermoresponsive aggregation behaviour of the synthesized polymers.

@article{tchoupa_type_2020,
	title = {The type {VII} secretion system protects {Staphylococcus} aureus against antimicrobial host fatty acids},
	volume = {10},
	issn = {2045-2322},
	doi = {10.1038/s41598-020-71653-z},
	abstract = {The Staphylococcus aureus type VII secretion system (T7SS) exports several proteins that are pivotal for bacterial virulence. The mechanisms underlying T7SS-mediated staphylococcal survival during infection nevertheless remain unclear. Here we report that S. aureus lacking T7SS components are more susceptible to host-derived antimicrobial fatty acids. Unsaturated fatty acids such as linoleic acid (LA) elicited an increased inhibition of S. aureus mutants lacking T7SS effectors EsxC, EsxA and EsxB, or the membrane-bound ATPase EssC, compared to the wild-type (WT). T7SS mutants generated in different S. aureus strain backgrounds also displayed an increased sensitivity to LA. Analysis of bacterial membrane lipid profiles revealed that the esxC mutant was less able to incorporate LA into its membrane phospholipids. Although the ability to bind labelled LA did not differ between the WT and mutant strains, LA induced more cell membrane damage in the T7SS mutants compared to the WT. Furthermore, proteomic analyses of WT and mutant cell fractions revealed that, in addition to compromising membranes, T7SS defects induce oxidative stress and hamper their response to LA challenge. Thus, our findings indicate that T7SS contribute to maintaining S. aureus membrane integrity and homeostasis when bacteria encounter antimicrobial fatty acids.},
	number = {1},
	urldate = {2020-09-09},
	journal = {SCIENTIFIC REPORTS},
	author = {Tchoupa, Arnaud Kengmo and Watkins, Kate E. and Jones, Rebekah A. and Kuroki, Agnes and Alam, Mohammad Tauqeer and Perrier, Sebastien and Chen, Yin and Unnikrishnan, Meera},
	month = sep,
	year = {2020},
}

The Staphylococcus aureus type VII secretion system (T7SS) exports several proteins that are pivotal for bacterial virulence. The mechanisms underlying T7SS-mediated staphylococcal survival during infection nevertheless remain unclear. Here we report that S. aureus lacking T7SS components are more susceptible to host-derived antimicrobial fatty acids. Unsaturated fatty acids such as linoleic acid (LA) elicited an increased inhibition of S. aureus mutants lacking T7SS effectors EsxC, EsxA and EsxB, or the membrane-bound ATPase EssC, compared to the wild-type (WT). T7SS mutants generated in different S. aureus strain backgrounds also displayed an increased sensitivity to LA. Analysis of bacterial membrane lipid profiles revealed that the esxC mutant was less able to incorporate LA into its membrane phospholipids. Although the ability to bind labelled LA did not differ between the WT and mutant strains, LA induced more cell membrane damage in the T7SS mutants compared to the WT. Furthermore, proteomic analyses of WT and mutant cell fractions revealed that, in addition to compromising membranes, T7SS defects induce oxidative stress and hamper their response to LA challenge. Thus, our findings indicate that T7SS contribute to maintaining S. aureus membrane integrity and homeostasis when bacteria encounter antimicrobial fatty acids.

@article{marathianos_dihydrolevoglucosenone_2020,
	title = {Dihydrolevoglucosenone ({Cyrene}™) as a bio-renewable solvent for {Cu}(0)wire-mediated reversible deactivation radical polymerization ({RDRP}) without external deoxygenation},
	volume = {22},
	issn = {1463-9262},
	doi = {10.1039/d0gc02184a},
	abstract = {Biorenewable dihydrolevoglucosenone (Cyrene (TM)) is used as an effective dipolar aprotic solvent for Cu(0) wire-mediated RDRP of various monomers without external deoxygenation being applied. The solvent is used to give products with a broad range of molar masses (M-n similar to 700-28 000),in situchain extension and as low as 7.8 x 10(-4)eq. of [Cu(ii)Br-2] relative to initiator.},
	number = {17},
	urldate = {2020-09-15},
	journal = {GREEN CHEMISTRY},
	author = {Marathianos, Arkadios and Liarou, Evelina and Hancox, Ellis and Grace, James L. and Lester, Daniel W. and Haddleton, David M.},
	month = sep,
	year = {2020},
	pages = {5833--5837},
}

Biorenewable dihydrolevoglucosenone (Cyrene (TM)) is used as an effective dipolar aprotic solvent for Cu(0) wire-mediated RDRP of various monomers without external deoxygenation being applied. The solvent is used to give products with a broad range of molar masses (M-n similar to 700-28 000),in situchain extension and as low as 7.8 x 10(-4)eq. of [Cu(ii)Br-2] relative to initiator.

@article{malina_stabilization_2020,
	title = {Stabilization of human telomeric {RNA} {G}-quadruplex by the water-compatible optically pure and biologically-active metallohelices},
	volume = {10},
	issn = {2045-2322},
	doi = {10.1038/s41598-020-71429-5},
	abstract = {RNA G-quadruplexes have been suggested to play key roles in fundamental biological processes and are linked to human diseases. Thus, they also represent good potential therapeutic targets. Here, we describe, using the methods of molecular biophysics, interactions of a series of biologically-active supramolecular cationic metallohelices with human telomeric RNA G-quadruplex. We demonstrate that the investigated metallohelices bind with a high affinity to human telomeric RNA G-quadruplex and that their binding selectivity considerably differs depending on the dimensions and overall shape of the metallohelices. Additionally, the investigated metallohelices inhibit DNA synthesis on the RNA template containing four repeats of the human telomeric sequence by stabilizing the RNA G-quadruplex structure. Collectively, the results of this study suggest that stabilization of RNA sequences capable of G-quadruplex formation by metallohelices investigated in this work might contribute to the mechanism of their biological activity.},
	number = {1},
	urldate = {2020-10-07},
	journal = {SCIENTIFIC REPORTS},
	author = {Malina, Jaroslav and Scott, Peter and Brabec, Viktor},
	month = sep,
	year = {2020},
}

RNA G-quadruplexes have been suggested to play key roles in fundamental biological processes and are linked to human diseases. Thus, they also represent good potential therapeutic targets. Here, we describe, using the methods of molecular biophysics, interactions of a series of biologically-active supramolecular cationic metallohelices with human telomeric RNA G-quadruplex. We demonstrate that the investigated metallohelices bind with a high affinity to human telomeric RNA G-quadruplex and that their binding selectivity considerably differs depending on the dimensions and overall shape of the metallohelices. Additionally, the investigated metallohelices inhibit DNA synthesis on the RNA template containing four repeats of the human telomeric sequence by stabilizing the RNA G-quadruplex structure. Collectively, the results of this study suggest that stabilization of RNA sequences capable of G-quadruplex formation by metallohelices investigated in this work might contribute to the mechanism of their biological activity.

@article{abdouni_effect_2020,
	title = {Effect of {Arm} {Number} and {Length} of {Star}-{Shaped} {Glycopolymers} on {Binding} to {Dendritic} and {Langerhans} {Cell} {Lectins}},
	volume = {21},
	issn = {1525-7797},
	doi = {10.1021/acs.biomac.0c00856},
	abstract = {Many cell types in Nature are covered by glycans with a sugar shell on their surface. Synthetic glycopolymer-based materials can mimic these glycans in terms of their variety of biological processes, such as cell growth regulation, adhesion, inflammation by bacteria and viruses, and immune responses. However, the complexity of glycans is still very challenging to be mimicked completely to obtain specific and selective binding ability. Therefore, in this study we aimed to understand how the complexity in the sense of the effect of number of arms and lengths in star-shaped glycopolymers affect the binding activity with different lectins. The Cu-mediated reversible deactivation radical polymerization (Cu-RDRP) technique was employed for the synthesis of mannose containing star-shaped glycopolymers with varying arm number and length. Two sets of star-shaped glycopolymers with on average 1, 3, 7, 8, and 15 arms were successfully synthesized and characterized via 1H NMR, GPC, and DLS. The first set of glycopolymers (SetS1) encompasses 5 star-shaped glycopolymers with a different amount of arms per macromolecule but with equal arm length, whereas in the second set of 5 glycopolymers (Set S2), the amount of sugars per macromolecule was kept constant to obtain glycopolymers with similar glycovalency but in different configuration. Both glycopolymer sets were subsequently evaluated for their lectin-binding affinity toward a series of both newly and previously studied C-type mannose specific lectins present on dendritic and Langerhans cells. Briefly, while Set S1 glycopolymers with the same arm length and different molecular weight showed considerably different biological activities, SetS2 glycopolymers with different arm lengths and the same molecular weight displayed very similar binding abilities, which can indicate that multivalency can be more important than structure complexity to improve the binding behavior of glycopolymers.},
	number = {9},
	urldate = {2020-10-09},
	journal = {BIOMACROMOLECULES},
	author = {Abdouni, Yamin and Yilmaz, Gokhan and Monaco, Alessandra and Aksakal, Resat and Becer, C. Remzi},
	month = sep,
	year = {2020},
	pages = {3756--3764},
}

Many cell types in Nature are covered by glycans with a sugar shell on their surface. Synthetic glycopolymer-based materials can mimic these glycans in terms of their variety of biological processes, such as cell growth regulation, adhesion, inflammation by bacteria and viruses, and immune responses. However, the complexity of glycans is still very challenging to be mimicked completely to obtain specific and selective binding ability. Therefore, in this study we aimed to understand how the complexity in the sense of the effect of number of arms and lengths in star-shaped glycopolymers affect the binding activity with different lectins. The Cu-mediated reversible deactivation radical polymerization (Cu-RDRP) technique was employed for the synthesis of mannose containing star-shaped glycopolymers with varying arm number and length. Two sets of star-shaped glycopolymers with on average 1, 3, 7, 8, and 15 arms were successfully synthesized and characterized via 1H NMR, GPC, and DLS. The first set of glycopolymers (SetS1) encompasses 5 star-shaped glycopolymers with a different amount of arms per macromolecule but with equal arm length, whereas in the second set of 5 glycopolymers (Set S2), the amount of sugars per macromolecule was kept constant to obtain glycopolymers with similar glycovalency but in different configuration. Both glycopolymer sets were subsequently evaluated for their lectin-binding affinity toward a series of both newly and previously studied C-type mannose specific lectins present on dendritic and Langerhans cells. Briefly, while Set S1 glycopolymers with the same arm length and different molecular weight showed considerably different biological activities, SetS2 glycopolymers with different arm lengths and the same molecular weight displayed very similar binding abilities, which can indicate that multivalency can be more important than structure complexity to improve the binding behavior of glycopolymers.

@article{monaco_multi-arm_2020,
	title = {Multi-{Arm} {Star}-{Shaped} {Glycopolymers} with {Precisely} {Controlled} {Core} {Size} and {Arm} {Length}},
	volume = {21},
	issn = {1525-7797},
	doi = {10.1021/acs.biomac.0c00838},
	abstract = {Star-shaped glycopolymers provide very high binding activities toward lectins. However, a straightforward synthesis method for the preparation of multi-arm glycopolymers in a one-pot approach has been challenging. Herein, we report a rapid synthesis of well-defined multi-arm glycopolymers via Cu(0)-mediated reversible deactivation radical polymerization in aqueous media. D-Mannose acrylamide has been homo- and copolymerized with NIPAM to provide linear arms and then core cross-linked with a bisacrylamide monomer. Thus, the arm length and core size of multi-arm glycopolymers were tuned. Moreover, the stability of multi-arm glycopolymers was investigated, and degradation reactions under acidic or basic conditions were observed. The binding activities of the obtained multi-arm glycopolymers with mannose-specific human lectins, DC-SIGN and MBL, were investigated via surface plasmon resonance spectroscopy. Finally, the encapsulation ability of multi-arm glycopolymers was examined using DHA and Saquinavir below and above the lower critical solution temperature (LCST) of P(NIPAM).},
	number = {9},
	urldate = {2020-10-09},
	journal = {BIOMACROMOLECULES},
	author = {Monaco, Alessandra and Beyer, Valentin P. and Napier, Richard and Becer, C. Remzi},
	month = sep,
	year = {2020},
	pages = {3736--3744},
}

Star-shaped glycopolymers provide very high binding activities toward lectins. However, a straightforward synthesis method for the preparation of multi-arm glycopolymers in a one-pot approach has been challenging. Herein, we report a rapid synthesis of well-defined multi-arm glycopolymers via Cu(0)-mediated reversible deactivation radical polymerization in aqueous media. D-Mannose acrylamide has been homo- and copolymerized with NIPAM to provide linear arms and then core cross-linked with a bisacrylamide monomer. Thus, the arm length and core size of multi-arm glycopolymers were tuned. Moreover, the stability of multi-arm glycopolymers was investigated, and degradation reactions under acidic or basic conditions were observed. The binding activities of the obtained multi-arm glycopolymers with mannose-specific human lectins, DC-SIGN and MBL, were investigated via surface plasmon resonance spectroscopy. Finally, the encapsulation ability of multi-arm glycopolymers was examined using DHA and Saquinavir below and above the lower critical solution temperature (LCST) of P(NIPAM).

@article{aljuaid_synthesis_2020,
	title = {Synthesis and [2+2]-photodimerisation of monothiomaleimide functionalised linear and brush-like polymers},
	volume = {56},
	issn = {1359-7345},
	doi = {10.1039/d0cc04067c},
	abstract = {[2+2]-Photodimerisation of monothiomaleimides has been demonstrated on functionalised linear and brush-like polymers. In water/acetonitrile (95 : 5) mixtures the rate of reaction is accelerated significantly by irradiation of the thiomaleimide end group (lambda(max)= 350 nm) with UV light, reaching full conversion within 10 minutes.},
	number = {66},
	urldate = {2020-09-01},
	journal = {CHEMICAL COMMUNICATIONS},
	author = {Aljuaid, Mohammed and Liarou, Evelina and Town, James and Baker, James R. and Haddleton, David M. and Wilson, Paul},
	month = aug,
	year = {2020},
	pages = {9545--9548},
}

[2+2]-Photodimerisation of monothiomaleimides has been demonstrated on functionalised linear and brush-like polymers. In water/acetonitrile (95 : 5) mixtures the rate of reaction is accelerated significantly by irradiation of the thiomaleimide end group (lambda(max)= 350 nm) with UV light, reaching full conversion within 10 minutes.

@article{guerra_surface_2020,
	title = {Surface {Cleaning} of {2D} {Materials}: {Boron} {Nitride} {Nanosheets} ({BNNS}) and {Exfoliated} {Graphite} {Nanoplatelets} ({GNP})},
	volume = {7},
	issn = {2196-7350},
	doi = {10.1002/admi.202000944},
	abstract = {Surface impurities such as water and surfactants can significantly affect the properties of 2D materials. They disrupt the 2D material lattice structure and surface chemistry and also promote electron and phonon scattering. Strategies to clean the surfaces of 2D materials are therefore critical to achieving optimal properties. Boron nitride nanosheets (BNNS) and exfoliated graphite nanoplatelets (GNP) are treated using three procedures: washing with ethanol, water-assisted freeze-drying, and freeze-drying without addition of water in an attempt to remove two impurities-water and an ionic surfactant (sodium cholate, SC). There is total removal of water from BNNS when the starting material is treated using either freeze drying method whereas some water (approximate to 40\%) and traces of ethanol are detected in BNNS when washed with ethanol. It is not possible to exclude the presence of SC on BNNS and GNP post treatment; however, the relatively high amount of sodium (from SC) in the samples after freeze-drying suggests the process contributed to the separation of BNNS and GNP aggregates. The BNNS flakes separate when washed with ethanol or freeze-dried in the absence of water. The crystalline structure of BNNS and GNP is retained post treatments. This approach provides a route to cleaning and separating 2D materials.},
	number = {19},
	urldate = {2020-08-28},
	journal = {ADVANCED MATERIALS INTERFACES},
	author = {Guerra, Valentina and McNally, Tony},
	month = oct,
	year = {2020},
}

Surface impurities such as water and surfactants can significantly affect the properties of 2D materials. They disrupt the 2D material lattice structure and surface chemistry and also promote electron and phonon scattering. Strategies to clean the surfaces of 2D materials are therefore critical to achieving optimal properties. Boron nitride nanosheets (BNNS) and exfoliated graphite nanoplatelets (GNP) are treated using three procedures: washing with ethanol, water-assisted freeze-drying, and freeze-drying without addition of water in an attempt to remove two impurities-water and an ionic surfactant (sodium cholate, SC). There is total removal of water from BNNS when the starting material is treated using either freeze drying method whereas some water (approximate to 40%) and traces of ethanol are detected in BNNS when washed with ethanol. It is not possible to exclude the presence of SC on BNNS and GNP post treatment; however, the relatively high amount of sodium (from SC) in the samples after freeze-drying suggests the process contributed to the separation of BNNS and GNP aggregates. The BNNS flakes separate when washed with ethanol or freeze-dried in the absence of water. The crystalline structure of BNNS and GNP is retained post treatments. This approach provides a route to cleaning and separating 2D materials.

@article{lin_transparent_2020,
	title = {Transparent semi-crystalline polymeric materials and their nanocomposites: {A} review},
	volume = {60},
	issn = {0032-3888},
	doi = {10.1002/pen.25489},
	abstract = {Optical transparency is an important property for a material, especially in certain fields like packaging, glazing, and displays. Existing commercial transparent polymeric materials are mostly amorphous. Semicrystalline polymers have often-superior chemical resistance and mechanical properties particularly at elevated temperatures or after solid-state drawing but they appear opaque or white in most cases. This review describes the present state-of-the-art of methodologies of fabricating optically transparent materials from semicrystalline polymers. A distinction is made between isotropic, biaxially stretched, and uniaxially stretched semicrystalline polymers. Furthermore, some functionalities of transparent nanocomposites based on semicrystalline polymers are also discussed. This review aims to provide guidelines regarding the principles of manufacturing transparent high-performance semicrystalline polymers and their nanocomposites for potential applications in fields like packaging, building, and construction, aerospace, automotive, and opto-electronics.},
	number = {10},
	urldate = {2020-08-19},
	journal = {POLYMER ENGINEERING AND SCIENCE},
	author = {Lin, Yunyin and Bilotti, Emiliano and Bastiaansen, Cees W. M. and Peijs, Ton},
	month = oct,
	year = {2020},
	pages = {2351--2376},
}

Optical transparency is an important property for a material, especially in certain fields like packaging, glazing, and displays. Existing commercial transparent polymeric materials are mostly amorphous. Semicrystalline polymers have often-superior chemical resistance and mechanical properties particularly at elevated temperatures or after solid-state drawing but they appear opaque or white in most cases. This review describes the present state-of-the-art of methodologies of fabricating optically transparent materials from semicrystalline polymers. A distinction is made between isotropic, biaxially stretched, and uniaxially stretched semicrystalline polymers. Furthermore, some functionalities of transparent nanocomposites based on semicrystalline polymers are also discussed. This review aims to provide guidelines regarding the principles of manufacturing transparent high-performance semicrystalline polymers and their nanocomposites for potential applications in fields like packaging, building, and construction, aerospace, automotive, and opto-electronics.

@article{du_neutrophil-membrane-directed_2020,
	title = {Neutrophil-{Membrane}-{Directed} {Bioorthogonal} {Synthesis} of {Inflammation}-{Targeting} {Chiral} {Drugs}},
	volume = {6},
	issn = {2451-9294},
	doi = {10.1016/j.chempr.2020.06.002},
	abstract = {Targeted bioorthogonal catalysis holds great potential for localized prodrug activation. Although enantiomerically pure drugs are of vital importance in the clinic, chiral drug synthesis by bioorthogonal reactions in living systems is scarcely reported. Toward this goal, we constructed chirally modified Pd catalysts for the asymmetric transfer hydrogenation (ATH) reaction by using sodium formate as the biocompatible reductant. By combining the ATH reaction and chemotaxis of neutrophil membrane, we achieved inflammation site-selective chiral drug synthesis in living cells. As a proof of concept, we synthesized the chiral model drug ibuprofen in situ by a targeted ATH reaction to alleviate inflammation in the mouse paw as an in vivo model. Compared with controls, the neutrophilmembrane-coated chiral Pd catalysts exhibited inflammation-targeted capability and enantioselectivity simultaneously in the anti-inflammatory action. This study could offer a novel perspective for bioorthogonal catalysis in targeted prodrug activation.},
	number = {8},
	urldate = {2020-08-06},
	journal = {CHEM},
	author = {Du, Zhi and Liu, Chun and Song, Hualong and Scott, Peter and Liu, Zhenqi and Ren, Jinsong and Qu, Xiaogang},
	month = aug,
	year = {2020},
	pages = {2060--2072},
}

Targeted bioorthogonal catalysis holds great potential for localized prodrug activation. Although enantiomerically pure drugs are of vital importance in the clinic, chiral drug synthesis by bioorthogonal reactions in living systems is scarcely reported. Toward this goal, we constructed chirally modified Pd catalysts for the asymmetric transfer hydrogenation (ATH) reaction by using sodium formate as the biocompatible reductant. By combining the ATH reaction and chemotaxis of neutrophil membrane, we achieved inflammation site-selective chiral drug synthesis in living cells. As a proof of concept, we synthesized the chiral model drug ibuprofen in situ by a targeted ATH reaction to alleviate inflammation in the mouse paw as an in vivo model. Compared with controls, the neutrophilmembrane-coated chiral Pd catalysts exhibited inflammation-targeted capability and enantioselectivity simultaneously in the anti-inflammatory action. This study could offer a novel perspective for bioorthogonal catalysis in targeted prodrug activation.

@article{chen_ionic_2020,
	title = {Ionic {Liquid} (1-{Ethyl}-3-methylimidazolium {Acetate}) {Plasticization} of {Chitosan}-{Based} {Bionanocomposites}},
	volume = {5},
	issn = {2470-1343},
	doi = {10.1021/acsomega.0c02418},
	abstract = {The structure and properties of different biopolymer composites based on chitosan and chitosan/carboxymethyl cellulose (CMC) are governed by multiple structure-property relationships associated with different phase interactions. Plasticization of these matrices with ionic liquid 1-ethyl-3-methylimidazolium acetate ([C(2)mim][OAc]) played a dominant role, increasing the mobility of biopolymer chains as well as ions and associated dipoles but reducing biopolymer chain interactions, crystallinity, and thermal stability. These structural changes led to higher matrix ionic conductivity, shorter electrical relaxation time, and greater matrix ductility. The inclusion of graphene oxide (GO) and reduced GO (rGO) also influenced the structure and properties of these bionanocomposites by disrupting the biopolymer hydrogen bonding and/or polyelectrolyte complexation (PEC) and interacting with [C(2)mim][OAc]. The impact of GO/rGO was more evident for 20 wt \% [C(2)mim] [OAc], such as increased crystallinity and thermal stability of chitosan. PEC was hindered with excess (40 wt \%) [C(2)mim][OAc] added and further hindered again when rGO was included. This study shows that the structure and properties of bionanocomposites are not just determined by the surface chemistry of GO/rGO but can also be influenced by multiple interactions involving plasticizers such as ILs and additional biopolymers.},
	number = {30},
	urldate = {2020-09-08},
	journal = {ACS OMEGA},
	author = {Chen, Pei and Xie, Fengwei and Tang, Fengzai and McNally, Tony},
	month = aug,
	year = {2020},
	pages = {19070--19081},
}

The structure and properties of different biopolymer composites based on chitosan and chitosan/carboxymethyl cellulose (CMC) are governed by multiple structure-property relationships associated with different phase interactions. Plasticization of these matrices with ionic liquid 1-ethyl-3-methylimidazolium acetate ([C(2)mim][OAc]) played a dominant role, increasing the mobility of biopolymer chains as well as ions and associated dipoles but reducing biopolymer chain interactions, crystallinity, and thermal stability. These structural changes led to higher matrix ionic conductivity, shorter electrical relaxation time, and greater matrix ductility. The inclusion of graphene oxide (GO) and reduced GO (rGO) also influenced the structure and properties of these bionanocomposites by disrupting the biopolymer hydrogen bonding and/or polyelectrolyte complexation (PEC) and interacting with [C(2)mim][OAc]. The impact of GO/rGO was more evident for 20 wt % [C(2)mim] [OAc], such as increased crystallinity and thermal stability of chitosan. PEC was hindered with excess (40 wt %) [C(2)mim][OAc] added and further hindered again when rGO was included. This study shows that the structure and properties of bionanocomposites are not just determined by the surface chemistry of GO/rGO but can also be influenced by multiple interactions involving plasticizers such as ILs and additional biopolymers.

@article{cheng_-situ_2020,
	title = {In-situ deposition of three-dimensional graphene on selective laser melted copper scaffolds for high performance applications},
	volume = {135},
	issn = {1359-835X},
	doi = {10.1016/j.compositesa.2020.105904},
	abstract = {Currently, three-dimensional graphene (3DG) fabrication was restricted by the complicated process, strict chemical reactions as well as structural accuracy. Herein we creatively propose a bottom-up strategy that leverages the selective laser melting (SLM) technique to manufacture a three-dimensional (3D) porous copper template. Graphene was then in-situ grown via chemical vapor deposition (CVD) on the obtained porous Cu template, forming 3DG composites. A combination of conventional graphene growth via CVD technique with SLM fabricated scaffold templates enabled an accurate design and regulation of 3DG from macro-structure (unit type, porosity, aperture) to micro-structure (texture, surface quality) through an elaborately manipulated porous copper scaffold. The 3DG/copper scaffold could achieve around 88\% and 27\% enhancement in electromagnetic interference (EMI) shielding and thermal diffusion, respectively. Particularly, the highest EMI shielding efficiency (SE) can reach up to 47.8 dB at 2.7 GHz and exhibit an average SE of 32.3 dB at the range of 2-18 GHz. The synergistic shielding mechanisms accounted for the improvement derived from the use of hybrid composite materials and precise architecture of the SLM porous structure.},
	urldate = {2020-06-17},
	journal = {COMPOSITES PART A-APPLIED SCIENCE AND MANUFACTURING},
	author = {Cheng, Kaka and Xiong, Wei and Li, Yan and Hao, Liang and Yan, Chunze and Li, Zhaoqing and Liu, Zhufeng and Wang, Yushen and Essa, Khamis and Lee, Li and Gong, Xin and Peijs, Ton},
	month = aug,
	year = {2020},
	note = {Hubei Gem \& Jewelry Engn Technol Res Ctr},
}

Currently, three-dimensional graphene (3DG) fabrication was restricted by the complicated process, strict chemical reactions as well as structural accuracy. Herein we creatively propose a bottom-up strategy that leverages the selective laser melting (SLM) technique to manufacture a three-dimensional (3D) porous copper template. Graphene was then in-situ grown via chemical vapor deposition (CVD) on the obtained porous Cu template, forming 3DG composites. A combination of conventional graphene growth via CVD technique with SLM fabricated scaffold templates enabled an accurate design and regulation of 3DG from macro-structure (unit type, porosity, aperture) to micro-structure (texture, surface quality) through an elaborately manipulated porous copper scaffold. The 3DG/copper scaffold could achieve around 88% and 27% enhancement in electromagnetic interference (EMI) shielding and thermal diffusion, respectively. Particularly, the highest EMI shielding efficiency (SE) can reach up to 47.8 dB at 2.7 GHz and exhibit an average SE of 32.3 dB at the range of 2-18 GHz. The synergistic shielding mechanisms accounted for the improvement derived from the use of hybrid composite materials and precise architecture of the SLM porous structure.

@article{smith_graphene_2020,
	title = {Graphene {Oxide} {Functionalized} with 2-{Ureido}-4[{1H}]-pyrimidinone for {Production} of {Nacre}-{Like} {Films}},
	volume = {3},
	issn = {2574-0970},
	doi = {10.1021/acsanm.0c01488},
	abstract = {The facile and efficient reaction of graphene oxide (GO) and 2-ureido-4[1H]-pyrimidinone (UPy), an isocyanate terminated 4-site hydrogen-bonding moiety, produces a functionalized GO (f-GO) that readily self-assembles into a freestanding nacre-like film using a vacuum filtration process. The reaction of UPy with GO occurs predominately via the epoxide and hydroxyl groups on the GO which was confirmed from a combination of Fourier-transform infrared (FTIR), Raman and X-ray photoelectron spectroscopy (XPS), and C-13 solid state nuclear magnetic resonance (SSNMR) measurements. The nacre-like films obtained were typically 50-100 mu m thick, from cross-section scanning-electron microscopy (SEM) imaging. The GO d-spacing (X-ray diffraction, XRD) increased with increasing UPy content from 0.934 to 1.45 nm, resulting in porous films with reduced tortuosity to oxygen, carbon dioxide, and water. However, at higher UPy content, reduced tortuosity is balanced with the ability of UPy dimers to readily dissociate and exchange with water. The tensile strength and tensile toughness of the GO nacre-like film increased by up to 470\% and 1100\% and the maximum strain by a factor of similar to 2, for the film with the highest UPy content. These improvements are achieved through a mechanism of extension and unfolding of the linear chain of six carbon atoms in UPy, enhancing strain under tensile loading permitting the platelets to slide more before failure. This work highlights the impact of enhanced interlayer interactions via hydrogen bonding in producing polymer-free nacre-like films.},
	number = {7},
	urldate = {2020-08-19},
	journal = {ACS APPLIED NANO MATERIALS},
	author = {Smith, Andrew J. and Kelly, Nicole L. and Figiel, Lukasz and Wan, Chaoying and Hanna, V, John and Farris, Stefano and McNally, Tony},
	month = jul,
	year = {2020},
	pages = {7161--7171},
}

The facile and efficient reaction of graphene oxide (GO) and 2-ureido-4[1H]-pyrimidinone (UPy), an isocyanate terminated 4-site hydrogen-bonding moiety, produces a functionalized GO (f-GO) that readily self-assembles into a freestanding nacre-like film using a vacuum filtration process. The reaction of UPy with GO occurs predominately via the epoxide and hydroxyl groups on the GO which was confirmed from a combination of Fourier-transform infrared (FTIR), Raman and X-ray photoelectron spectroscopy (XPS), and C-13 solid state nuclear magnetic resonance (SSNMR) measurements. The nacre-like films obtained were typically 50-100 mu m thick, from cross-section scanning-electron microscopy (SEM) imaging. The GO d-spacing (X-ray diffraction, XRD) increased with increasing UPy content from 0.934 to 1.45 nm, resulting in porous films with reduced tortuosity to oxygen, carbon dioxide, and water. However, at higher UPy content, reduced tortuosity is balanced with the ability of UPy dimers to readily dissociate and exchange with water. The tensile strength and tensile toughness of the GO nacre-like film increased by up to 470% and 1100% and the maximum strain by a factor of similar to 2, for the film with the highest UPy content. These improvements are achieved through a mechanism of extension and unfolding of the linear chain of six carbon atoms in UPy, enhancing strain under tensile loading permitting the platelets to slide more before failure. This work highlights the impact of enhanced interlayer interactions via hydrogen bonding in producing polymer-free nacre-like films.

@article{bhatti_ultra-high_2020,
	title = {Ultra-{High} {Actuation} {Stress} {Polymer} {Actuators} as {Light}-{Driven} {Artificial} {Muscles}},
	volume = {12},
	issn = {1944-8244},
	doi = {10.1021/acsami.0c07684},
	abstract = {Remotely addressable actuators are of great interest in fields like microrobotics and smart textiles because of their simplicity, integrity, flexibility, and lightweight. However, most of the existing actuator systems are composed of complex assemblies and/or offer a low response rate. Here, the actuation performance of a light-driven, highly oriented film based on ultra-high molecular weight polyethylene (UHMW-PE), containing a photo-responsive additive, 2-(2H-benzotriazol-2-y1)-4,6-ditertpentylphenol (BZT), is reported. The material exhibits a fast ({\textless}1 s) and reversible photo-induced thermal response upon exposure to UV light, which results in an exceptionally high actuation stress (similar to 70 MPa) at a low strain ({\textless}0.1\%). The proposed actuation mechanism originates from light absorption by BZT and energy transfer into heat, in combination with the intrinsic high stiffness (similar to 80 GPa) and a negative thermal expansion (NTE) of the oriented polymer films. This unique set of properties of this actuator, in particular the very high specific actuation stress, compared to existing organic and inorganic actuators, and the remote optical actuation, promises impact in fields related to soft robotics, composites, medical devices, optics, prosthetics, and smart textiles.},
	number = {29},
	urldate = {2020-08-19},
	journal = {ACS APPLIED MATERIALS \& INTERFACES},
	author = {Bhatti, Muhammad Rehan Asghar and Bilotti, Emiliano and Zhang, Han and Varghese, Shaji and Verpaalen, Rob C. P. and Schenning, Albert P. H. J. and Bastiaansen, Cees W. M. and Peijs, Ton},
	month = jul,
	year = {2020},
	pages = {33210--33218},
}

Remotely addressable actuators are of great interest in fields like microrobotics and smart textiles because of their simplicity, integrity, flexibility, and lightweight. However, most of the existing actuator systems are composed of complex assemblies and/or offer a low response rate. Here, the actuation performance of a light-driven, highly oriented film based on ultra-high molecular weight polyethylene (UHMW-PE), containing a photo-responsive additive, 2-(2H-benzotriazol-2-y1)-4,6-ditertpentylphenol (BZT), is reported. The material exhibits a fast (\textless1 s) and reversible photo-induced thermal response upon exposure to UV light, which results in an exceptionally high actuation stress (similar to 70 MPa) at a low strain (\textless0.1%). The proposed actuation mechanism originates from light absorption by BZT and energy transfer into heat, in combination with the intrinsic high stiffness (similar to 80 GPa) and a negative thermal expansion (NTE) of the oriented polymer films. This unique set of properties of this actuator, in particular the very high specific actuation stress, compared to existing organic and inorganic actuators, and the remote optical actuation, promises impact in fields related to soft robotics, composites, medical devices, optics, prosthetics, and smart textiles.

@article{hand_application_2020,
	title = {Application of molecularly imprinted polymers in the anti-doping field: sample purification and compound analysis},
	volume = {145},
	issn = {0003-2654},
	doi = {10.1039/d0an00682c},
	abstract = {The problem posed by anti-doping requirements is one of the great analytical challenges; multiple compound detection at low ng ml(-1)levels from complex samples, with requirements for exceptional confidence in results. This review surveys the design, synthesis and application of molecularly imprinted polymers (MIPs) in this field, focusing on the templating of androgenous anabolic steroids (AASs), as the most commonly abused substances, but also other WADA prohibited substances. Commentary on the application of these materials in detection, clean-up and sensing is offered, alongside views on the future of imprinting in this field.},
	number = {14},
	urldate = {2020-07-28},
	journal = {ANALYST},
	author = {Hand, Rachel A. and Piletska, Elena and Bassindale, Thomas and Morgan, Geraint and Turner, Nicholas},
	month = jul,
	year = {2020},
	pages = {4716--4736},
}

The problem posed by anti-doping requirements is one of the great analytical challenges; multiple compound detection at low ng ml(-1)levels from complex samples, with requirements for exceptional confidence in results. This review surveys the design, synthesis and application of molecularly imprinted polymers (MIPs) in this field, focusing on the templating of androgenous anabolic steroids (AASs), as the most commonly abused substances, but also other WADA prohibited substances. Commentary on the application of these materials in detection, clean-up and sensing is offered, alongside views on the future of imprinting in this field.

@article{donald_when_2020,
	title = {When {Mayo} falls short ({Ctr}⟫ 1): the use of cumulative chain length distribution data in the determination of chain transfer constants ({Ctr}) for radical polymerizations},
	volume = {11},
	issn = {1759-9954},
	doi = {10.1039/d0py00348d},
	abstract = {We report a new method of determining the chain transfer constant in free radical polymerization using molecular weight distribution data. It is specifically designed for systems where its value is substantially greater than 1. In these cases the classical Mayo equation and Gilbert's chain length distribution (CLD) method fall short, in that the concentration ratio of chain transfer agent to monomer can no longer be assumed to be constant. Marked composition drift invalidates the use of both. In our proposed method we use the analytical concentration ratio of chain transfer agent to monomer (t= 0 s) and monomer conversion data, in combination with data for the cumulative molecular weight distributions as input. We determined an analytical solution for the cumulative weight distribution, which is used to calculate the cumulative number and chain length distributions. Chain transfer constants are found either by fitting the natural logarithmic chain length distribution (CLD) data at a given monomer conversion, or by plotting the fitted values for the slopes obtained from the natural logarithmic chain length distribution (CLD) data at a set degree of polymerization, as a function of monomer conversion. Our method is validated by analyses of molecular weight data obtained from Monte Carlo simulations. We used our methodology to determine an experimental value ofca.223 as a chain transfer constant ofn-dodecanethiol in vinyl acetate free radical polymerization at 333.15 K, which we showed was in excellent agreement with the Smith method.},
	number = {26},
	urldate = {2020-07-20},
	journal = {POLYMER CHEMISTRY},
	author = {Donald, Matt K. and Bon, Stefan A. F.},
	month = jul,
	year = {2020},
	pages = {4281--4289},
}

We report a new method of determining the chain transfer constant in free radical polymerization using molecular weight distribution data. It is specifically designed for systems where its value is substantially greater than 1. In these cases the classical Mayo equation and Gilbert's chain length distribution (CLD) method fall short, in that the concentration ratio of chain transfer agent to monomer can no longer be assumed to be constant. Marked composition drift invalidates the use of both. In our proposed method we use the analytical concentration ratio of chain transfer agent to monomer (t= 0 s) and monomer conversion data, in combination with data for the cumulative molecular weight distributions as input. We determined an analytical solution for the cumulative weight distribution, which is used to calculate the cumulative number and chain length distributions. Chain transfer constants are found either by fitting the natural logarithmic chain length distribution (CLD) data at a given monomer conversion, or by plotting the fitted values for the slopes obtained from the natural logarithmic chain length distribution (CLD) data at a set degree of polymerization, as a function of monomer conversion. Our method is validated by analyses of molecular weight data obtained from Monte Carlo simulations. We used our methodology to determine an experimental value ofca.223 as a chain transfer constant ofn-dodecanethiol in vinyl acetate free radical polymerization at 333.15 K, which we showed was in excellent agreement with the Smith method.

@article{chen_unexpected_2020,
	title = {Unexpected {Plasticization} {Effects} on the {Structure} and {Properties} of {Polyelectrolyte} {Complexed} {Chitosan}/{Alginate} {Materials}},
	volume = {2},
	issn = {2637-6105},
	doi = {10.1021/acsapm.0c00433},
	abstract = {This work describes the effects of different plasticizers, namely, glycerol, triacetin, and 1-ethyl-3-methylimidazolium acetate ([C-2 mim][OAc]), on the structure and properties of thermomechanically processed, bulk chitosan and chitosan/alginate materials. Mechanical data shows that, for the chitosan matrix, glycerol and [C-2 mirn][OAc] were highly effective at reducing intraand intermolecular forces between biopolymer chains, leading to increased ductility, while the plasticization effect of triacetin was minor. Nonetheless, this triester effectively suppressed biopolymer recrystallization, whereas [C-2 mim] [OAc] promoted it. In contrast, for the chitosan/alginate matrix, inclusion of triacetin resulted in increased recrystallization, higher thermal stability, and excellent mechanical properties. The triacetin assisted the interactions between biopolymer chains in this polyelectrolyte complexed system. In contrast, the chitosan/alginate material plasticized by [C-2 mim] [OAc] displayed the most apparent phase separation, poorest mechanical properties, and highest surface hydrophilicity, behavior associated with the disruption of polyelectrolyte complexation and hydrogen bonding between biopolymer chains. Interestingly, the formation of a "new structure" under the electron beam during microscopy imaging was observed, likely from coordination between alginate and [C-2 mim][OAc]. Thus, this work has revealed the strong and unexpected effects of three different plasticizers on the hydrogen bonding and electrostatic interactions within chitosan/alginate polyelectrolyte complexed materials, which have potential for biomedical applications where balanced hydrophilicity and mechanical properties are required.},
	number = {7},
	urldate = {2020-08-07},
	journal = {ACS APPLIED POLYMER MATERIALS},
	author = {Chen, Pei and Xie, Fengwei and Tang, Fengzai and McNally, Tony},
	month = jul,
	year = {2020},
	pages = {2957--2966},
}

This work describes the effects of different plasticizers, namely, glycerol, triacetin, and 1-ethyl-3-methylimidazolium acetate ([C-2 mim][OAc]), on the structure and properties of thermomechanically processed, bulk chitosan and chitosan/alginate materials. Mechanical data shows that, for the chitosan matrix, glycerol and [C-2 mirn][OAc] were highly effective at reducing intraand intermolecular forces between biopolymer chains, leading to increased ductility, while the plasticization effect of triacetin was minor. Nonetheless, this triester effectively suppressed biopolymer recrystallization, whereas [C-2 mim] [OAc] promoted it. In contrast, for the chitosan/alginate matrix, inclusion of triacetin resulted in increased recrystallization, higher thermal stability, and excellent mechanical properties. The triacetin assisted the interactions between biopolymer chains in this polyelectrolyte complexed system. In contrast, the chitosan/alginate material plasticized by [C-2 mim] [OAc] displayed the most apparent phase separation, poorest mechanical properties, and highest surface hydrophilicity, behavior associated with the disruption of polyelectrolyte complexation and hydrogen bonding between biopolymer chains. Interestingly, the formation of a "new structure" under the electron beam during microscopy imaging was observed, likely from coordination between alginate and [C-2 mim][OAc]. Thus, this work has revealed the strong and unexpected effects of three different plasticizers on the hydrogen bonding and electrostatic interactions within chitosan/alginate polyelectrolyte complexed materials, which have potential for biomedical applications where balanced hydrophilicity and mechanical properties are required.

@article{houck_shining_2020,
	title = {Shining {Light} on {Poly}(ethylene glycol): {From} {Polymer} {Modification} to {3D} {Laser} {Printing} of {Water} {Erasable} {Microstructures}},
	volume = {32},
	issn = {0935-9648},
	doi = {10.1002/adma.202003060},
	abstract = {The implementation of stimuli-responsive bonds into 3D network assemblies is a key concept to design adaptive materials that can reshape and degrade. Here, a straightforward but unique photoresist is introduced for the tailored fabrication of poly(ethylene glycol) (PEG) materials that can be readily erased by water, even without the need for acidic or basic additives. Specifically, a new class of photoresist is developed that operates through the backbone crosslinking of PEG when irradiated in the presence of a bivalent triazolinedione. Hence, macroscopic gels are obtained upon visible light-emitting diode irradiation (lambda {\textgreater} 515 nm) that are stable in organic media but rapidly degrade upon the addition of water. Photoinduced curing is also applicable to multiphoton laser lithography (lambda {\textgreater} 700 nm), hence providing access to 3D printed microstructures that vanish when immersed in water at 37 degrees C. Materials with varying crosslinking densities are accessed by adapting the applied laser writing power, thereby allowing for tunable hydrolytic erasing timescales. A new platform technology is thus presented that enables the crosslinking and 3D laser printing of PEG-based materials, which can be cleaved and erased in water, and additionally holds potential for the facile modification and backbone degradation of polyether-containing materials in general.},
	number = {34},
	urldate = {2020-07-09},
	journal = {ADVANCED MATERIALS},
	author = {Houck, Hannes A. and Mueller, Patrick and Wegener, Martin and Barner-Kowollik, Christopher and Du Prez, Filip E. and Blasco, Eva},
	month = aug,
	year = {2020},
}

The implementation of stimuli-responsive bonds into 3D network assemblies is a key concept to design adaptive materials that can reshape and degrade. Here, a straightforward but unique photoresist is introduced for the tailored fabrication of poly(ethylene glycol) (PEG) materials that can be readily erased by water, even without the need for acidic or basic additives. Specifically, a new class of photoresist is developed that operates through the backbone crosslinking of PEG when irradiated in the presence of a bivalent triazolinedione. Hence, macroscopic gels are obtained upon visible light-emitting diode irradiation (lambda \textgreater 515 nm) that are stable in organic media but rapidly degrade upon the addition of water. Photoinduced curing is also applicable to multiphoton laser lithography (lambda \textgreater 700 nm), hence providing access to 3D printed microstructures that vanish when immersed in water at 37 degrees C. Materials with varying crosslinking densities are accessed by adapting the applied laser writing power, thereby allowing for tunable hydrolytic erasing timescales. A new platform technology is thus presented that enables the crosslinking and 3D laser printing of PEG-based materials, which can be cleaved and erased in water, and additionally holds potential for the facile modification and backbone degradation of polyether-containing materials in general.

@article{hayes_levulinic_2020,
	title = {Levulinic acid: a sustainable platform chemical for novel polymer architectures},
	volume = {11},
	issn = {1759-9954},
	doi = {10.1039/d0py00705f},
	abstract = {Levulinic acid is a multipurpose platform chemical that is currently used in a wide variety of applications. The potential of levulinic acid is formidable, as can be seen by the diversity and quantity of literature regarding its transformation into different chemicals. Development in industrial production of levulinic acid from lignocellulosic biomass has resulted in a surge of interest in levulinic acid as a cheap, readily available, biobased material. This minireview will analyse the application of levulinic acid as a reagent in polymer chemistry. Levulinic acid has been used in step-growth polymerization, chain-growth polymerization, as a post polymerization functionality, and finally as a method to introduce post polymerisation modificationto sustainable polymers.},
	number = {25},
	urldate = {2020-07-14},
	journal = {POLYMER CHEMISTRY},
	author = {Hayes, Graham C. and Becer, C. Remzi},
	month = jul,
	year = {2020},
	pages = {4068--4077},
}

Levulinic acid is a multipurpose platform chemical that is currently used in a wide variety of applications. The potential of levulinic acid is formidable, as can be seen by the diversity and quantity of literature regarding its transformation into different chemicals. Development in industrial production of levulinic acid from lignocellulosic biomass has resulted in a surge of interest in levulinic acid as a cheap, readily available, biobased material. This minireview will analyse the application of levulinic acid as a reagent in polymer chemistry. Levulinic acid has been used in step-growth polymerization, chain-growth polymerization, as a post polymerization functionality, and finally as a method to introduce post polymerisation modificationto sustainable polymers.

@article{samantaray_polyglycolic_2020,
	title = {Poly(glycolic acid) ({PGA}): a versatile building block expanding high performance and sustainable bioplastic applications},
	volume = {22},
	issn = {1463-9262},
	doi = {10.1039/d0gc01394c},
	abstract = {The concerns about the accumulating plastic waste pollution have stimulated the rapid development of bioplastics, in particular biodegradable bioplastics derived from renewable resources. Driven by a low carbon circular economy, bioplastics production is estimated to reach a 40\% share of the plastics market by 2030 (Bioplastics Market Data, 2018). It is expected to substitute petrochemical-based plastics in many applications, from food packaging, pharmaceuticals, electronics, agriculture to textiles. The current biodegradable bioplastics have met challenges in competing with engineering polymers such as PET and Nylon in terms of processing capacity at the industry scale, mechanical robustness, thermal resistance, and stability. Poly(glycolic acid) (PGA) has a similar chemical structure to PLA but without the methyl side group, which allows the polymer chains to pack together tightly and results in a high degree of crystallinity (45-55\%), high thermal stability (T-m= 220-230 degrees C), exceptionally high gas barrier (3 times higher than EVOH), as well as high mechanical strength (115 MPa) and stiffness (7 GPa). Meanwhile, PGA is rapidly biodegradable and 100\% compostable, showing a similar biodegradation profile to cellulose. To date, PGA has been mainly used in the form of copolymers, such as poly(lactic-co-glycolic acid) (PLGA). Its unique properties have often been overlooked and are yet to be explored. This is caused by its intrinsic characteristics such as high hydrophilicity, rapid degradation, insolubility in most organic solvents and brittleness that have hindered its practical applications. Here we introduced the synthetic chemistry, processing methods, modification, and applications of PGA, aiming to provide a critical discussion about the technical challenges, development opportunities, and solutions for PGA-based materials. The future direction and perspectives for high-performance PGA are proposed. Given its synthesis diversity and unique properties, PGA shows great potential to substitute engineering petrochemical-based polymers for high temperature and high gas barrier packaging applications.},
	number = {13},
	urldate = {2020-07-20},
	journal = {GREEN CHEMISTRY},
	author = {Samantaray, Paresh Kumar and Little, Alastair and Haddleton, David M. and McNally, Tony and Tan, Bowen and Sun, Zhaoyang and Huang, Weijie and Ji, Yang and Wan, Chaoying},
	month = jul,
	year = {2020},
	note = {PJIM Polymer Sci Co Ltd},
	pages = {4055--4081},
}

The concerns about the accumulating plastic waste pollution have stimulated the rapid development of bioplastics, in particular biodegradable bioplastics derived from renewable resources. Driven by a low carbon circular economy, bioplastics production is estimated to reach a 40% share of the plastics market by 2030 (Bioplastics Market Data, 2018). It is expected to substitute petrochemical-based plastics in many applications, from food packaging, pharmaceuticals, electronics, agriculture to textiles. The current biodegradable bioplastics have met challenges in competing with engineering polymers such as PET and Nylon in terms of processing capacity at the industry scale, mechanical robustness, thermal resistance, and stability. Poly(glycolic acid) (PGA) has a similar chemical structure to PLA but without the methyl side group, which allows the polymer chains to pack together tightly and results in a high degree of crystallinity (45-55%), high thermal stability (T-m= 220-230 degrees C), exceptionally high gas barrier (3 times higher than EVOH), as well as high mechanical strength (115 MPa) and stiffness (7 GPa). Meanwhile, PGA is rapidly biodegradable and 100% compostable, showing a similar biodegradation profile to cellulose. To date, PGA has been mainly used in the form of copolymers, such as poly(lactic-co-glycolic acid) (PLGA). Its unique properties have often been overlooked and are yet to be explored. This is caused by its intrinsic characteristics such as high hydrophilicity, rapid degradation, insolubility in most organic solvents and brittleness that have hindered its practical applications. Here we introduced the synthetic chemistry, processing methods, modification, and applications of PGA, aiming to provide a critical discussion about the technical challenges, development opportunities, and solutions for PGA-based materials. The future direction and perspectives for high-performance PGA are proposed. Given its synthesis diversity and unique properties, PGA shows great potential to substitute engineering petrochemical-based polymers for high temperature and high gas barrier packaging applications.

@article{song_glycoconjugated_2020,
	title = {Glycoconjugated {Metallohelices} have {Improved} {Nuclear} {Delivery} and {Suppress} {Tumour} {Growth} {In} {Vivo}},
	volume = {59},
	issn = {1433-7851},
	doi = {10.1002/anie.202006814},
	abstract = {Monosaccharides are added to the hydrophilic face of a self-assembled asymmetric Fe(II)metallohelix, using CuAAC chemistry. The sixteen resulting architectures are water-stable and optically pure, and exhibit improved antiproliferative selectivity against colon cancer cells (HCT116 p53(+/+)) with respect to the non-cancerous ARPE-19 cell line. While the most selective compound is a glucose-appended enantiomer, its cellular entry is not mainly glucose transporter-mediated. Glucose conjugation nevertheless increases nuclear delivery ca 2.5-fold, and a non-destructive interaction with DNA is indicated. Addition of the glucose units affects the binding orientation of the metallohelix to naked DNA, but does not substantially alter the overall affinity. In a mouse model, the glucose conjugated compound was far better tolerated, and tumour growth delays for the parent compound (2.6 d) were improved to 4.3 d; performance as good as cisplatin but with the advantage of no weight loss in the subjects.},
	number = {34},
	urldate = {2020-07-07},
	journal = {ANGEWANDTE CHEMIE-INTERNATIONAL EDITION},
	author = {Song, Hualong and Allison, Simon J. and Brabec, Viktor and Bridgewater, Hannah E. and Kasparkova, Jana and Kostrhunova, Hana and Novohradsky, Vojtech and Phillips, Roger M. and Pracharova, Jitka and Rogers, Nicola J. and Shepherd, Samantha L. and Scott, Peter},
	month = aug,
	year = {2020},
	pages = {14677--14685},
}

Monosaccharides are added to the hydrophilic face of a self-assembled asymmetric Fe(II)metallohelix, using CuAAC chemistry. The sixteen resulting architectures are water-stable and optically pure, and exhibit improved antiproliferative selectivity against colon cancer cells (HCT116 p53(+/+)) with respect to the non-cancerous ARPE-19 cell line. While the most selective compound is a glucose-appended enantiomer, its cellular entry is not mainly glucose transporter-mediated. Glucose conjugation nevertheless increases nuclear delivery ca 2.5-fold, and a non-destructive interaction with DNA is indicated. Addition of the glucose units affects the binding orientation of the metallohelix to naked DNA, but does not substantially alter the overall affinity. In a mouse model, the glucose conjugated compound was far better tolerated, and tumour growth delays for the parent compound (2.6 d) were improved to 4.3 d; performance as good as cisplatin but with the advantage of no weight loss in the subjects.

@article{eriksson_influence_2020-1,
	title = {The {Influence} of {Melt}-{Mixing} {Conditions} and {State} of {Dispersion} on {Crystallisation}, {Rheology} and {Mechanical} {Properties} of {PCL}/{Sepiolite} {Nanocomposites}},
	volume = {35},
	issn = {0930-777X},
	doi = {10.3139/217.3890},
	abstract = {It is generally accepted that the benefit of anisotropic nanofiller addition is strongly dependent on the state of the dispersion of these fillers in a polymer matrix. In this paper the influence of melt-compounding conditions on the dispersion of a needle-like clay, i.e. sepiolite, in poly(e-caprolactone) (PCL) is investigated. The crystallisation behavior as well as the rheological and mechanical properties of PCL/sepiolite nanocomposites with filler contents up to 5 wt.\% are studied. By changing the screw speed during melt-mixing in a micro-compounder, the state of dispersion was varied, with the higher speed leading to better dispersion and breakdown of the sepiolite agglomerates or bundles. Rheometry showed that better dispersed nanocomposites displayed an increase in viscosity due to network formation at slightly higher filler loadings. Likewise, better dispersed composites showed a modest increase in crystallisation temperature at low filler content, accompanied by a decrease in both nucleation efficiency and degree of crystallisation at higher loadings. Better dispersed nanocomposite systems also showed superior mechanical properties, particularly at higher filler loadings. However, overall the reinforcing efficiency of sepiolite in all nanocomposites was relatively low. This was mainly a consequence of the relatively low filler aspect ratio and the simultaneous breakup of sepiolite needles together with a breakdown of bundles during compounding.},
	number = {3},
	urldate = {2020-07-16},
	journal = {INTERNATIONAL POLYMER PROCESSING},
	author = {Eriksson, M. and Meuwissen, M. and Peijs, T. and Goossens, H.},
	month = jul,
	year = {2020},
	note = {Tetra Pak Packaging Solut AB
Sabic},
	pages = {302--313},
}

It is generally accepted that the benefit of anisotropic nanofiller addition is strongly dependent on the state of the dispersion of these fillers in a polymer matrix. In this paper the influence of melt-compounding conditions on the dispersion of a needle-like clay, i.e. sepiolite, in poly(e-caprolactone) (PCL) is investigated. The crystallisation behavior as well as the rheological and mechanical properties of PCL/sepiolite nanocomposites with filler contents up to 5 wt.% are studied. By changing the screw speed during melt-mixing in a micro-compounder, the state of dispersion was varied, with the higher speed leading to better dispersion and breakdown of the sepiolite agglomerates or bundles. Rheometry showed that better dispersed nanocomposites displayed an increase in viscosity due to network formation at slightly higher filler loadings. Likewise, better dispersed composites showed a modest increase in crystallisation temperature at low filler content, accompanied by a decrease in both nucleation efficiency and degree of crystallisation at higher loadings. Better dispersed nanocomposite systems also showed superior mechanical properties, particularly at higher filler loadings. However, overall the reinforcing efficiency of sepiolite in all nanocomposites was relatively low. This was mainly a consequence of the relatively low filler aspect ratio and the simultaneous breakup of sepiolite needles together with a breakdown of bundles during compounding.

@article{zhang_functionalization_2020,
	title = {Functionalization of electrospun {PLA} fibers using amphiphilic block copolymers for use in carboxy-methyl-cellulose hydrogel composites},
	volume = {6},
	issn = {2055-0324},
	doi = {10.1080/20550324.2020.1784600},
	abstract = {Carboxy-methyl-cellulose (CMC) hydrogels, prepared in the presence of a crosslinker and photoinitiator, were reinforced with 3.7 wt\% electrospun PLA fibers to create CMC hydrogel composites. To improve fiber-matrix adhesion, electrospun fiber mats based on hybrids of PLA and amphiphilic block copolymer (BCP) poly(D,L-lactide)-block-poly[2-(dimethylamino)ethyl methacrylate] (PLA-b-PDMAEMA) were produced. The presence of PDMAEMA at the fiber surface induced hydrophilic surface properties, which could be controlled by varying the PDMAEMA chain length. PDMAEMA was quaternized and co-electrospun with PLA fibers, which further enhanced the interaction between fibers and hydrogel matrixviaionic interactions. Physicochemical properties of the electrospun fiber mats and their CMC hydrogel based composites were assessed and revealed a nearly two orders of magnitude increase in modulus. Continuous electrospun fiber mats were chopped into discontinuous fibers to create short fiber reinforced CMC hydrogels. Rheological properties of these reinforced hydrogels incorporating 0.5 wt\% discontinuous fibers were evaluated and showed potential as injectable composite systems for biomedical applications.},
	number = {3},
	urldate = {2020-08-07},
	journal = {NANOCOMPOSITES},
	author = {Zhang, Xi and Megone, William and Peijs, Ton and Gautrot, Julien E.},
	year = {2020},
	pages = {85--98},
}

Carboxy-methyl-cellulose (CMC) hydrogels, prepared in the presence of a crosslinker and photoinitiator, were reinforced with 3.7 wt% electrospun PLA fibers to create CMC hydrogel composites. To improve fiber-matrix adhesion, electrospun fiber mats based on hybrids of PLA and amphiphilic block copolymer (BCP) poly(D,L-lactide)-block-poly[2-(dimethylamino)ethyl methacrylate] (PLA-b-PDMAEMA) were produced. The presence of PDMAEMA at the fiber surface induced hydrophilic surface properties, which could be controlled by varying the PDMAEMA chain length. PDMAEMA was quaternized and co-electrospun with PLA fibers, which further enhanced the interaction between fibers and hydrogel matrixviaionic interactions. Physicochemical properties of the electrospun fiber mats and their CMC hydrogel based composites were assessed and revealed a nearly two orders of magnitude increase in modulus. Continuous electrospun fiber mats were chopped into discontinuous fibers to create short fiber reinforced CMC hydrogels. Rheological properties of these reinforced hydrogels incorporating 0.5 wt% discontinuous fibers were evaluated and showed potential as injectable composite systems for biomedical applications.

@article{zhang_effective_2020,
	title = {Effective {Thermal}-{Oxidative} {Reclamation} of {Waste} {Tire} {Rubbers} for {Producing} {High}-{Performance} {Rubber} {Composites}},
	volume = {8},
	issn = {2168-0485},
	doi = {10.1021/acssuschemeng.0c02292},
	abstract = {The disposal and accumulation of waste tire rubbers has a significant negative impact on the development of a circular economy and sustainable environment. To reuse and recycle ground tire rubber, we developed a thermal-oxidative reclamation process using a newly designed dynamic reclamation reactor. In the absence of any chemical agent, a high scission efficiency was achieved at a sol fraction of 66.53 wt \% at 200 degrees C after 20 min from the thermal oxidation of GTR. The physical and chemical structural evolutions of GTR during the thermo-oxidation process were systemically investigated by monitoring the Mooney viscosity, sol-gel ratio, molecular weight, and chemical structure changes. The reclaimed ground tire rubber containing ultrafine fillers and soluble elastomer can be easily dispersed into a natural rubber matrix. The mechanical properties and aging resistance of the modified natural rubber were enhanced with the addition of up to 40 wt \% reclaimed ground tire rubber. This work demonstrates a green and up-scalable approach for reclamation and reuse of waste tire rubbers for a sustainable rubber industry.},
	number = {24},
	urldate = {2020-07-14},
	journal = {ACS SUSTAINABLE CHEMISTRY \& ENGINEERING},
	author = {Zhang, Yuxin and Zhang, Zhen and Wemyss, Alan M. and Wan, Chaoying and Liu, Yongtao and Song, Pan and Wang, Shifeng},
	month = jun,
	year = {2020},
	pages = {9079--9087},
}

The disposal and accumulation of waste tire rubbers has a significant negative impact on the development of a circular economy and sustainable environment. To reuse and recycle ground tire rubber, we developed a thermal-oxidative reclamation process using a newly designed dynamic reclamation reactor. In the absence of any chemical agent, a high scission efficiency was achieved at a sol fraction of 66.53 wt % at 200 degrees C after 20 min from the thermal oxidation of GTR. The physical and chemical structural evolutions of GTR during the thermo-oxidation process were systemically investigated by monitoring the Mooney viscosity, sol-gel ratio, molecular weight, and chemical structure changes. The reclaimed ground tire rubber containing ultrafine fillers and soluble elastomer can be easily dispersed into a natural rubber matrix. The mechanical properties and aging resistance of the modified natural rubber were enhanced with the addition of up to 40 wt % reclaimed ground tire rubber. This work demonstrates a green and up-scalable approach for reclamation and reuse of waste tire rubbers for a sustainable rubber industry.

@article{atkins_branched_2020,
	title = {Branched macromonomers from catalytic chain transfer polymerisation ({CCTP}) as precursors for emulsion-templated porous polymers},
	volume = {11},
	issn = {1759-9954},
	doi = {10.1039/d0py00539h},
	abstract = {Efforts in the synthesis of macroporous polymers have mostly been directed towards the formation of stable high internal phase emulsions (HIPEs) from commercially available monomers, limiting their scope of application. Therefore, the development of simple synthetic approaches to access tailor-made macromonomers that can be used as precursors for the formation of HIPEs, allowing the design of new generations of polyHIPE materials with bespoke chemical and physical properties, is desirable in the search for new applications. In this work, cobalt(ii) mediated catalytic chain transfer polymerisation (CCTP) is used to polymerise ethylene glycol dimethacrylate (EGDMA), producing multi vinyl-terminated branched EGDMA polymers with tuneable branching density and degree of unsaturation. These materials are subsequently implemented as macromonomer crosslinking agents for the formulation of HIPEs. The use of acrylate comonomers as propagation promoters is found to be essential and 2-ethylhexyl acrylate (EHA), isobornyl acrylate (IBOA) and 2-methoxyethyl acrylate (MEA) are investigated as comonomers in the formulations to both facilitate the photochemical curing of the HIPEs and to impart material properties to the products. The CCTP derived branched macromonomers are fully charaterised by GPC,H-1-NMR and MALDI-ToF spectroscopy. Scanning electron microscopy (SEM) is used to explore the morphology of the produced materials. Surface wettability experiments are conducted to evaluate the hydrophilicity of the polyHIPE surface. Compression tests are used to investigate the influence of the branching density of the CCTP macromonomers as well as the nature of comonomers on the mechanical properties of the materials.},
	number = {23},
	urldate = {2020-07-08},
	journal = {POLYMER CHEMISTRY},
	author = {Atkins, Christophe J. and Seow, David K. and Burns, Gerard and Town, James S. and Hand, Rachel A. and Lester, Daniel W. and Cameron, Neil R. and Haddleton, David M. and Eissa, Ahmed M.},
	month = jun,
	year = {2020},
	pages = {3841--3848},
}

Efforts in the synthesis of macroporous polymers have mostly been directed towards the formation of stable high internal phase emulsions (HIPEs) from commercially available monomers, limiting their scope of application. Therefore, the development of simple synthetic approaches to access tailor-made macromonomers that can be used as precursors for the formation of HIPEs, allowing the design of new generations of polyHIPE materials with bespoke chemical and physical properties, is desirable in the search for new applications. In this work, cobalt(ii) mediated catalytic chain transfer polymerisation (CCTP) is used to polymerise ethylene glycol dimethacrylate (EGDMA), producing multi vinyl-terminated branched EGDMA polymers with tuneable branching density and degree of unsaturation. These materials are subsequently implemented as macromonomer crosslinking agents for the formulation of HIPEs. The use of acrylate comonomers as propagation promoters is found to be essential and 2-ethylhexyl acrylate (EHA), isobornyl acrylate (IBOA) and 2-methoxyethyl acrylate (MEA) are investigated as comonomers in the formulations to both facilitate the photochemical curing of the HIPEs and to impart material properties to the products. The CCTP derived branched macromonomers are fully charaterised by GPC,H-1-NMR and MALDI-ToF spectroscopy. Scanning electron microscopy (SEM) is used to explore the morphology of the produced materials. Surface wettability experiments are conducted to evaluate the hydrophilicity of the polyHIPE surface. Compression tests are used to investigate the influence of the branching density of the CCTP macromonomers as well as the nature of comonomers on the mechanical properties of the materials.

@article{malina_shape-selective_2020,
	title = {Shape-{Selective} {Targeting} on {RNA} {Bulges} by {Peptidomimetic} {Metallohelices}},
	volume = {26},
	issn = {0947-6539},
	doi = {10.1002/chem.202001107},
	abstract = {RNA bulges represent one of the most common motifs in the RNA secondary structure and serve in a variety of biological functions. Compounds stabilizing RNA bulges are important for probing RNA structure and function and for therapy of some diseases. Here, the ability of a series of enantiomeric pairs of optically pure bimetallic metallohelices with different flexible linkers to target various RNA bulges is investigated. The results show that binding affinities of the metallohelices to bulged RNA differ and strongly depend on the size of the bulge and the base composition of the bulge loop. Notably, the shorter, more compact, and less flexible metallohelices bind to RNA bulges most efficiently and selectively. Interestingly, the ability of the metallohelices to bind to RNA bulges correlates with their previously reported antimicrobial activity, which suggests that the selective recognition of bulged regions in RNA by the metallohelices might also contribute to their biological activity.},
	number = {38},
	urldate = {2020-06-25},
	journal = {CHEMISTRY-A EUROPEAN JOURNAL},
	author = {Malina, Jaroslav and Scott, Peter and Brabec, Viktor},
	month = jul,
	year = {2020},
	pages = {8435--8442},
}

RNA bulges represent one of the most common motifs in the RNA secondary structure and serve in a variety of biological functions. Compounds stabilizing RNA bulges are important for probing RNA structure and function and for therapy of some diseases. Here, the ability of a series of enantiomeric pairs of optically pure bimetallic metallohelices with different flexible linkers to target various RNA bulges is investigated. The results show that binding affinities of the metallohelices to bulged RNA differ and strongly depend on the size of the bulge and the base composition of the bulge loop. Notably, the shorter, more compact, and less flexible metallohelices bind to RNA bulges most efficiently and selectively. Interestingly, the ability of the metallohelices to bind to RNA bulges correlates with their previously reported antimicrobial activity, which suggests that the selective recognition of bulged regions in RNA by the metallohelices might also contribute to their biological activity.

@article{blakney_precisely_2020,
	title = {Precisely targeted gene delivery in human skin using supramolecular cationic glycopolymers},
	volume = {11},
	issn = {1759-9954},
	doi = {10.1039/d0py00449a},
	abstract = {Gene delivery has become the focus of clinical treatments, thus motivating delivery strategies that are capable of targeting certain cell types in the context of both vaccines and therapeutics. Here, we present a gene delivery platform enabled by host-guest interaction between a cyclodextrin with emanating chains of cationic polymers, poly(2-dimethylaminoethyl meth-acrylate) (PDMAEMA) paired with a glycosylated adamantane containing copolymer. By decoupling the cationic polymer and glycosylation chemistries, we were able to vary each independently to study the transfection efficiency bothin vitroandex vivoin human skin explants. Medium length PDMAEMA enabled optimal DNA complexation, and glycosylation specifically enhanced the number of cells transfected 100-foldin vitroand 3-foldex vivo. Furthermore, these glycopolymers enabled greater immune cell up take, specifically in skin resident leukocytes. This platform is a facile and clinically translatable way to study how glycosylation affects cellular uptake and targeting in a complex cellular medium.},
	number = {22},
	urldate = {2020-07-06},
	journal = {POLYMER CHEMISTRY},
	author = {Blakney, Anna K. and Liu, Renjie and Yilmaz, Gokhan and Abdouni, Yamin and McKay, Paul F. and Bouton, Clement R. and Shattock, Robin J. and Becer, C. Remzi},
	month = jun,
	year = {2020},
	pages = {3768--3774},
}

Gene delivery has become the focus of clinical treatments, thus motivating delivery strategies that are capable of targeting certain cell types in the context of both vaccines and therapeutics. Here, we present a gene delivery platform enabled by host-guest interaction between a cyclodextrin with emanating chains of cationic polymers, poly(2-dimethylaminoethyl meth-acrylate) (PDMAEMA) paired with a glycosylated adamantane containing copolymer. By decoupling the cationic polymer and glycosylation chemistries, we were able to vary each independently to study the transfection efficiency bothin vitroandex vivoin human skin explants. Medium length PDMAEMA enabled optimal DNA complexation, and glycosylation specifically enhanced the number of cells transfected 100-foldin vitroand 3-foldex vivo. Furthermore, these glycopolymers enabled greater immune cell up take, specifically in skin resident leukocytes. This platform is a facile and clinically translatable way to study how glycosylation affects cellular uptake and targeting in a complex cellular medium.

@article{song_triazole-based_2020,
	title = {Triazole-based, optically-pure metallosupramolecules; highly potent and selective anticancer compounds},
	volume = {56},
	issn = {1359-7345},
	doi = {10.1039/d0cc02429e},
	abstract = {Functionalised triazole aldehydes are used in the highly selective self-assembly of water-compatible, optically pure, low symmetry Fe(ii)- and Zn(ii)-based metallohelices. Sub-micromolar antiproliferative activity is observed against various cancerous cell lines, accompanied by excellent selectivityversusnon-cancerous cells and potential for synergistic combinatorial therapy with cisplatin.},
	number = {47},
	urldate = {2020-07-01},
	journal = {CHEMICAL COMMUNICATIONS},
	author = {Song, Hualong and Rogers, Nicola J. and Brabec, Viktor and Clarkson, Guy J. and Coverdale, James P. C. and Kostrhunova, Hana and Phillips, Roger M. and Postings, Miles and Shepherd, Samantha L. and Scott, Peter},
	month = jun,
	year = {2020},
	pages = {6392--6395},
}

Functionalised triazole aldehydes are used in the highly selective self-assembly of water-compatible, optically pure, low symmetry Fe(ii)- and Zn(ii)-based metallohelices. Sub-micromolar antiproliferative activity is observed against various cancerous cell lines, accompanied by excellent selectivityversusnon-cancerous cells and potential for synergistic combinatorial therapy with cisplatin.

@article{verpaalen_fast_2020,
	title = {Fast, {Light}-{Responsive}, {Metal}-{Like} {Polymer} {Actuators} {Generating} {High} {Stresses} at {Low} {Strain}},
	volume = {2},
	issn = {2590-2393},
	doi = {10.1016/j.matt.2020.03.001},
	abstract = {Producing lightweight polymeric actuators able to generate high stresses typical of hard metals and/or ceramics remains challenging. The photo-mechanical responses of ultra-drawn ultrahigh molecular weight polyethylene (UHMWPE) actuators containing azobenzene photo-switches with symmetrically attached polyethylene (PE) side chains are reported. Long PE side chains promote dispersion within the apolar UHMWPE matrix, and the ultra-drawn films are highly aligned. The ultra-drawn azobenzenedoped UHMWPE films have high Young's moduli (similar to 100 GPa) and are viscoelastic at room temperature at strains below 1\%. The photo-mechanical response of the films is fast ({\textless}1 s), showing a high specific actuation stress response ({\textgreater}6 x 10(4) Pa (kg m(-3))(-1)) to UV or visible light at a low strain (similar to 0.06\%). The actuator responds to rotating linearly polarized light, causing a photoinduced stress wave response. Such rapid, high-stress, low-strain, photo-mechanical responses are unique in soft polymer systems with physical values approaching hard metals/ceramics.},
	number = {6},
	urldate = {2020-06-23},
	journal = {MATTER},
	author = {Verpaalen, Rob C. P. and Varghese, Shaji and Froyen, Arne and da Cunha, Marina Pilz and Pouderoijen, Maarten J. and Severn, John R. and Bhatti, Muhammad R. and Peijs, Ton and Bastiaansen, Cees W. M. and Debije, Michael G. and Engels, Tom A. P. and Schenning, Albertus P. H. J.},
	month = jun,
	year = {2020},
	note = {SyMO Chem BV},
	pages = {1522--1534},
}

Producing lightweight polymeric actuators able to generate high stresses typical of hard metals and/or ceramics remains challenging. The photo-mechanical responses of ultra-drawn ultrahigh molecular weight polyethylene (UHMWPE) actuators containing azobenzene photo-switches with symmetrically attached polyethylene (PE) side chains are reported. Long PE side chains promote dispersion within the apolar UHMWPE matrix, and the ultra-drawn films are highly aligned. The ultra-drawn azobenzenedoped UHMWPE films have high Young's moduli (similar to 100 GPa) and are viscoelastic at room temperature at strains below 1%. The photo-mechanical response of the films is fast (\textless1 s), showing a high specific actuation stress response (\textgreater6 x 10(4) Pa (kg m(-3))(-1)) to UV or visible light at a low strain (similar to 0.06%). The actuator responds to rotating linearly polarized light, causing a photoinduced stress wave response. Such rapid, high-stress, low-strain, photo-mechanical responses are unique in soft polymer systems with physical values approaching hard metals/ceramics.

@article{arevalo_turning_2020,
	title = {Turning low-cost recycled paper into highvalue binder-free all-cellulose panel products},
	volume = {8},
	issn = {2049-1220},
	doi = {10.1680/jgrma.19.00042},
	abstract = {In this work, the feasibility of producing low-cost, recyclable and biodegradable binderless all-cellulose fibreboards was demonstrated through the successful manufacturing of self-binding composites based on recycled paper and kraft fibres. These all-cellulose composites were made by a simple and environmentally friendly solvent-free mechanical fibrillation method using water as a processing aid. Kraft fibres and recycled paper pulp were mixed in a 30/70 w/w ratio and refined simultaneously in a Valley beater for different periods of time. The mechanical properties of the composites, consisting of a 'matrix' of recycled paper reinforced with kraft fibres, were highly dependent on the level of fibrillation of the kraft fibres. Optimal levels of fibrillation resulted in a good balance of self-binding properties and reinforcing efficiency. The hot-pressed all-cellulose panels exhibited a flexural strength of 75 MPa and a modulus of 5.9 GPa, which are impressive values compared with those of conventional fibreboard materials. In addition, these panels showed better water resistance than some existing wood panel products. These binder-free all-cellulose composites have potential as cost-effective sustainable alternatives to existing panel board products, as they are entirely made from renewable and recycled materials, which at the end of life can potentially be recycled or composted, making them perfectly fit for a circular economy.},
	number = {2},
	urldate = {2020-07-07},
	journal = {GREEN MATERIALS},
	author = {Arevalo, Raquel and Soykeabkaew, Nattakan and Peijs, Ton},
	month = jun,
	year = {2020},
	pages = {51--59},
}

In this work, the feasibility of producing low-cost, recyclable and biodegradable binderless all-cellulose fibreboards was demonstrated through the successful manufacturing of self-binding composites based on recycled paper and kraft fibres. These all-cellulose composites were made by a simple and environmentally friendly solvent-free mechanical fibrillation method using water as a processing aid. Kraft fibres and recycled paper pulp were mixed in a 30/70 w/w ratio and refined simultaneously in a Valley beater for different periods of time. The mechanical properties of the composites, consisting of a 'matrix' of recycled paper reinforced with kraft fibres, were highly dependent on the level of fibrillation of the kraft fibres. Optimal levels of fibrillation resulted in a good balance of self-binding properties and reinforcing efficiency. The hot-pressed all-cellulose panels exhibited a flexural strength of 75 MPa and a modulus of 5.9 GPa, which are impressive values compared with those of conventional fibreboard materials. In addition, these panels showed better water resistance than some existing wood panel products. These binder-free all-cellulose composites have potential as cost-effective sustainable alternatives to existing panel board products, as they are entirely made from renewable and recycled materials, which at the end of life can potentially be recycled or composted, making them perfectly fit for a circular economy.

@article{beyer_bottlebrush_2020,
	title = {Bottlebrush {Glycopolymers} from 2-{Oxazolines} and {Acrylamides} for {Targeting} {Dendritic} {Cell}-{Specific} {Intercellular} {Adhesion} {Molecule}-3-{Grabbing} {Nonintegrin} and {Mannose}-{Binding} {Lectin}},
	volume = {21},
	issn = {1525-7797},
	doi = {10.1021/acs.biomac.0c00246},
	abstract = {Lectins are omnipresent carbohydrate binding proteins that are involved in a multitude of biological processes. Unearthing their binding properties is a powerful tool toward the understanding and modification of their functions in biological applications. Herein, we present the synthesis of glycopolymers with a brush architecture via a "grafting from" methodology. The use of a versatile 2-oxazoline inimer was demonstrated to open avenues for a wide range of 2-oxazoline/acrylamide bottle brush polymers utilizing aqueous Cu-mediated reversible deactivation radical polymerization (Cu-RDRP). The polymers in the obtained library were assessed for their thermal properties in aqueous solution and their binding toward the C-type animal lectins dendritic cell-specific intercellular adhesion molecule-3-grabbing nonintegrin DC-SIGN) and mannose-binding lectin (MBL) via surface plasmon resonance spectrometry. The encapsulation properties of a hydrophobic drug-mimicking compound demonstrated the potential use of glyco brush copolymers in biological applications.},
	number = {6},
	urldate = {2020-07-07},
	journal = {BIOMACROMOLECULES},
	author = {Beyer, Valentin P. and Monaco, Alessandra and Napier, Richard and Yilmaz, Gokhan and Becer, C. Remzi},
	month = jun,
	year = {2020},
	pages = {2298--2308},
}

Lectins are omnipresent carbohydrate binding proteins that are involved in a multitude of biological processes. Unearthing their binding properties is a powerful tool toward the understanding and modification of their functions in biological applications. Herein, we present the synthesis of glycopolymers with a brush architecture via a "grafting from" methodology. The use of a versatile 2-oxazoline inimer was demonstrated to open avenues for a wide range of 2-oxazoline/acrylamide bottle brush polymers utilizing aqueous Cu-mediated reversible deactivation radical polymerization (Cu-RDRP). The polymers in the obtained library were assessed for their thermal properties in aqueous solution and their binding toward the C-type animal lectins dendritic cell-specific intercellular adhesion molecule-3-grabbing nonintegrin DC-SIGN) and mannose-binding lectin (MBL) via surface plasmon resonance spectrometry. The encapsulation properties of a hydrophobic drug-mimicking compound demonstrated the potential use of glyco brush copolymers in biological applications.

@article{blakney_mannosylated_2020,
	title = {Mannosylated {Poly}(ethylene imine) {Copolymers} {Enhance} {saRNA} {Uptake} and {Expression} in {Human} {Skin} {Explants}},
	volume = {21},
	issn = {1525-7797},
	doi = {10.1021/acs.biomac.0c00445},
	abstract = {Messenger RNA (mRNA) is a promising platform for both vaccines and therapeutics, and self-amplifying RNA (saRNA)is particularly advantageous, as it enables higher protein expression and dose minimization. Here, we present a delivery platform for targeted delivery of saRNA using mannosylated poly(ethylene imine) (PEI) enabled by the host-guest interaction between cyclodextrin and adamantane. We show that the host-guest complexation does not interfere with the electrostatic interaction with saRNA and observed that increasing the degree of mannosylation inhibited transfection efficiency in vitro, but enhanced the number of cells expressing GFP by 8-fold in human skin explants. Besides, increasing the ratio of glycopolymer to saRNA also enhanced the percentage of transfected cells ex vivo. We identified that these mannosylated PEIs specifically increased protein expression in the epithelial cells resident in human skin in a mannose-dependent manner. This platform is promising for further study of glycosylation of PEI and targeted saRNA delivery.},
	number = {6},
	urldate = {2020-07-07},
	journal = {BIOMACROMOLECULES},
	author = {Blakney, Anna K. and Abdouni, Yamin and Yilmaz, Gokhan and Liu, Renjie and McKay, Paul F. and Bouton, Clement R. and Shattock, Robin J. and Becer, Remzi},
	month = jun,
	year = {2020},
	pages = {2482--2492},
}

Messenger RNA (mRNA) is a promising platform for both vaccines and therapeutics, and self-amplifying RNA (saRNA)is particularly advantageous, as it enables higher protein expression and dose minimization. Here, we present a delivery platform for targeted delivery of saRNA using mannosylated poly(ethylene imine) (PEI) enabled by the host-guest interaction between cyclodextrin and adamantane. We show that the host-guest complexation does not interfere with the electrostatic interaction with saRNA and observed that increasing the degree of mannosylation inhibited transfection efficiency in vitro, but enhanced the number of cells expressing GFP by 8-fold in human skin explants. Besides, increasing the ratio of glycopolymer to saRNA also enhanced the percentage of transfected cells ex vivo. We identified that these mannosylated PEIs specifically increased protein expression in the epithelial cells resident in human skin in a mannose-dependent manner. This platform is promising for further study of glycosylation of PEI and targeted saRNA delivery.

@article{lin_high-performance_2020,
	title = {High-{Performance} {Transparent} {Laminates} {Based} on {Highly} {Oriented} {Polyethylene} {Films}},
	volume = {2},
	issn = {2637-6105},
	doi = {10.1021/acsapm.0c00404},
	abstract = {Advanced composite materials reinforced with high-performance fibers like carbon, glass, aramid, or ultra-high-molecular-weight polyethylene are widely used as lightweight materials in the fields of automotive, aerospace, sports, and protection. However, nearly always these composites are opaque and/or absorb light, which greatly limits their application in areas where high optical transparency is desired such as impact-resistant windows and visors. In this work, composite laminates that combine high optical clarity with high mechanical properties are reported for the first time using highly oriented high-density polyethylene (HDPE) films as the reinforcing phase. A high optical transparency with a far-field light transmittance of around 85\% was achieved for four-layer HDPE-reinforced laminates sandwiched between glass or polycarbonate (PC) sheets with either unidirectional (UD) or bidirectional (BD) orientations. In combination with outer layers of glass or PC, the fabricated transparent composite laminates show high tensile strength and also high penetration energy absorption, outperforming existing transparent materials like glass, laminated glass, or PC. These transparent composites combine both high mechanical performance and high optical clarity, providing great potential for future applications in structural glazing, automotive glazing, safety shields, visors, and displays for portable electronics.},
	number = {6},
	urldate = {2020-07-06},
	journal = {ACS APPLIED POLYMER MATERIALS},
	author = {Lin, Yunyin and Cao, Jun and Zhu, Meifang and Bilotti, Emiliano and Zhang, Han and Bastiaansen, Cees W. M. and Peijs, Ton},
	month = jun,
	year = {2020},
	note = {Nanoforce Technol Ltd},
	pages = {2458--2468},
}

Advanced composite materials reinforced with high-performance fibers like carbon, glass, aramid, or ultra-high-molecular-weight polyethylene are widely used as lightweight materials in the fields of automotive, aerospace, sports, and protection. However, nearly always these composites are opaque and/or absorb light, which greatly limits their application in areas where high optical transparency is desired such as impact-resistant windows and visors. In this work, composite laminates that combine high optical clarity with high mechanical properties are reported for the first time using highly oriented high-density polyethylene (HDPE) films as the reinforcing phase. A high optical transparency with a far-field light transmittance of around 85% was achieved for four-layer HDPE-reinforced laminates sandwiched between glass or polycarbonate (PC) sheets with either unidirectional (UD) or bidirectional (BD) orientations. In combination with outer layers of glass or PC, the fabricated transparent composite laminates show high tensile strength and also high penetration energy absorption, outperforming existing transparent materials like glass, laminated glass, or PC. These transparent composites combine both high mechanical performance and high optical clarity, providing great potential for future applications in structural glazing, automotive glazing, safety shields, visors, and displays for portable electronics.

@article{tao_fatigue_2020,
	title = {Fatigue of carbon cord-rubber composites: {Effect} of frequency, {R} ratio and life prediction using constant life models},
	volume = {135},
	issn = {0142-1123},
	doi = {10.1016/j.ijfatigue.2020.105558},
	abstract = {The influence of frequency and R ratio on tensile fatigue of carbon cord reinforced HNBR composites has been studied. Frequency was found to have negligible effect on fatigue life, due to minimal heat build-up even at the highest frequency. Longer fatigue life at higher R ratios at a given maximum cyclic stress level was associated with the dynamic process of forming and melting of crystallites during loading and unloading, leading to a crackarresting effect. The applicability of various analytical constant life diagram (CLD) models showed that the modified Harris's CLD and piecewise linear CLD gave a reasonably good agreement with experimental fatigue data.},
	urldate = {2020-04-23},
	journal = {INTERNATIONAL JOURNAL OF FATIGUE},
	author = {Tao, Yinping and Stevens, Christopher A. and Bilotti, Emiliano and Peijs, Ton and Busfield, James J. C.},
	month = jun,
	year = {2020},
	note = {NGF Europe Ltd},
}

The influence of frequency and R ratio on tensile fatigue of carbon cord reinforced HNBR composites has been studied. Frequency was found to have negligible effect on fatigue life, due to minimal heat build-up even at the highest frequency. Longer fatigue life at higher R ratios at a given maximum cyclic stress level was associated with the dynamic process of forming and melting of crystallites during loading and unloading, leading to a crackarresting effect. The applicability of various analytical constant life diagram (CLD) models showed that the modified Harris's CLD and piecewise linear CLD gave a reasonably good agreement with experimental fatigue data.

@article{liarou_rapidly_2020,
	title = {Rapidly self-deoxygenating controlled radical polymerization in water via in situ disproportionation of {Cu}(i)},
	volume = {11},
	issn = {2041-6520},
	doi = {10.1039/d0sc01512a},
	abstract = {Rapidly self-deoxygenating Cu-RDRP in aqueous media is investigated. The disproportionation of Cu(i)/Me(6)Tren in water towards Cu(ii) and highly reactive Cu(0) leads to O-2-free reaction environments within the first seconds of the reaction, even when the reaction takes place in the open-air. By leveraging this significantly fast O-2-reducing activity of the disproportionation reaction, a range of well-defined water-soluble polymers with narrow dispersity are attained in a few minutes or less. This methodology provides the ability to prepare block copolymers via sequential monomer addition with little evidence for chain termination over the lifetime of the polymerization and allows for the synthesis of star-shaped polymers with the use of multi-functional initiators. The mechanism of self-deoxygenation is elucidated with the use of various characterization tools, and the species that participate in the rapid oxygen consumption is identified and discussed in detail.},
	number = {20},
	urldate = {2020-06-12},
	journal = {CHEMICAL SCIENCE},
	author = {Liarou, Evelina and Han, Yisong and Sanchez, Ana M. and Walker, Marc and Haddleton, David M.},
	month = may,
	year = {2020},
	pages = {5257--5266},
}

Rapidly self-deoxygenating Cu-RDRP in aqueous media is investigated. The disproportionation of Cu(i)/Me(6)Tren in water towards Cu(ii) and highly reactive Cu(0) leads to O-2-free reaction environments within the first seconds of the reaction, even when the reaction takes place in the open-air. By leveraging this significantly fast O-2-reducing activity of the disproportionation reaction, a range of well-defined water-soluble polymers with narrow dispersity are attained in a few minutes or less. This methodology provides the ability to prepare block copolymers via sequential monomer addition with little evidence for chain termination over the lifetime of the polymerization and allows for the synthesis of star-shaped polymers with the use of multi-functional initiators. The mechanism of self-deoxygenation is elucidated with the use of various characterization tools, and the species that participate in the rapid oxygen consumption is identified and discussed in detail.

@article{ma_aggregation-induced_2020,
	title = {Aggregation-{Induced} {Emission} {Active} {Polyacrylates} via {Cu}-{Mediated} {Reversible} {Deactivation} {Radical} {Polymerization} with {Bioimaging} {Applications}},
	volume = {9},
	issn = {2161-1653},
	doi = {10.1021/acsmacrolett.0c00281},
	abstract = {The introduction of aggregation-induced emission (AIE) moieties into polymers results in smart materials with AIE characteristics, expanding their scope of applications. Herein, well-defined polymers with controlled molecular weight, low dispersity, and high end-group fidelity are produced via copper(0)-mediated reversible-deactivation radical polymerizations (Cu(0)-RDRPs). An AIE-containing initiator tetraphenylethene bromoisobutyrate (TPEBIB) has been synthesized, fully characterized, and utilized for the construction of different polyacrylate homopolymers and block copolymers bearing the TPE group with a range of molecular weights and architectures. All of the polymers exhibited AIE behavior. Notably, the hydrophobic TPE-poly(tert-butyl acrylate) (TPE-PtBA)containing block copolymers are transformed to TPE-poly(acrylic acid) (TPEPAA)-based amphiphilic copolymers by facile deprotection, enabling pH-tunable self-assembly in aqueous media to give fluorescent nanoparticles with various sizes. The low cytotoxicity, high specificity, and excellent photostability render them promising candidates as lysosome-specific probes in biological imaging applications.},
	number = {5},
	urldate = {2020-06-15},
	journal = {ACS MACRO LETTERS},
	author = {Ma, Congkai and Han, Ting and Kang, Miaomiao and Liarou, Evelina and Wemyss, Alan and Efstathiou, Spyridon and Tang, Ben Zhong and Haddleton, David M.},
	month = may,
	year = {2020},
	pages = {769--775},
}

The introduction of aggregation-induced emission (AIE) moieties into polymers results in smart materials with AIE characteristics, expanding their scope of applications. Herein, well-defined polymers with controlled molecular weight, low dispersity, and high end-group fidelity are produced via copper(0)-mediated reversible-deactivation radical polymerizations (Cu(0)-RDRPs). An AIE-containing initiator tetraphenylethene bromoisobutyrate (TPEBIB) has been synthesized, fully characterized, and utilized for the construction of different polyacrylate homopolymers and block copolymers bearing the TPE group with a range of molecular weights and architectures. All of the polymers exhibited AIE behavior. Notably, the hydrophobic TPE-poly(tert-butyl acrylate) (TPE-PtBA)containing block copolymers are transformed to TPE-poly(acrylic acid) (TPEPAA)-based amphiphilic copolymers by facile deprotection, enabling pH-tunable self-assembly in aqueous media to give fluorescent nanoparticles with various sizes. The low cytotoxicity, high specificity, and excellent photostability render them promising candidates as lysosome-specific probes in biological imaging applications.

@article{abbas_situ_2020,
	title = {In {Situ} {Cross}-{Linking} of {Silane} {Functionalized} {Reduced} {Graphene} {Oxide} and {Low}-{Density} {Polyethylene}},
	volume = {2},
	issn = {2637-6105},
	doi = {10.1021/acsapm.0c00115},
	abstract = {Vinyl trimethoxysilane (VTMOS) functionalized reduced graphene oxide (rGO) was melt blended with low-density polyethylene (LDPE) and cross-linked through the vinyl group using a free radical initiator, dicumyl peroxide (DCP), in an extruder. The cross-linking reaction of the pendant vinyl group on the silane with LDPE via peroxide initiation was confirmed by solid-state magic angle spinning (MAS) C-13 and Si-29 nuclear magnetic resonance (NMR) measurements. The Raman spectrum of the cross-linked VTMOS-rGO and LDPE confirmed the formation of a 3D network. Scanning electron (SEM) and transmission electron (TEM) microscopy with elemental mapping showed the VTMOS forms nanospheres located interstitially between rGO layers dispersed within the LDPE matrix. From oscillatory rheology measurements, the transition to more "solid-like" behavior due to cross-linking was detected from a significant decrease in the crossover frequency (G' vs G '') from 31.6 to as low as 0.603 rad/s and an increase in relaxation times (lambda) from 0.032 to 1.66 s for a rGO loading of 1 wt \%. The formation of a 3D interconnected cross-linked VTMOS-rGO-LDPE network resulted in an increase in the tensile strength (up arrow 31\%) and tensile stress at break (up arrow 55\%) of LDPE. The onset of thermal degradation of LDPE was delayed by up to 31 degrees C due to the formation of cross-links and inclusion of silane functionalized rGO which requires a higher activation energy to initiate degradation.},
	number = {5},
	urldate = {2020-06-09},
	journal = {ACS APPLIED POLYMER MATERIALS},
	author = {Abbas, Syeda S. and Rees, Gregory J. and Patias, Georgios and Dancer, Claire E. J. and Hanna, V, John and McNally, Tony},
	month = may,
	year = {2020},
	pages = {1897--1908},
}

Vinyl trimethoxysilane (VTMOS) functionalized reduced graphene oxide (rGO) was melt blended with low-density polyethylene (LDPE) and cross-linked through the vinyl group using a free radical initiator, dicumyl peroxide (DCP), in an extruder. The cross-linking reaction of the pendant vinyl group on the silane with LDPE via peroxide initiation was confirmed by solid-state magic angle spinning (MAS) C-13 and Si-29 nuclear magnetic resonance (NMR) measurements. The Raman spectrum of the cross-linked VTMOS-rGO and LDPE confirmed the formation of a 3D network. Scanning electron (SEM) and transmission electron (TEM) microscopy with elemental mapping showed the VTMOS forms nanospheres located interstitially between rGO layers dispersed within the LDPE matrix. From oscillatory rheology measurements, the transition to more "solid-like" behavior due to cross-linking was detected from a significant decrease in the crossover frequency (G' vs G '') from 31.6 to as low as 0.603 rad/s and an increase in relaxation times (lambda) from 0.032 to 1.66 s for a rGO loading of 1 wt %. The formation of a 3D interconnected cross-linked VTMOS-rGO-LDPE network resulted in an increase in the tensile strength (up arrow 31%) and tensile stress at break (up arrow 55%) of LDPE. The onset of thermal degradation of LDPE was delayed by up to 31 degrees C due to the formation of cross-links and inclusion of silane functionalized rGO which requires a higher activation energy to initiate degradation.

@article{carlotta-jones_improved_2020,
	title = {Improved hydrogen gas production in microbial electrolysis cells using inexpensive recycled carbon fibre fabrics},
	volume = {304},
	issn = {0960-8524},
	doi = {10.1016/j.biortech.2020.122983},
	abstract = {Growing energy demands of wastewater treatment have made it vital for water companies to develop less energy intensive processes for treating wastewater if net zero emissions are to be achieved by 2050. Microbial electrolysis cells (MECs) have the potential to do this by treating water and producing renewable hydrogen gas as a product, but capital and operational costs have slowed their deployment. By using recycled carbon fibre mats, commercially viable MECs can brought closer to reality, where recycled carbon fibre anode MECs treating real wastewater (normalised similar to 3100 L d(-1)) were producing 66.77 L H-2 d(-1) while graphite felt anode MECs produced 3.65 L H-2 d(-1) per 1 m(3) reactor, anodes costing 5.53 pound m(-2) and 88.36 pound m(-2) respectively, resulting in a total anode cost saving of 93\%. This could incentivise the development of larger pilot systems, opening the door for generating greater value and a more sustainable wastewater treatment industry.},
	urldate = {2020-03-27},
	journal = {BIORESOURCE TECHNOLOGY},
	author = {Carlotta-Jones, Daniel Indiana and Purdy, Kevin and Kirwan, Kerry and Stratford, James and Coles, Stuart R.},
	month = may,
	year = {2020},
	note = {Cytecom},
}

Growing energy demands of wastewater treatment have made it vital for water companies to develop less energy intensive processes for treating wastewater if net zero emissions are to be achieved by 2050. Microbial electrolysis cells (MECs) have the potential to do this by treating water and producing renewable hydrogen gas as a product, but capital and operational costs have slowed their deployment. By using recycled carbon fibre mats, commercially viable MECs can brought closer to reality, where recycled carbon fibre anode MECs treating real wastewater (normalised similar to 3100 L d(-1)) were producing 66.77 L H-2 d(-1) while graphite felt anode MECs produced 3.65 L H-2 d(-1) per 1 m(3) reactor, anodes costing 5.53 pound m(-2) and 88.36 pound m(-2) respectively, resulting in a total anode cost saving of 93%. This could incentivise the development of larger pilot systems, opening the door for generating greater value and a more sustainable wastewater treatment industry.

@article{li_review_2020,
	title = {A {Review} on {Functionally} {Graded} {Materials} and {Structures} via {Additive} {Manufacturing}: {From} {Multi}-{Scale} {Design} to {Versatile} {Functional} {Properties}},
	volume = {5},
	issn = {2365-709X},
	doi = {10.1002/admt.201900981},
	abstract = {Functionally graded materials (FGMs) and functionally graded structures (FGSs) are special types of advanced composites with peculiar features and advantages. This article reviews the design criteria of functionally graded additive manufacturing (FGAM), which is capable of fabricating gradient components with versatile functional properties. Conventional geometrical-based design concepts have limited potential for FGAM and multi-scale design concepts (from geometrical patterning to microstructural design) are needed to develop gradient components with specific graded properties at different locations. FGMs and FGSs are of great interest to a larger range of industrial sectors and applications including aerospace, automotive, biomedical implants, optoelectronic devices, energy absorbing structures, geological models, and heat exchangers. This review presents an overview of various fabrication ideas and suggestions for future research in terms of design and creation of FGMs and FGSs, benefiting a wide variety of scientific fields.},
	number = {6},
	urldate = {2020-05-14},
	journal = {ADVANCED MATERIALS TECHNOLOGIES},
	author = {Li, Yan and Feng, Zuying and Hao, Liang and Huang, Lijing and Xin, Chenxing and Wang, Yushen and Bilotti, Emiliano and Essa, Khamis and Zhang, Han and Li, Zheng and Yan, Feifei and Peijs, Ton},
	month = jun,
	year = {2020},
}

Functionally graded materials (FGMs) and functionally graded structures (FGSs) are special types of advanced composites with peculiar features and advantages. This article reviews the design criteria of functionally graded additive manufacturing (FGAM), which is capable of fabricating gradient components with versatile functional properties. Conventional geometrical-based design concepts have limited potential for FGAM and multi-scale design concepts (from geometrical patterning to microstructural design) are needed to develop gradient components with specific graded properties at different locations. FGMs and FGSs are of great interest to a larger range of industrial sectors and applications including aerospace, automotive, biomedical implants, optoelectronic devices, energy absorbing structures, geological models, and heat exchangers. This review presents an overview of various fabrication ideas and suggestions for future research in terms of design and creation of FGMs and FGSs, benefiting a wide variety of scientific fields.

@article{beyer_brush_2020,
	title = {Brush {Copolymers} from 2-{Oxazoline} and {Acrylic} {Monomers} via an {Inimer} {Approach}},
	volume = {53},
	issn = {0024-9297},
	doi = {10.1021/acs.macromol.0c00243},
	abstract = {Brush-shaped macromolecular architectures provide unique material properties because of their dense branched structures. However, there are major challenges in obtaining brush-shaped macromolecules when the required functional monomers are not compatible for copolymerization using the same synthetic technique. Herein, we present an inimer molecule structure that has both an initiating group for Cu-mediated radical polymerization and a 2-oxazoline monomer ring for cationic ring-opening polymerization. Thus, various combinations of poly(2-oxazoline-brush-acrylate/acrylamide) copolymers could be obtained by grafting from a poly(2-oxazoline) backbone bearing radical initiator units. A simple two-step synthesis method for a novel 2-oxazoline inimer was established and used in the homo and block copolymerization with 2-ethyl-2-oxazoline to yield the brush initiator structure. Moreover, selected acrylates and acrylamides were utilized for Cu(0)-mediated reversible deactivation radical polymerization (RDRP) initiated through the brush initiator. Finally, because of the understanding obtained via optimization reactions, high/low density, block, and amphiphilic brush copolymers with narrow molecular weight distributions were successfully obtained.},
	number = {8},
	urldate = {2020-05-14},
	journal = {MACROMOLECULES},
	author = {Beyer, Valentin P. and Cattoz, Beatrice and Strong, Anthony and Schwarz, Andrew and Becer, C. Remzi},
	month = apr,
	year = {2020},
	note = {Infineum UK Ltd},
	pages = {2950--2958},
}

Brush-shaped macromolecular architectures provide unique material properties because of their dense branched structures. However, there are major challenges in obtaining brush-shaped macromolecules when the required functional monomers are not compatible for copolymerization using the same synthetic technique. Herein, we present an inimer molecule structure that has both an initiating group for Cu-mediated radical polymerization and a 2-oxazoline monomer ring for cationic ring-opening polymerization. Thus, various combinations of poly(2-oxazoline-brush-acrylate/acrylamide) copolymers could be obtained by grafting from a poly(2-oxazoline) backbone bearing radical initiator units. A simple two-step synthesis method for a novel 2-oxazoline inimer was established and used in the homo and block copolymerization with 2-ethyl-2-oxazoline to yield the brush initiator structure. Moreover, selected acrylates and acrylamides were utilized for Cu(0)-mediated reversible deactivation radical polymerization (RDRP) initiated through the brush initiator. Finally, because of the understanding obtained via optimization reactions, high/low density, block, and amphiphilic brush copolymers with narrow molecular weight distributions were successfully obtained.

@article{ellingford_understanding_2020,
	title = {Understanding the enhancement and temperature-dependency of the self-healing and electromechanical properties of dielectric elastomers containing mixed pendant polar groups},
	volume = {8},
	issn = {2050-7526},
	doi = {10.1039/d0tc00509f},
	abstract = {High permittivity self-healing dielectric elastomers have the potential to achieve long life, reusability, damage tolerance and enhanced energy density for energy harvesting devices and actuators. The self-healing performance of elastomers and usable temperature range can be affected by the chemical interactions present in the material. Self-healing thermoplastic elastomer styrene-butadiene-styrene (SBS) copolymers were prepared by introducing hydrogen bonding and electrostatic interactions through chemically grafting of polar groups to SBS: methyl thioglycolate (MG) and thioglycolic acid (TG). The mechanical properties were significantly affected by the strength of the hydrogen bonding network in the elastomers, whilst a high relative permittivity of epsilon(r)approximate to 9.2 with a low loss of tan delta approximate to 0.01 was achieved. In addition, a disorder-to-order phase morphology transition was observed upon increasing the TG content due to the increased hydrogen-bonding network within SBS. At room temperature the self-healed 80/20 MG/TG-SBS exhibited a strain at break of 139\% with a recovery ratio of 47.7\%, and when healed at 80 degrees C for 3 hours exhibited an increased strain at break of 230\% with a recovery ratio of 79\%. Analysis of FTIR and(1)H NMR indicated that the presence of a stronger hydrogen bonding network increased the thermal resistance of the elastomers. The temperature-dependency of the self-healing behaviour was interpreted as the combined effect of hydrogen bonding, electrostatic interactions and chain interdiffusion. This work provides an in-depth understanding of how to tune the electromechanical and self-healing properties of elastomers by tailoring the type and concentration of pendent polar groups. It indicates that intrinsic modification is critical for the development of next generation high performance dielectric elastomers for actuator or energy harvesting devices operating at elevated temperatures.},
	number = {16},
	urldate = {2020-07-23},
	journal = {JOURNAL OF MATERIALS CHEMISTRY C},
	author = {Ellingford, Christopher and Wemyss, Alan M. and Zhang, Runan and Prokes, Ivan and Pickford, Tom and Bowen, Chris and Coveney, Vincent A. and Wan, Chaoying},
	month = apr,
	year = {2020},
	pages = {5426--5436},
}

High permittivity self-healing dielectric elastomers have the potential to achieve long life, reusability, damage tolerance and enhanced energy density for energy harvesting devices and actuators. The self-healing performance of elastomers and usable temperature range can be affected by the chemical interactions present in the material. Self-healing thermoplastic elastomer styrene-butadiene-styrene (SBS) copolymers were prepared by introducing hydrogen bonding and electrostatic interactions through chemically grafting of polar groups to SBS: methyl thioglycolate (MG) and thioglycolic acid (TG). The mechanical properties were significantly affected by the strength of the hydrogen bonding network in the elastomers, whilst a high relative permittivity of epsilon(r)approximate to 9.2 with a low loss of tan delta approximate to 0.01 was achieved. In addition, a disorder-to-order phase morphology transition was observed upon increasing the TG content due to the increased hydrogen-bonding network within SBS. At room temperature the self-healed 80/20 MG/TG-SBS exhibited a strain at break of 139% with a recovery ratio of 47.7%, and when healed at 80 degrees C for 3 hours exhibited an increased strain at break of 230% with a recovery ratio of 79%. Analysis of FTIR and(1)H NMR indicated that the presence of a stronger hydrogen bonding network increased the thermal resistance of the elastomers. The temperature-dependency of the self-healing behaviour was interpreted as the combined effect of hydrogen bonding, electrostatic interactions and chain interdiffusion. This work provides an in-depth understanding of how to tune the electromechanical and self-healing properties of elastomers by tailoring the type and concentration of pendent polar groups. It indicates that intrinsic modification is critical for the development of next generation high performance dielectric elastomers for actuator or energy harvesting devices operating at elevated temperatures.

@article{tanaka_orthogonal_2020,
	title = {Orthogonal {Cationic} and {Radical} {RAFT} {Polymerizations} to {Prepare} {Bottlebrush} {Polymers}},
	volume = {59},
	issn = {1433-7851},
	doi = {10.1002/anie.202000700},
	abstract = {An orthogonal combination of cationic and radical RAFT polymerizations is used to synthesize bottlebrush polymers using two distinct RAFT agents. Selective consumption of the first RAFT agent is used to control the cationic RAFT polymerization of a vinyl ether monomer bearing a secondary dormant RAFT agent, which subsequently allows side-chain polymers to be grafted from the pendant RAFT agent by a radical-mediated RAFT polymerization of a different monomer, thus completing the synthesis of bottlebrush polymers. The high efficiency and selectivity of the cationic and radical RAFT polymerizations allow both polymerizations to be conducted in one-pot tandem without intermediate purification.},
	number = {18},
	urldate = {2020-04-29},
	journal = {ANGEWANDTE CHEMIE-INTERNATIONAL EDITION},
	author = {Tanaka, Joji and Hakkinen, Satu and Boeck, Parker T. and {Cong Yidan} and Perrier, Sebastien and Sheiko, Sergei S. and {You Wei}},
	month = apr,
	year = {2020},
	pages = {7203--7208},
}

An orthogonal combination of cationic and radical RAFT polymerizations is used to synthesize bottlebrush polymers using two distinct RAFT agents. Selective consumption of the first RAFT agent is used to control the cationic RAFT polymerization of a vinyl ether monomer bearing a secondary dormant RAFT agent, which subsequently allows side-chain polymers to be grafted from the pendant RAFT agent by a radical-mediated RAFT polymerization of a different monomer, thus completing the synthesis of bottlebrush polymers. The high efficiency and selectivity of the cationic and radical RAFT polymerizations allow both polymerizations to be conducted in one-pot tandem without intermediate purification.

@article{li_manganese_2020,
	title = {Manganese carbonyl induced cationic reversible addition-fragmentation chain transfer ({C}-{RAFT}) polymerization under visible light},
	volume = {11},
	issn = {1759-9954},
	doi = {10.1039/c9py01785b},
	abstract = {The manganese carbonyl induced cationic reversible addition-fragmentation chain transfer (C-RAFT) polymerization under mild conditions such as visible light, room temperature and even in the presence of small quantities of water is reported. In this method, halide abstraction reaction between organic halide and manganese carbonyl is used to generate the oxidant and initiate radicals. The C-RAFT agents are generated in situ from radical transfer reactions between vinyl ethers and three traditional RAFT agents including xanthate, trithiocarbonate and dithiocarbamate species. Poly(vinyl ether)s with RAFT agent terminated chain ends have been successfully obtained and used as macroRAFT agents for preparation of block copolymers combining RAFT radical polymerization. Poly(isobutyl vinyl ether)-b-poly(vinyl acetate) and poly(isobutyl vinyl ether)-b-poly(methyl acrylate) are successfully prepared. In addition, poly(butyl acrylate)-b-poly(isobutyl vinyl ether) have also been obtained using poly(butyl acrylate) prepared by RAFT radical polymerization as macroRAFT agent. Our results show that poly(vinyl ether)s with controlled molecular weight and narrow molecular weight distribution ({\textless}1.2) can be obtained when using dithiocarbamate.},
	number = {15},
	urldate = {2020-04-30},
	journal = {POLYMER CHEMISTRY},
	author = {Li, Jiajia and Kerr, Andrew and Haekkinen, Satu and Floyd, Thomas and Zhang, Mengmeng and Pan, Xiangqiang and Zhu, Xiulin and Perrier, Sebastien and Zhu, Jian},
	month = apr,
	year = {2020},
	pages = {2724--2731},
}

The manganese carbonyl induced cationic reversible addition-fragmentation chain transfer (C-RAFT) polymerization under mild conditions such as visible light, room temperature and even in the presence of small quantities of water is reported. In this method, halide abstraction reaction between organic halide and manganese carbonyl is used to generate the oxidant and initiate radicals. The C-RAFT agents are generated in situ from radical transfer reactions between vinyl ethers and three traditional RAFT agents including xanthate, trithiocarbonate and dithiocarbamate species. Poly(vinyl ether)s with RAFT agent terminated chain ends have been successfully obtained and used as macroRAFT agents for preparation of block copolymers combining RAFT radical polymerization. Poly(isobutyl vinyl ether)-b-poly(vinyl acetate) and poly(isobutyl vinyl ether)-b-poly(methyl acrylate) are successfully prepared. In addition, poly(butyl acrylate)-b-poly(isobutyl vinyl ether) have also been obtained using poly(butyl acrylate) prepared by RAFT radical polymerization as macroRAFT agent. Our results show that poly(vinyl ether)s with controlled molecular weight and narrow molecular weight distribution (\textless1.2) can be obtained when using dithiocarbamate.

@article{tanaka_functionalisation_2020,
	title = {Functionalisation and stabilisation of polymeric arsenical nanoparticles prepared by sequential reductive and radical cross-linking},
	volume = {11},
	issn = {1759-9954},
	doi = {10.1039/d0py00229a},
	abstract = {The chemical reactivity of arsenic is diverse and distinctive depending upon its interchangeable oxidation states. Alkyl and aryl arsines (As(i)) exist as oligomers, composed of labile and redox responsive As-As bonds which have been exploited to form reactive and responsive materials. Here, the lability and reactivity of As(i)-functional polymeric nanoparticles, derived from thermoresponsive polymers P(PEGA(20)-b-[NIPAm80-n-co-AsAmn]) (P1, n = 4; P2, n = 11; P3, n = 15; P4, n = 18), is elaborated by in situ reaction with functional acetylenes, resulting in the formation of vinylene-arsine cross-linked polymeric arsenical nanoparticles (NPV-As). Spherical particles with sizes {\textless}35 nm have been prepared, which are advantageous for potential drug-delivery (e.g. tumour accumulation) applications. Functional acetylenes enable the introduction of reactive amine, acid and alcohol functional groups into the particles, while the use of propargyl-O-rhodamine ester results in the formation of fluorescent nanoparticles. The vinylene-arsine cross-linking confers increased stability of the polymeric arsenical nanoparticles in model biological redox conditions (GSH, H2O2, 5 mM) compared to those reported previously, with nanoparticle structures retained over 7 days. The parent polymeric arsenicals and the resulting nanoparticles were all shown to exhibit limited cytotoxicity in vitro and cell uptake was confirmed by incubating fluorescent-labelled nanoparticles with PC3 cells. Furthermore, fluorescent confocal microscopy using the PC3 cell-line, confirmed that the nanoparticles were internalised by the cells with evidence of mitochondrial co-localisation, which supports a mitochondria-targeting of arsenic hypothesized based on work involving organoarsenical chemotherapeutics. Thus, this work demonstrates a novel strategy for the preparation of polymeric arsenical nanoparticles, with broad functional group tolerance, and expands our emerging understanding of the in vitro behaviour of this family of nanomaterials.},
	number = {14},
	urldate = {2020-04-21},
	journal = {POLYMER CHEMISTRY},
	author = {Tanaka, Joji and Evans, Alexander and Gurnani, Pratik and Kerr, Andrew and Wilson, Paul},
	month = apr,
	year = {2020},
	pages = {2519--2531},
}

The chemical reactivity of arsenic is diverse and distinctive depending upon its interchangeable oxidation states. Alkyl and aryl arsines (As(i)) exist as oligomers, composed of labile and redox responsive As-As bonds which have been exploited to form reactive and responsive materials. Here, the lability and reactivity of As(i)-functional polymeric nanoparticles, derived from thermoresponsive polymers P(PEGA(20)-b-[NIPAm80-n-co-AsAmn]) (P1, n = 4; P2, n = 11; P3, n = 15; P4, n = 18), is elaborated by in situ reaction with functional acetylenes, resulting in the formation of vinylene-arsine cross-linked polymeric arsenical nanoparticles (NPV-As). Spherical particles with sizes \textless35 nm have been prepared, which are advantageous for potential drug-delivery (e.g. tumour accumulation) applications. Functional acetylenes enable the introduction of reactive amine, acid and alcohol functional groups into the particles, while the use of propargyl-O-rhodamine ester results in the formation of fluorescent nanoparticles. The vinylene-arsine cross-linking confers increased stability of the polymeric arsenical nanoparticles in model biological redox conditions (GSH, H2O2, 5 mM) compared to those reported previously, with nanoparticle structures retained over 7 days. The parent polymeric arsenicals and the resulting nanoparticles were all shown to exhibit limited cytotoxicity in vitro and cell uptake was confirmed by incubating fluorescent-labelled nanoparticles with PC3 cells. Furthermore, fluorescent confocal microscopy using the PC3 cell-line, confirmed that the nanoparticles were internalised by the cells with evidence of mitochondrial co-localisation, which supports a mitochondria-targeting of arsenic hypothesized based on work involving organoarsenical chemotherapeutics. Thus, this work demonstrates a novel strategy for the preparation of polymeric arsenical nanoparticles, with broad functional group tolerance, and expands our emerging understanding of the in vitro behaviour of this family of nanomaterials.

@article{liu_sustainable_2020,
	title = {Sustainable and self-regulating out-of-oven manufacturing of {FRPs} with integrated multifunctional capabilities},
	volume = {190},
	issn = {0266-3538},
	doi = {10.1016/j.compscitech.2020.108032},
	abstract = {With the ever increasing demand for energy reduction to stimulate sustainable development, new energy efficient manufacturing processes for advanced fibre-reinforced plastics (FRPs) are of great interest to overcome limitations of conventional autoclave or oven based manufacturing processes such as high energy consumption and size restrictions. Herein, a highly energy efficient and safe out-of-oven curing method is presented by integrating a pyroresistive surface layer with intrinsic self-regulating heating capabilities, into a composite laminate. This surface layer consists of a nanocomposite film based on graphene nanoplatelets (GNPs) and high density polyethylene (HDPE) and possesses self-regulating Joule heating capabilities, which can be used to cure epoxy based composites at a desired temperature without the risk of over-heating. Moreover, the thermoplastic nature of the surface layer enables easy fabrication with good flexibility for complex shapes. Compared to state-of-the-art out-of-autoclave oven curing, the proposed out-of-oven Joule heating approach consumed only 1\% of the energy required for curing, with no effect on mechanical performance and glass transition temperature (Td of the final composite. Moreover, the integration of the self-regulating heating layer offers additional functionalities to the cured composites, like strain or damage sensing as well as the potential of de-icing without affecting the internal structure and performance of the laminate. The presented smart heating layer provides a novel solution for sustainable manufacturing as well as real-time structural health monitoring (SHM) throughout the components' life for multifunctional composite applications in the field of renewable wind energy and aerospace.},
	urldate = {2020-04-10},
	journal = {COMPOSITES SCIENCE AND TECHNOLOGY},
	author = {Liu, Yi and van Vliet, Tim and Tao, Yinping and Busfield, James J. C. and Peijs, Ton and Bilotti, Emiliano and Zhang, Han},
	month = apr,
	year = {2020},
}

With the ever increasing demand for energy reduction to stimulate sustainable development, new energy efficient manufacturing processes for advanced fibre-reinforced plastics (FRPs) are of great interest to overcome limitations of conventional autoclave or oven based manufacturing processes such as high energy consumption and size restrictions. Herein, a highly energy efficient and safe out-of-oven curing method is presented by integrating a pyroresistive surface layer with intrinsic self-regulating heating capabilities, into a composite laminate. This surface layer consists of a nanocomposite film based on graphene nanoplatelets (GNPs) and high density polyethylene (HDPE) and possesses self-regulating Joule heating capabilities, which can be used to cure epoxy based composites at a desired temperature without the risk of over-heating. Moreover, the thermoplastic nature of the surface layer enables easy fabrication with good flexibility for complex shapes. Compared to state-of-the-art out-of-autoclave oven curing, the proposed out-of-oven Joule heating approach consumed only 1% of the energy required for curing, with no effect on mechanical performance and glass transition temperature (Td of the final composite. Moreover, the integration of the self-regulating heating layer offers additional functionalities to the cured composites, like strain or damage sensing as well as the potential of de-icing without affecting the internal structure and performance of the laminate. The presented smart heating layer provides a novel solution for sustainable manufacturing as well as real-time structural health monitoring (SHM) throughout the components' life for multifunctional composite applications in the field of renewable wind energy and aerospace.

@article{heeley_-situ_2020,
	title = {In-situ uniaxial drawing of poly-{L}-lactic acid ({PLLA}): {Following} the crystalline morphology development using time-resolved {SAXS}/{WAXS}},
	volume = {193},
	issn = {0032-3861},
	doi = {10.1016/j.polymer.2020.122353},
	abstract = {Simultaneous synchrotron small- and wide-angle X-ray scattering (SAXS/WAXS) was used to follow the crystalline morphology evolution of poly-L-lactic acid (PLLA) during uniaxial deformation at various draw temperatures (T-d). The mechanical behaviour of PLLA, was found to be strongly dependent on T-d. 2D SAXS/WAXS data taken during the draw showed that at low T(d)s cavitation and voiding occurred and the initial crystallites underwent 'overdrawing' where they slip and are partially destroyed. SEM confirmed that surface voiding and cavitation had occurred at T-d = 60 and 65 degrees C but was absent at higher T(d)s. During the draw, no long-range macromolecular lamellar structure was seen in the SAXS, but small crystallites of the disordered alpha' crystal form of PLLA were observed in the WAXS at all T(d)s. The PLLA samples were then step annealed in a second processing stage (post-draw) to develop the oriented crystalline lamellar structure and increase the amount of the stable a crystalline form. SAXS/WAXS data showed that a highly oriented lamellar stack macrostructure developed on annealing, with increased crystallite size and crystallinity at all T(d)s. Furthermore, step annealing drove the crystalline transition in all samples from the disordered alpha' crystal form to the stable alpha crystal form. Therefore, varying pre- and post-processing parameters can significantly influence the mechanical properties, orientation, crystalline morphology and crystal phase transition of the final PLLA material.},
	urldate = {2020-04-20},
	journal = {POLYMER},
	author = {Heeley, Ellen L. and Billimoria, Kharmen and Parsons, Nathan and Figiel, Lukasz and Keating, Elspeth M. and Cafolla, Conor T. and Crabb, Eleanor M. and Hughes, Darren J.},
	month = apr,
	year = {2020},
}

Simultaneous synchrotron small- and wide-angle X-ray scattering (SAXS/WAXS) was used to follow the crystalline morphology evolution of poly-L-lactic acid (PLLA) during uniaxial deformation at various draw temperatures (T-d). The mechanical behaviour of PLLA, was found to be strongly dependent on T-d. 2D SAXS/WAXS data taken during the draw showed that at low T(d)s cavitation and voiding occurred and the initial crystallites underwent 'overdrawing' where they slip and are partially destroyed. SEM confirmed that surface voiding and cavitation had occurred at T-d = 60 and 65 degrees C but was absent at higher T(d)s. During the draw, no long-range macromolecular lamellar structure was seen in the SAXS, but small crystallites of the disordered alpha' crystal form of PLLA were observed in the WAXS at all T(d)s. The PLLA samples were then step annealed in a second processing stage (post-draw) to develop the oriented crystalline lamellar structure and increase the amount of the stable a crystalline form. SAXS/WAXS data showed that a highly oriented lamellar stack macrostructure developed on annealing, with increased crystallite size and crystallinity at all T(d)s. Furthermore, step annealing drove the crystalline transition in all samples from the disordered alpha' crystal form to the stable alpha crystal form. Therefore, varying pre- and post-processing parameters can significantly influence the mechanical properties, orientation, crystalline morphology and crystal phase transition of the final PLLA material.

@article{roman_effect_2020,
	title = {Effect of selective distribution of {MWCNTs} on the solid-state rheological and dielectric properties of blends of {PMMA} and {LDPE}},
	volume = {55},
	issn = {0022-2461},
	doi = {10.1007/s10853-020-04622-6},
	abstract = {The effects of adding multi-walled carbon nanotubes (MWCNTs) on the solid-state rheological and dielectric properties of blends of poly(methyl methacrylate) (PMMA) and low-density polyethylene (LDPE) were studied as a function of varying polymer ratio. Dynamic mechanical thermal analysis (DMTA) was performed in torsion mode, on the blends and their composites with MWCNTs. For a PMMA/LDPE blend with a ratio of 80:20, the evolution of the loss tangent with temperature showed a single thermal event, associated with the glass transition (T-g) of PMMA, confirming that co-continuity has not been achieved. Upon loading with 2 wt.\% MWCNTs, a decrease in the magnitude of this peak is observed. Even though the MWCNTs preferentially locate in the polymer phase first to melt, i.e., LDPE, selective solvent extraction on this sample demonstrated that some of the MWCNTs are trapped in the major phase, PMMA. Moreover, DMTA measurements also revealed the formation of a "rheological" percolated network at similar to 3.5 wt.\% MWCNTs in PMMA/LDPE blends with polymer ratios of 50:50 and 20:80, but not in 80:20. In contrast, for the same MWCNT concentration, a 80:20 blend displayed a well-developed AC conductivity plateau at low frequencies and highly enhanced dielectric properties, as a consequence of the high concentration of micro-capacitors formed by polymer films sandwiched by nanotubes within the LDPE phase, as proven from atomic force microscopy observations.},
	number = {20},
	urldate = {2020-04-21},
	journal = {JOURNAL OF MATERIALS SCIENCE},
	author = {Roman, Claudia and Garcia-Morales, Moises and Olariu, Marius A. and McNally, Tony},
	month = jul,
	year = {2020},
	pages = {8526--8540},
}

The effects of adding multi-walled carbon nanotubes (MWCNTs) on the solid-state rheological and dielectric properties of blends of poly(methyl methacrylate) (PMMA) and low-density polyethylene (LDPE) were studied as a function of varying polymer ratio. Dynamic mechanical thermal analysis (DMTA) was performed in torsion mode, on the blends and their composites with MWCNTs. For a PMMA/LDPE blend with a ratio of 80:20, the evolution of the loss tangent with temperature showed a single thermal event, associated with the glass transition (T-g) of PMMA, confirming that co-continuity has not been achieved. Upon loading with 2 wt.% MWCNTs, a decrease in the magnitude of this peak is observed. Even though the MWCNTs preferentially locate in the polymer phase first to melt, i.e., LDPE, selective solvent extraction on this sample demonstrated that some of the MWCNTs are trapped in the major phase, PMMA. Moreover, DMTA measurements also revealed the formation of a "rheological" percolated network at similar to 3.5 wt.% MWCNTs in PMMA/LDPE blends with polymer ratios of 50:50 and 20:80, but not in 80:20. In contrast, for the same MWCNT concentration, a 80:20 blend displayed a well-developed AC conductivity plateau at low frequencies and highly enhanced dielectric properties, as a consequence of the high concentration of micro-capacitors formed by polymer films sandwiched by nanotubes within the LDPE phase, as proven from atomic force microscopy observations.

@article{chandra_size-dependent_2020,
	title = {Size-dependent dynamic characteristics of graphene based multi-layer nano hetero-structures},
	volume = {31},
	issn = {0957-4484},
	doi = {10.1088/1361-6528/ab6231},
	abstract = {Carbon-based nano hetero-structures are receiving increasing attention due their ability in multi-synchronous modulation of a range of mechanical and other critically desirable properties. In this paper, the vibration characteristics of two different graphene based heterostructures, graphene-hexagonal boron nitride (hBN) and graphene-molybdenum disulfide (MoS2), are explored based on atomistic finite element approach. Such vibrational characteristics of nanostructures are of utmost importance in order to access their suitability as structural members for adoption in various nano-scale devices and systems. In the current analysis, the developed atomistic finite element model for nano-heterostructures is extensively validated first with the results available in literature considering elastic responses and natural frequencies. Thereafter a range of insightful new results are presented for the dynamic behaviour of various configurations of graphene-hBN and graphene-MoS2 heterostructures including their size, chirality and boundary dependence. The investigation of tunable vibrational properties along with simultaneous modulation of other mechanical, electronic, optical, thermal and chemical attributes of such nano-heterostructures would accelerate their application as prospective candidates for manufacturing nanosensors, electromechanical resonators, and a wide range of other devices and systems across the length-scales.},
	number = {14},
	urldate = {2020-03-31},
	journal = {NANOTECHNOLOGY},
	author = {Chandra, Y. and Mukhopadhyay, T. and Adhikari, S. and Figiel, L.},
	month = apr,
	year = {2020},
}

Carbon-based nano hetero-structures are receiving increasing attention due their ability in multi-synchronous modulation of a range of mechanical and other critically desirable properties. In this paper, the vibration characteristics of two different graphene based heterostructures, graphene-hexagonal boron nitride (hBN) and graphene-molybdenum disulfide (MoS2), are explored based on atomistic finite element approach. Such vibrational characteristics of nanostructures are of utmost importance in order to access their suitability as structural members for adoption in various nano-scale devices and systems. In the current analysis, the developed atomistic finite element model for nano-heterostructures is extensively validated first with the results available in literature considering elastic responses and natural frequencies. Thereafter a range of insightful new results are presented for the dynamic behaviour of various configurations of graphene-hBN and graphene-MoS2 heterostructures including their size, chirality and boundary dependence. The investigation of tunable vibrational properties along with simultaneous modulation of other mechanical, electronic, optical, thermal and chemical attributes of such nano-heterostructures would accelerate their application as prospective candidates for manufacturing nanosensors, electromechanical resonators, and a wide range of other devices and systems across the length-scales.

@article{huang_tailoring_2020,
	title = {Tailoring the electrical and thermal conductivity of multi-component and multi-phase polymer composites},
	volume = {65},
	issn = {0950-6608},
	doi = {10.1080/09506608.2019.1582180},
	abstract = {The majority of polymers are electrical and thermal insulators. In order to create electrically active and thermally conductive polymers and composites, the hybrid-filler systems is an effective approach, i.e. combining different types of fillers with different dimensions, in order to facilitate the formation of interconnected conducting networks and to enhance the electrical, thermal, mechanical and processing properties synergistically. By tailoring polymer-filler interactions both thermodynamically and kinetically, the selective localisation of fillers in polymer blends and at the interface of co-continuous polymer blends can enhance the electrical conductivity at a low percolation threshold. Moreover, selective localisation of different filler types in different co-continuous phases can result in multiple functionalities, such as high electrical conductivity, thermal conductivity or electromagnetic interference shielding. In this review, we discuss the latest progress towards the development of electrically active and thermally conductive polymer composites, and highlight the technical challenges and future research directions.},
	number = {3},
	urldate = {2020-04-02},
	journal = {INTERNATIONAL MATERIALS REVIEWS},
	author = {Huang, Yao and Ellingford, Christopher and Bowen, Chris and McNally, Tony and Wu, Daming and Wan, Chaoying},
	month = apr,
	year = {2020},
	pages = {129--163},
}

The majority of polymers are electrical and thermal insulators. In order to create electrically active and thermally conductive polymers and composites, the hybrid-filler systems is an effective approach, i.e. combining different types of fillers with different dimensions, in order to facilitate the formation of interconnected conducting networks and to enhance the electrical, thermal, mechanical and processing properties synergistically. By tailoring polymer-filler interactions both thermodynamically and kinetically, the selective localisation of fillers in polymer blends and at the interface of co-continuous polymer blends can enhance the electrical conductivity at a low percolation threshold. Moreover, selective localisation of different filler types in different co-continuous phases can result in multiple functionalities, such as high electrical conductivity, thermal conductivity or electromagnetic interference shielding. In this review, we discuss the latest progress towards the development of electrically active and thermally conductive polymer composites, and highlight the technical challenges and future research directions.

@article{chandra_advances_2020,
	title = {Advances in finite element modelling of graphene and associated nanostructures},
	volume = {140},
	issn = {0927-796X},
	doi = {10.1016/j.mser.2020.100544},
	abstract = {Graphene and its associated nanostructures (GANS) have been widely investigated by means of experimental and numerical approaches over the last decade. GANS and GANS reinforced composite materials show exceptional promise towards superior mechanical and thermal properties along with limitless opportunity to tailor, control, design, modify and manipulate such properties. These attributes make graphene and its associated nanostructures as one of the most important future material technologies in aerospace, automotive, medical, civil and military sectors of the 21st century. Among the various numerical methods used to analyse GANS and GANS reinforced composite materials, the finite element method (FEM) plays a prominent role. The FEM has been the standard analysis and simulation method for conventional structural and mechanical problems over the past half a century. However, its growing role and impact in atomistic-scale numerical simulation in general, and GANS, in particular, is not well known within the wider scientific and engineering modelling and simulation research community. There is a compelling need to document the expansive use of the finite element method, its advantages, shortcomings, relevance and purpose in a way which is pertinent to both material science and numerical simulation researchers. This paper serves this need by discussing the current state of the art of finite element methodologies available to study GANS and GANS reinforced composites in the most comprehensive manner. A detailed description of the popular space frame based numerical simulation strategy widely used to represent GANS is given. An extensive survey is conducted on more than 600 research papers in order to examine the finite element predictions of the mechanical and thermal properties of graphene and its associated composite materials. These properties are selected in view of their direct relevance to crucial future technologies, such as high-performance automotive components, aerospace and bioengineering systems, energy technologies, and advanced therapeutic and surgical devices. Omissions of some fundamental mechanical and thermal modelling issues for GANS have been identified and insightful guidance towards future research directions to comprehensively address them is given. By reviewing a significant breadth of publications across several academic disciples, a large scatter in the numerical predictions of essential material constants arising from the differences in fundamental assumptions and approximations has been reported. The origin of such discrepancies has been identified, analysed and established. The paper further focuses on the idealization of nanostructures and nanocomposites by means of representative volume elements (RVEs). The need for this multiscale modelling strategy to mature in order to include the simultaneous description of different material length scales within multiphysics simulation problems has been discussed. This paper will serve as standalone reference material for future research works and will pave the way for novel investigations in the context of atomistic simulations and their potential applications to the development of next-generation engineering devices and cutting-edge technological applications.},
	urldate = {2020-05-14},
	journal = {MATERIALS SCIENCE \& ENGINEERING R-REPORTS},
	author = {Chandra, Y. and Adhikari, S. and Flores, E. I. Saavedra and Figiei, L.},
	month = apr,
	year = {2020},
}

Graphene and its associated nanostructures (GANS) have been widely investigated by means of experimental and numerical approaches over the last decade. GANS and GANS reinforced composite materials show exceptional promise towards superior mechanical and thermal properties along with limitless opportunity to tailor, control, design, modify and manipulate such properties. These attributes make graphene and its associated nanostructures as one of the most important future material technologies in aerospace, automotive, medical, civil and military sectors of the 21st century. Among the various numerical methods used to analyse GANS and GANS reinforced composite materials, the finite element method (FEM) plays a prominent role. The FEM has been the standard analysis and simulation method for conventional structural and mechanical problems over the past half a century. However, its growing role and impact in atomistic-scale numerical simulation in general, and GANS, in particular, is not well known within the wider scientific and engineering modelling and simulation research community. There is a compelling need to document the expansive use of the finite element method, its advantages, shortcomings, relevance and purpose in a way which is pertinent to both material science and numerical simulation researchers. This paper serves this need by discussing the current state of the art of finite element methodologies available to study GANS and GANS reinforced composites in the most comprehensive manner. A detailed description of the popular space frame based numerical simulation strategy widely used to represent GANS is given. An extensive survey is conducted on more than 600 research papers in order to examine the finite element predictions of the mechanical and thermal properties of graphene and its associated composite materials. These properties are selected in view of their direct relevance to crucial future technologies, such as high-performance automotive components, aerospace and bioengineering systems, energy technologies, and advanced therapeutic and surgical devices. Omissions of some fundamental mechanical and thermal modelling issues for GANS have been identified and insightful guidance towards future research directions to comprehensively address them is given. By reviewing a significant breadth of publications across several academic disciples, a large scatter in the numerical predictions of essential material constants arising from the differences in fundamental assumptions and approximations has been reported. The origin of such discrepancies has been identified, analysed and established. The paper further focuses on the idealization of nanostructures and nanocomposites by means of representative volume elements (RVEs). The need for this multiscale modelling strategy to mature in order to include the simultaneous description of different material length scales within multiphysics simulation problems has been discussed. This paper will serve as standalone reference material for future research works and will pave the way for novel investigations in the context of atomistic simulations and their potential applications to the development of next-generation engineering devices and cutting-edge technological applications.

@article{lawton_determining_2020,
	title = {Determining the sequence and backbone structure of "semi-statistical" copolymers as donor-acceptor polymers in organic solar cells},
	volume = {4},
	issn = {2398-4902},
	doi = {10.1039/c9se01261c},
	abstract = {Organic photovoltaics (OPVs) are attracting significant attention due to the growing demand for economically viable and renewable energy sources. With efficiencies exceeding 16.5\%, single junction bulk heterojunction (BHJ) devices are amongst the most promising and are nearing commercialisation. One recent avenue of research has focused on statistical conjugated copolymers. However, a detailed investigation as to why these materials can achieve higher power conversion efficiencies than their regular alternating counterparts is seldom reported. This work describes an investigation into donor-acceptor polymers demonstrating how differing monomer activities can lead to differing microstructures in a simple batch reaction, which in turn demonstrates promising optoelectronic and morphological properties required for organic photovoltaic devices. A one pot condensation polymerisation reaction with three monomers leads to an ABA triblock structure from differing monomer reactivities. This structure in turn leads to visualised phase separation which is possibly linked to an increase in performance. Further to this we report on the reliability of the Stille coupling for the synthesis of conjugated polymers.},
	number = {4},
	urldate = {2020-04-30},
	journal = {SUSTAINABLE ENERGY \& FUELS},
	author = {Lawton, Samuel S. and Warr, Daniel and Perdigao, Luis M. A. and Chang, Yujing and Pron, Agnieszka and Costantini, Giovanni and Haddleton, David M.},
	month = apr,
	year = {2020},
	note = {Merck Chem Ltd},
	pages = {2026--2034},
}

Organic photovoltaics (OPVs) are attracting significant attention due to the growing demand for economically viable and renewable energy sources. With efficiencies exceeding 16.5%, single junction bulk heterojunction (BHJ) devices are amongst the most promising and are nearing commercialisation. One recent avenue of research has focused on statistical conjugated copolymers. However, a detailed investigation as to why these materials can achieve higher power conversion efficiencies than their regular alternating counterparts is seldom reported. This work describes an investigation into donor-acceptor polymers demonstrating how differing monomer activities can lead to differing microstructures in a simple batch reaction, which in turn demonstrates promising optoelectronic and morphological properties required for organic photovoltaic devices. A one pot condensation polymerisation reaction with three monomers leads to an ABA triblock structure from differing monomer reactivities. This structure in turn leads to visualised phase separation which is possibly linked to an increase in performance. Further to this we report on the reliability of the Stille coupling for the synthesis of conjugated polymers.

@article{richards_polymer-stabilized_2020,
	title = {Polymer-{Stabilized} {Sialylated} {Nanoparticles}: {Synthesis}, {Optimization}, and {Differential} {Binding} to {Influenza} {Hemagglutinins}},
	volume = {21},
	issn = {1525-7797},
	doi = {10.1021/acs.biomac.0c00179},
	abstract = {During influenza infection, hemagglutinins (HAs) on the viral surface bind to sialic acids on the host cell's surface. While all HAs bind sialic acids, human influenza targets terminal alpha 2,6 sialic acids and avian influenza targets alpha 2,3 sialic acids. For interspecies transmission (zoonosis), HA must mutate to adapt to these differences. Here, multivalent gold nanoparticles bearing either alpha 2,6- or alpha 2,3-sialyllactosamine have been developed to interrogate a panel of HAs from pathogenic human, low pathogenic avian, and other species' influenza. This method exploits the benefits of multivalent glycan presentation compared to monovalent presentation to increase affinity and investigate how multivalency affects selectivity. Using a library-orientated approach, parameters including polymer coating and core diameter were optimized for maximal binding and specificity were probed using galactosylated particles and a panel of biophysical techniques [ultraviolet-visible spectroscopy, dynamic light scattering, and biolayer interferometry]. The optimized particles were then functionalized with sialyllactosamine and their binding analyzed against a panel of HAs derived from pathogenic influenza strains including low pathogenic avian strains. This showed significant specificity crossover, which is not observed in monovalent formats, with binding of avian HAs to human sialic acids and vice versa in agreement with alternate assay formats. These results demonstrate that precise multivalent presentation is essential to dissect the interactions of HAs and may aid the discovery of tools for disease and zoonosis transmission.},
	number = {4},
	urldate = {2020-04-01},
	journal = {BIOMACROMOLECULES},
	author = {Richards, Sarah-Jane and Baker, Alexander N. and Walker, Marc and Gibson, I, Matthew},
	month = apr,
	year = {2020},
	pages = {1604--1612},
}

During influenza infection, hemagglutinins (HAs) on the viral surface bind to sialic acids on the host cell's surface. While all HAs bind sialic acids, human influenza targets terminal alpha 2,6 sialic acids and avian influenza targets alpha 2,3 sialic acids. For interspecies transmission (zoonosis), HA must mutate to adapt to these differences. Here, multivalent gold nanoparticles bearing either alpha 2,6- or alpha 2,3-sialyllactosamine have been developed to interrogate a panel of HAs from pathogenic human, low pathogenic avian, and other species' influenza. This method exploits the benefits of multivalent glycan presentation compared to monovalent presentation to increase affinity and investigate how multivalency affects selectivity. Using a library-orientated approach, parameters including polymer coating and core diameter were optimized for maximal binding and specificity were probed using galactosylated particles and a panel of biophysical techniques [ultraviolet-visible spectroscopy, dynamic light scattering, and biolayer interferometry]. The optimized particles were then functionalized with sialyllactosamine and their binding analyzed against a panel of HAs derived from pathogenic influenza strains including low pathogenic avian strains. This showed significant specificity crossover, which is not observed in monovalent formats, with binding of avian HAs to human sialic acids and vice versa in agreement with alternate assay formats. These results demonstrate that precise multivalent presentation is essential to dissect the interactions of HAs and may aid the discovery of tools for disease and zoonosis transmission.

@article{wu_coupling_2020,
	title = {Coupling {Dynamic} {Covalent} {Bonds} and {Ionic} {Crosslinking} {Network} to {Promote} {Shape} {Memory} {Properties} of {Ethylene}-vinyl {Acetate} {Copolymers}},
	volume = {12},
	issn = {2073-4360},
	doi = {10.3390/polym12040983},
	abstract = {Dynamic crosslinking networks based on Diels-Alder (DA) chemistry and ionic interactions were introduced to maleic anhydride modified ethylene-vinyl acetate copolymer (mEVA) via in situ melt processing. The dual dynamic crosslinking networks were characterized by temperature-dependent FTIR, and the effects on the shape memory properties of mEVA were evaluated with dynamic mechanical thermal analysis and cyclic tensile testing. A crosslinking density was achieved at 2.36 x 10(-4) molcm(-3) for DA-crosslinked mEVA; as a result, the stress at 100\% extension was increased from 3.8 to 5.6 MPa, and tensile strength and elongation at break were kept as high as 30.3 MPa and 486\%, respectively. The further introduction of 10 wt \% zinc methacrylate increased the dynamic crosslinking density to 3.74 x 10(-4) molcm(-3) and the stress at 100\% extension to 9.0 MPa, while providing a tensile strength of 28.4 MPa and strain at break of 308\%. The combination of reversible DA covalent crosslinking and ionic network in mEVA enabled a fixing ratio of 76.4\% and recovery ratio of 99.4\%, exhibiting an enhanced shape memory performance, especially at higher temperatures. The enhanced shape memory and mechanical performance of the dual crosslinked mEVA showed promising reprocessing and recycling abilities of the end-of-life products in comparison to traditional peroxide initiated covalent crosslinked counterparts.},
	number = {4},
	urldate = {2020-06-08},
	journal = {POLYMERS},
	author = {Wu, Wenjing and Kurup, Sreeni Narayana and Ellingford, Christopher and Li, Jie and Wan, Chaoying},
	month = apr,
	year = {2020},
	note = {Aerosp Res Inst Mat \& Proc Technol},
}

Dynamic crosslinking networks based on Diels-Alder (DA) chemistry and ionic interactions were introduced to maleic anhydride modified ethylene-vinyl acetate copolymer (mEVA) via in situ melt processing. The dual dynamic crosslinking networks were characterized by temperature-dependent FTIR, and the effects on the shape memory properties of mEVA were evaluated with dynamic mechanical thermal analysis and cyclic tensile testing. A crosslinking density was achieved at 2.36 x 10(-4) molcm(-3) for DA-crosslinked mEVA; as a result, the stress at 100% extension was increased from 3.8 to 5.6 MPa, and tensile strength and elongation at break were kept as high as 30.3 MPa and 486%, respectively. The further introduction of 10 wt % zinc methacrylate increased the dynamic crosslinking density to 3.74 x 10(-4) molcm(-3) and the stress at 100% extension to 9.0 MPa, while providing a tensile strength of 28.4 MPa and strain at break of 308%. The combination of reversible DA covalent crosslinking and ionic network in mEVA enabled a fixing ratio of 76.4% and recovery ratio of 99.4%, exhibiting an enhanced shape memory performance, especially at higher temperatures. The enhanced shape memory and mechanical performance of the dual crosslinked mEVA showed promising reprocessing and recycling abilities of the end-of-life products in comparison to traditional peroxide initiated covalent crosslinked counterparts.

@article{yilmaz_glycopolymer_2020,
	title = {Glycopolymer {Code}: {Programming} {Synthetic} {Macromolecules} for {Biological} {Targeting}},
	volume = {221},
	issn = {1022-1352},
	doi = {10.1002/macp.202000006},
	abstract = {Targeting in a cellular level is still one of the major challenges in biomedical treatments. However, new synthetic and analytical techniques now allow the development of precisely prepared macromolecules. Thus, glycopolymer chains are reported to be prepared with controlled length, monomer sequences, as well as chain-folded structures. A high level of complexity in synthetic macromolecules also allows increased selectivity in targeting, which is a key factor in biomedical applications.},
	number = {7},
	urldate = {2020-04-21},
	journal = {MACROMOLECULAR CHEMISTRY AND PHYSICS},
	author = {Yilmaz, Gokhan and Becer, Caglar Remzi},
	month = apr,
	year = {2020},
}

Targeting in a cellular level is still one of the major challenges in biomedical treatments. However, new synthetic and analytical techniques now allow the development of precisely prepared macromolecules. Thus, glycopolymer chains are reported to be prepared with controlled length, monomer sequences, as well as chain-folded structures. A high level of complexity in synthetic macromolecules also allows increased selectivity in targeting, which is a key factor in biomedical applications.

@article{yang_hierarchical_2020,
	title = {Hierarchical {Self}-{Assembled} {Photo}-{Responsive} {Tubisomes} from a {Cyclic} {Peptide}-{Bridged} {Amphiphilic} {Block} {Copolymer}},
	volume = {59},
	issn = {1433-7851},
	doi = {10.1002/anie.201916111},
	abstract = {Typically, the morphologies of the self-assembled nanostructures from block copolymers are limited to spherical micelles, wormlike micelles and vesicles. Now, a new generation of materials with unique shape and structures, cylindrical soft matter particles (tubisomes), are obtained from the hierarchical self-assembly of cyclic peptide-bridged amphiphilic diblock copolymers. The capacity of obtained photo-responsive tubisomes as potential drug carriers is evaluated. The supramolecular tubisomes pave an alternative way for fabricating polymeric tubular structures, and will expand the toolbox for the rational design of functional hierarchical nanostructures.},
	number = {23},
	urldate = {2020-04-03},
	journal = {ANGEWANDTE CHEMIE-INTERNATIONAL EDITION},
	author = {Yang, Jie and Song, Ji-Inn and Song, Qiao and Rho, Julia Y. and Mansfield, Edward D. H. and Hall, Stephen C. L. and Sambrook, Megan and Huang, Feihe and Perrier, Sebastien},
	month = jun,
	year = {2020},
	pages = {8860--8863},
}

Typically, the morphologies of the self-assembled nanostructures from block copolymers are limited to spherical micelles, wormlike micelles and vesicles. Now, a new generation of materials with unique shape and structures, cylindrical soft matter particles (tubisomes), are obtained from the hierarchical self-assembly of cyclic peptide-bridged amphiphilic diblock copolymers. The capacity of obtained photo-responsive tubisomes as potential drug carriers is evaluated. The supramolecular tubisomes pave an alternative way for fabricating polymeric tubular structures, and will expand the toolbox for the rational design of functional hierarchical nanostructures.

@article{zhou_structure_2020,
	title = {Structure and electrochemical properties of hierarchically porous carbon nanomaterials derived from hybrid {ZIF}-8/{ZIF}-67 bi-{MOF} coated cyclomatrix poly(organophosphazene) nanospheres},
	volume = {44},
	issn = {1144-0546},
	doi = {10.1039/d0nj00040j},
	abstract = {Hybrid bi-ZIF nanocrystals consisting of ZIF-8/ZIF-67 were synthesised in the presence of cyclomatrix poly(organophosphazene) (POP) nanospheres and formed POP/bi-ZIF core@shell nanospheres. POP/bi-ZIF showed excellent thermal stability up to 478 degrees C, with well-preserved core@shell structures during carbonization at 850 degrees C. The resultant core@shell carbon nanospheres exhibited hierarchically mesoporous structures. The porous carbon core was derived from the carbonised covalent inorganic-organic polyphosphazene framework, containing in situ doped heteroatoms such as N, P, S and O; the shell structure was derived from bi-ZIF containing up to 40\% Zn and Co elements. The bi-ZIF derived carbon shell showed a BET surface area of 1347.76 m(2) g(-1) and a Langmuir surface area of 1882.71 m(2) g(-1), and the total BET surface area of the core@shell structure reached 1025.00 m(2) g(-1). When applied as an anode material in lithium ion batteries, the core@shell carbon structure exhibited a charge capacity of 595 mA h g(-1) with a discharge capacity of 546 mA h g(-1) and maintained a reversible charge/discharge capacity of 400 mA h g(-1) after 140 cycles, which is higher than the theoretical capacity of a graphite anode. A good cycling stability with 83\% capacity retention in the C-rate tests was achieved. This work provides a facile and scalable method to produce mesoporous carbon nanostructures with in situ doped metal elements and heteroatoms, which benefits the high rate electrochemical properties of lithium ion batteries.},
	number = {11},
	urldate = {2020-04-09},
	journal = {NEW JOURNAL OF CHEMISTRY},
	author = {Zhou, Yutao and Wemyss, Alan M. and Brown, Oliver B. and Huang, Qianye and Wan, Chaoying},
	month = mar,
	year = {2020},
	pages = {4353--4362},
}

Hybrid bi-ZIF nanocrystals consisting of ZIF-8/ZIF-67 were synthesised in the presence of cyclomatrix poly(organophosphazene) (POP) nanospheres and formed POP/bi-ZIF core@shell nanospheres. POP/bi-ZIF showed excellent thermal stability up to 478 degrees C, with well-preserved core@shell structures during carbonization at 850 degrees C. The resultant core@shell carbon nanospheres exhibited hierarchically mesoporous structures. The porous carbon core was derived from the carbonised covalent inorganic-organic polyphosphazene framework, containing in situ doped heteroatoms such as N, P, S and O; the shell structure was derived from bi-ZIF containing up to 40% Zn and Co elements. The bi-ZIF derived carbon shell showed a BET surface area of 1347.76 m(2) g(-1) and a Langmuir surface area of 1882.71 m(2) g(-1), and the total BET surface area of the core@shell structure reached 1025.00 m(2) g(-1). When applied as an anode material in lithium ion batteries, the core@shell carbon structure exhibited a charge capacity of 595 mA h g(-1) with a discharge capacity of 546 mA h g(-1) and maintained a reversible charge/discharge capacity of 400 mA h g(-1) after 140 cycles, which is higher than the theoretical capacity of a graphite anode. A good cycling stability with 83% capacity retention in the C-rate tests was achieved. This work provides a facile and scalable method to produce mesoporous carbon nanostructures with in situ doped metal elements and heteroatoms, which benefits the high rate electrochemical properties of lithium ion batteries.

@article{theodorou_protein-polymer_2020,
	title = {Protein-polymer bioconjugates via a versatile oxygen tolerant photoinduced controlled radical polymerization approach},
	volume = {11},
	issn = {2041-1723},
	doi = {10.1038/s41467-020-15259-z},
	abstract = {The immense application potential of amphiphilic protein-polymer conjugates remains largely unexplored, as established "grafting from" synthetic protocols involve time-consuming, harsh and disruptive deoxygenation methods, while "grafting to" approaches result in low yields. Here we report an oxygen tolerant, photoinduced CRP approach which readily affords quantitative yields of protein-polymer conjugates within 2h, avoiding damage to the secondary structure of the protein and providing easily accessible means to produce biomacromolecular assemblies. Importantly, our methodology is compatible with multiple proteins (e.g. BSA, HSA, GOx, beta-galactosidase) and monomer classes including acrylates, methacrylates, styrenics and acrylamides. The polymerizations are conveniently conducted in plastic syringes and in the absence of any additives or external deoxygenation procedures using low-organic content media and ppm levels of copper. The robustness of the protocol is further exemplified by its implementation under UV, blue light or even sunlight irradiation as well as in buffer, nanopure, tap or even sea water. Amphiphilic protein-polymer conjugates remain largely unexplored due to synthetic protocols being complex. Here the authors explore an oxygen tolerant, photoinduced reversible-deactivated radical polymerization approach, which readily affords quantitative yields within 2h and thus avoids damage to the secondary structure of the proteins.},
	number = {1},
	urldate = {2020-04-09},
	journal = {NATURE COMMUNICATIONS},
	author = {Theodorou, Alexis and Liarou, Evelina and Haddleton, David M. and Stavrakaki, Iren Georgia and Skordalidis, Panagiotis and Whitfield, Richard and Anastasaki, Athina and Velonia, Kelly},
	month = mar,
	year = {2020},
}

The immense application potential of amphiphilic protein-polymer conjugates remains largely unexplored, as established "grafting from" synthetic protocols involve time-consuming, harsh and disruptive deoxygenation methods, while "grafting to" approaches result in low yields. Here we report an oxygen tolerant, photoinduced CRP approach which readily affords quantitative yields of protein-polymer conjugates within 2h, avoiding damage to the secondary structure of the protein and providing easily accessible means to produce biomacromolecular assemblies. Importantly, our methodology is compatible with multiple proteins (e.g. BSA, HSA, GOx, beta-galactosidase) and monomer classes including acrylates, methacrylates, styrenics and acrylamides. The polymerizations are conveniently conducted in plastic syringes and in the absence of any additives or external deoxygenation procedures using low-organic content media and ppm levels of copper. The robustness of the protocol is further exemplified by its implementation under UV, blue light or even sunlight irradiation as well as in buffer, nanopure, tap or even sea water. Amphiphilic protein-polymer conjugates remain largely unexplored due to synthetic protocols being complex. Here the authors explore an oxygen tolerant, photoinduced reversible-deactivated radical polymerization approach, which readily affords quantitative yields within 2h and thus avoids damage to the secondary structure of the proteins.

@article{holloway_sequence-defined_2020,
	title = {From {Sequence}-{Defined} {Macromolecules} to {Macromolecular} {Pin} {Codes}},
	volume = {7},
	issn = {2198-3844},
	doi = {10.1002/advs.201903698},
	abstract = {Dynamic sequence-defined oligomers carrying a chemically written pin code are obtained through a strategy combining multicomponent reactions with the thermoreversible addition of 1,2,4-triazoline-3,5-diones (TADs) to indole substrates. The precision oligomers are specifically designed to be encrypted upon heating as a result of the random reshuffling of the TAD-indole covalent bonds within the backbone, thereby resulting in the scrambling of the encoded information. The encrypted pin code can eventually be decrypted following a second heating step that enables the macromolecular pin code to be deciphered using 1D electrospray ionization-mass spectrometry (ESI-MS). The herein introduced concept of encryption/decryption represents a key advancement compared with current strategies that typically use uncontrolled degradation to erase and tandem mass spectrometry (MS/MS) to analyze, decipher, and read-out chemically encrypted information. Additionally, the synthesized macromolecules are coated onto a high-value polymer material, which demonstrates their potential application as coded product tags for anti-counterfeiting purposes.},
	number = {8},
	urldate = {2020-03-17},
	journal = {ADVANCED SCIENCE},
	author = {Holloway, Joshua O. and Van Lysebetten, Filip and Badi, Nezha and Houck, Hannes A. and Du Prez, Filip E.},
	month = apr,
	year = {2020},
}

Dynamic sequence-defined oligomers carrying a chemically written pin code are obtained through a strategy combining multicomponent reactions with the thermoreversible addition of 1,2,4-triazoline-3,5-diones (TADs) to indole substrates. The precision oligomers are specifically designed to be encrypted upon heating as a result of the random reshuffling of the TAD-indole covalent bonds within the backbone, thereby resulting in the scrambling of the encoded information. The encrypted pin code can eventually be decrypted following a second heating step that enables the macromolecular pin code to be deciphered using 1D electrospray ionization-mass spectrometry (ESI-MS). The herein introduced concept of encryption/decryption represents a key advancement compared with current strategies that typically use uncontrolled degradation to erase and tandem mass spectrometry (MS/MS) to analyze, decipher, and read-out chemically encrypted information. Additionally, the synthesized macromolecules are coated onto a high-value polymer material, which demonstrates their potential application as coded product tags for anti-counterfeiting purposes.

@article{hrabina_optically_2020,
	title = {Optically {Pure} {Metallohelices} {That} {Accumulate} in {Cell} {Nuclei}, {Condense}/{Aggregate} {DNA}, and {Inhibit} {Activities} of {DNA} {Processing} {Enzymes}},
	volume = {59},
	issn = {0020-1669},
	doi = {10.1021/acs.inorgchem.0c00092},
	abstract = {The water-compatible optically pure metallohelices made by self-assembly of simple nonpeptidic organic components around Fe(II) ions are now recognized as a distinct subclass of helicates that exhibit similar architecture to some natural cationic antimicrobial peptides. Notably, a new series of metallohelices was recently shown to exhibit biological activity, displaying high, structure-dependent activity against bacteria. It is also important that, thanks to their properties, such metallohelices can exhibit specific interactions with biomacromolecules. Here, following our prior report on the metallohelices that have high, structure-dependent activity against bacteria, we investigated the interactions of the series of iron(II) metallohelices with DNA, which is a potential pharmacological target of this class of coordination compounds. The results obtained with the aid of biophysical and molecular biology methods show that the investigated metallohelices accumulate in eukaryotic cells and that a significant fraction of the metallohelices accumulates in the cell nucleus, allowing them to interact also with nuclear DNA. Additionally, we have demonstrated that some metallohelices have a high affinity to DNA and are able to condense/aggregate DNA molecules more efficiently than conventional DNA-condensing agents, such as polyamines. Moreover, this capability of the metallohelices correlates with their efficiency to inhibit DNA-related enzymatic activities, such as those connected with DNA transcription, catalysis of DNA relaxation by DNA topoisomerase 1, and cleavage by restriction enzymes.},
	number = {5},
	urldate = {2020-04-02},
	journal = {INORGANIC CHEMISTRY},
	author = {Hrabina, Ondrej and Malina, Jaroslav and Kostrhunova, Hana and Novohradsky, Vojtech and Pracharova, Jitka and Rogers, Nicola and Simpson, Daniel H. and Scott, Peter and Brabec, Viktor},
	month = mar,
	year = {2020},
	pages = {3304--3311},
}

The water-compatible optically pure metallohelices made by self-assembly of simple nonpeptidic organic components around Fe(II) ions are now recognized as a distinct subclass of helicates that exhibit similar architecture to some natural cationic antimicrobial peptides. Notably, a new series of metallohelices was recently shown to exhibit biological activity, displaying high, structure-dependent activity against bacteria. It is also important that, thanks to their properties, such metallohelices can exhibit specific interactions with biomacromolecules. Here, following our prior report on the metallohelices that have high, structure-dependent activity against bacteria, we investigated the interactions of the series of iron(II) metallohelices with DNA, which is a potential pharmacological target of this class of coordination compounds. The results obtained with the aid of biophysical and molecular biology methods show that the investigated metallohelices accumulate in eukaryotic cells and that a significant fraction of the metallohelices accumulates in the cell nucleus, allowing them to interact also with nuclear DNA. Additionally, we have demonstrated that some metallohelices have a high affinity to DNA and are able to condense/aggregate DNA molecules more efficiently than conventional DNA-condensing agents, such as polyamines. Moreover, this capability of the metallohelices correlates with their efficiency to inhibit DNA-related enzymatic activities, such as those connected with DNA transcription, catalysis of DNA relaxation by DNA topoisomerase 1, and cleavage by restriction enzymes.

@article{ellingford_structure_2020,
	title = {Structure and {Dielectric} {Properties} of {Electroactive} {Tetraaniline} {Grafted} {Non}-{Polar} {Elastomers}},
	volume = {4},
	issn = {2504-477X},
	doi = {10.3390/jcs4010025},
	abstract = {Intrinsic modification of polybutadiene and block copolymer styrene-butadiene-styrene with the electrically conducting emeraldine salt of tetraaniline (TANI) via a three-step grafting method, is reported in this work. Whilst the TANI oligomer grafted at a similar rate to both polybutadiene and styrene-butadiene-styrene under the same conditions, the resulting elastomers exhibited vastly different properties. 1 mol\% TANI-PB exhibited an increased relative permittivity of 5.9, and a high strain at break of 156\%, whilst 25 mol\% TANI-SBS demonstrated a relative permittivity of 6.2 and a strain at break of 186\%. The difference in the behaviour of the two polymers was due to the compatibilisation of TANI by styrene in SBS through pi-pi stacking, which prevented the formation of a conducting TANI network in SBS at. Without the styrene group, TANI-PB formed a phase separated structure with high levels of TANI grafting. Overall, it was concluded that the polymer chain structure, the morphology of the modified elastomers, and the degree of grafting of TANI, had the greatest effect on the mechanical and dielectric properties of the resultant elastomers. This work paves the way for an alternative approach to the extrinsic incorporation of conducting groups into unsaturated elastomers, and demonstrates dielectric elastomers with enhanced electrical properties for use in actuation devices and energy harvesting applications.},
	number = {1},
	urldate = {2020-12-07},
	journal = {JOURNAL OF COMPOSITES SCIENCE},
	author = {Ellingford, Christopher and Pengchaicharoen, Atcharaporn and Wemyss, Alan M. and Wan, Chaoying},
	month = mar,
	year = {2020},
}

Intrinsic modification of polybutadiene and block copolymer styrene-butadiene-styrene with the electrically conducting emeraldine salt of tetraaniline (TANI) via a three-step grafting method, is reported in this work. Whilst the TANI oligomer grafted at a similar rate to both polybutadiene and styrene-butadiene-styrene under the same conditions, the resulting elastomers exhibited vastly different properties. 1 mol% TANI-PB exhibited an increased relative permittivity of 5.9, and a high strain at break of 156%, whilst 25 mol% TANI-SBS demonstrated a relative permittivity of 6.2 and a strain at break of 186%. The difference in the behaviour of the two polymers was due to the compatibilisation of TANI by styrene in SBS through pi-pi stacking, which prevented the formation of a conducting TANI network in SBS at. Without the styrene group, TANI-PB formed a phase separated structure with high levels of TANI grafting. Overall, it was concluded that the polymer chain structure, the morphology of the modified elastomers, and the degree of grafting of TANI, had the greatest effect on the mechanical and dielectric properties of the resultant elastomers. This work paves the way for an alternative approach to the extrinsic incorporation of conducting groups into unsaturated elastomers, and demonstrates dielectric elastomers with enhanced electrical properties for use in actuation devices and energy harvesting applications.

@article{gurnani_controlled_2020,
	title = {Controlled radical polymerization in dispersed systems for biological applications},
	volume = {102},
	issn = {0079-6700},
	doi = {10.1016/j.progpolymsci.2020.101209},
	abstract = {Polymeric nanoparticles show great promise in a range of biomedical applications, improving pharmacokinetic properties, dose requirements and immune response in drug delivery and bioimaging. Common synthesis techniques such as self-assembly, while prevalent, are unscalable and require the use of organic solvents, or extensive purification. In contrast, recent developments in dispersed state reversible deactivation radical polymerization allow the preparation of well-defined nanomaterials in fully aqueous environments often achieving full monomer conversion, and thus direct use in biological environments without purification in high quantities. These techniques have allowed the preparation of a variety of nanoparticle architectures (nanogel, latex, micelle, nanoworms, vesicles), using ATRP, RAFT and NMP, which in many cases perform significantly better than free radical alternatives. This review focuses on the biological relevance of RDRP in dispersed systems, covering miniemulsion, dispersion, suspension and emulsion polymerizations. (C) 2020 Elsevier B.V. All rights reserved.},
	urldate = {2020-04-28},
	journal = {PROGRESS IN POLYMER SCIENCE},
	author = {Gurnani, Pratik and Perrier, Sebastien},
	month = mar,
	year = {2020},
}

Polymeric nanoparticles show great promise in a range of biomedical applications, improving pharmacokinetic properties, dose requirements and immune response in drug delivery and bioimaging. Common synthesis techniques such as self-assembly, while prevalent, are unscalable and require the use of organic solvents, or extensive purification. In contrast, recent developments in dispersed state reversible deactivation radical polymerization allow the preparation of well-defined nanomaterials in fully aqueous environments often achieving full monomer conversion, and thus direct use in biological environments without purification in high quantities. These techniques have allowed the preparation of a variety of nanoparticle architectures (nanogel, latex, micelle, nanoworms, vesicles), using ATRP, RAFT and NMP, which in many cases perform significantly better than free radical alternatives. This review focuses on the biological relevance of RDRP in dispersed systems, covering miniemulsion, dispersion, suspension and emulsion polymerizations. (C) 2020 Elsevier B.V. All rights reserved.

@article{kaya_aging_2020,
	title = {Aging effects on the composition and thermal properties of styrene-butadiene-styrene ({SBS}) modified bitumen},
	volume = {235},
	issn = {0950-0618},
	doi = {10.1016/j.conbuildmat.2019.117450},
	abstract = {The effect of shear rate and mixing time on the composition and thermal properties of unaged and aged bitumen and, SBS modified bitumen was studied using a combination of Fourier Transform Infrared (FTIR) spectroscopy, Modulated Differential Scanning Calorimetry (MDSC) and Thermo-gravimetric Analysis (TGA). The increase in intensity of IR absorbance bands for carbonyl, sulfoxide and aromatic functional groups can be correlated with the oxidation of bitumen as, a consequence of processing, as well as for simulated long-term aging. Modification of bitumen with 5 wt\% SBS enhanced the thermal stability of bitumen, altered the mechanism of degradation from a single process to one with three steps and resulted in increases (to 85 degrees C) in the onset temperature of degradation of aged samples. Irrespective of whether the samples were aged or not, the specific heat capacity (C-p) of the blends, determined from MDSC measurements, increased with increasing shear rate and mixing time, but all C-p values were greater for aged samples. The application of heat and pressure in simulated long-term aging alters the structure of SBS modified bitumen blends via degradation and crosslinking reactions manifest by changes in the glass transition temperature (T-g) of the bitumen components, as measured by MDSC. (C) 2019 Elsevier Ltd. All rights reserved.},
	urldate = {2020-03-27},
	journal = {CONSTRUCTION AND BUILDING MATERIALS},
	author = {Kaya, Derya and Topal, Ali and Gupta, Jaipal and McNally, Tony},
	month = feb,
	year = {2020},
}

The effect of shear rate and mixing time on the composition and thermal properties of unaged and aged bitumen and, SBS modified bitumen was studied using a combination of Fourier Transform Infrared (FTIR) spectroscopy, Modulated Differential Scanning Calorimetry (MDSC) and Thermo-gravimetric Analysis (TGA). The increase in intensity of IR absorbance bands for carbonyl, sulfoxide and aromatic functional groups can be correlated with the oxidation of bitumen as, a consequence of processing, as well as for simulated long-term aging. Modification of bitumen with 5 wt% SBS enhanced the thermal stability of bitumen, altered the mechanism of degradation from a single process to one with three steps and resulted in increases (to 85 degrees C) in the onset temperature of degradation of aged samples. Irrespective of whether the samples were aged or not, the specific heat capacity (C-p) of the blends, determined from MDSC measurements, increased with increasing shear rate and mixing time, but all C-p values were greater for aged samples. The application of heat and pressure in simulated long-term aging alters the structure of SBS modified bitumen blends via degradation and crosslinking reactions manifest by changes in the glass transition temperature (T-g) of the bitumen components, as measured by MDSC. (C) 2019 Elsevier Ltd. All rights reserved.

@article{beyer_synthetic_2020,
	title = {Synthetic approaches for multiblock copolymers},
	volume = {11},
	issn = {1759-9954},
	doi = {10.1039/c9py01571j},
	abstract = {Multiblock copolymers (MBCs) are an emerging class of synthetic polymers that exhibit different macromolecular architectures and behaviours to those of homopolymers or di/triblock copolymers. Owing to the rapidly expanding field of synthetic methodologies applied in the field of polymer chemistry, sequenced controlled MBCs are becoming the new functional materials of this decade. MBCs can now be synthesised with precision and control unlike before and yet some of the synthetic limitations remain a challenge. In this review article, we summarise the various synthetic methodologies that have been reported to date with recent advances in different polymerisation techniques and applications.},
	number = {7},
	urldate = {2020-03-16},
	journal = {POLYMER CHEMISTRY},
	author = {Beyer, Valentin P. and Kim, Jungyeon and Becer, C. Remzi},
	month = feb,
	year = {2020},
	pages = {1271--1291},
}

Multiblock copolymers (MBCs) are an emerging class of synthetic polymers that exhibit different macromolecular architectures and behaviours to those of homopolymers or di/triblock copolymers. Owing to the rapidly expanding field of synthetic methodologies applied in the field of polymer chemistry, sequenced controlled MBCs are becoming the new functional materials of this decade. MBCs can now be synthesised with precision and control unlike before and yet some of the synthetic limitations remain a challenge. In this review article, we summarise the various synthetic methodologies that have been reported to date with recent advances in different polymerisation techniques and applications.

@article{shegiwal_polymerisable_2020,
	title = {Polymerisable surfactants for polymethacrylates using catalytic chain transfer polymerisation ({CCTP}) combined with sulfur free-{RAFT} in emulsion polymerisation},
	volume = {125},
	issn = {0014-3057},
	doi = {10.1016/j.eurpolymj.2020.109491},
	abstract = {Statistical copolymers of methacrylic acid and methyl methacrylate were synthesised via free radical catalytic chain transfer polymerisation (CCTP) in emulsion to form a hydrophilic emulsifier/surfactant. The vinyl-terminated oligomers were in turn utilised as chain transfer agents, with no further purification, for the formation of diblock copolymers with butyl and methyl methacrylate which constitutes the emulsifier via sulfur-free reversible addition-fragmentation chain transfer polymerisation (SF-RAFT). In turn these polymers were solubilized with various concentrations of ammonium hydroxide and utilised in the surfactant-free emulsion polymerization of butyl methacrylate using persulfate initiators, which also stabilized the polymer particles with observed no coagulation, with solid contents as high as 40\%.},
	urldate = {2020-03-24},
	journal = {EUROPEAN POLYMER JOURNAL},
	author = {Shegiwal, Ataulla and Wemyss, Alan M. and Liarou, Evelina and Town, James and Patias, Geogios and Atkins, Christophe J. and Marathianos, Arkadios and Lester, Daniel W. and Efstathiou, Spyridon and Haddleton, David M.},
	month = feb,
	year = {2020},
}

Statistical copolymers of methacrylic acid and methyl methacrylate were synthesised via free radical catalytic chain transfer polymerisation (CCTP) in emulsion to form a hydrophilic emulsifier/surfactant. The vinyl-terminated oligomers were in turn utilised as chain transfer agents, with no further purification, for the formation of diblock copolymers with butyl and methyl methacrylate which constitutes the emulsifier via sulfur-free reversible addition-fragmentation chain transfer polymerisation (SF-RAFT). In turn these polymers were solubilized with various concentrations of ammonium hydroxide and utilised in the surfactant-free emulsion polymerization of butyl methacrylate using persulfate initiators, which also stabilized the polymer particles with observed no coagulation, with solid contents as high as 40%.

@article{gurnani_pcr-raft_2020,
	title = {{PCR}-{RAFT}: rapid high throughput oxygen tolerant {RAFT} polymer synthesis in a biology laboratory},
	volume = {11},
	issn = {1759-9954},
	doi = {10.1039/c9py01521c},
	abstract = {Some of the main applications for synthetic polymers are found within the medical field (drug delivery, diagnostics, medical imaging). However, preparation of these macromolecules has been limited to those with access to chemistry facilities, potentially delaying biological evaluation. In this work, we aim to address this issue by utilising equipment typically found within a biological lab to establish a protocol for the preparation of well-defined macromolecules via RAFT polymerisation. By exploiting thermocycler technology, libraries of homopolymers, block- and statistical-copolymers were prepared in under 5 minutes per heating cycle using acrylamide monomers with ultrafast RAFT polymerisation. All the polymers prepared had excellent molar mass control and could be generated in under 15 min.},
	number = {6},
	urldate = {2020-03-03},
	journal = {POLYMER CHEMISTRY},
	author = {Gurnani, Pratik and Floyd, Thomas and Tanaka, Joji and Stubbs, Christopher and Lester, Daniel and Sanchez-Cano, Carlos and Perrier, Sebastien},
	month = feb,
	year = {2020},
	pages = {1230--1236},
}

Some of the main applications for synthetic polymers are found within the medical field (drug delivery, diagnostics, medical imaging). However, preparation of these macromolecules has been limited to those with access to chemistry facilities, potentially delaying biological evaluation. In this work, we aim to address this issue by utilising equipment typically found within a biological lab to establish a protocol for the preparation of well-defined macromolecules via RAFT polymerisation. By exploiting thermocycler technology, libraries of homopolymers, block- and statistical-copolymers were prepared in under 5 minutes per heating cycle using acrylamide monomers with ultrafast RAFT polymerisation. All the polymers prepared had excellent molar mass control and could be generated in under 15 min.

@article{hartlieb_guide_2020,
	title = {A guide to supramolecular polymerizations},
	volume = {11},
	issn = {1759-9954},
	doi = {10.1039/c9py01342c},
	abstract = {Supramolecular polymers or fibers are non-covalent assemblies of unimeric building blocks connected by secondary interactions such as hydrogen bonds or pi-pi interactions. Such structures hold enormous potential in the development of future materials, as their non-covalent nature makes them highly modular and adaptive. Within this review we aim to provide a broad overview over the area of linear supramolecular polymers including the different mechanisms of their polymerization as well as methods essential for their characterization. The different non-covalent interactions able to form supramolecular polymers are discussed, and key examples for each species are shown. Particular emphasis is laid on the development of living supramolecular polymerization able to produce fibers with a controlled length and low length dispersity, and even enable the production of supramolecular block copolymers. Another important and very recent field is the development of out-of-equilibrium supramolecular polymers, where the polymerization process can be temporally controlled enabling access to highly adaptive materials.},
	number = {6},
	urldate = {2020-03-03},
	journal = {POLYMER CHEMISTRY},
	author = {Hartlieb, Matthias and Mansfield, Edward D. H. and Perrier, Sebastien},
	month = feb,
	year = {2020},
	pages = {1083--1110},
}

Supramolecular polymers or fibers are non-covalent assemblies of unimeric building blocks connected by secondary interactions such as hydrogen bonds or pi-pi interactions. Such structures hold enormous potential in the development of future materials, as their non-covalent nature makes them highly modular and adaptive. Within this review we aim to provide a broad overview over the area of linear supramolecular polymers including the different mechanisms of their polymerization as well as methods essential for their characterization. The different non-covalent interactions able to form supramolecular polymers are discussed, and key examples for each species are shown. Particular emphasis is laid on the development of living supramolecular polymerization able to produce fibers with a controlled length and low length dispersity, and even enable the production of supramolecular block copolymers. Another important and very recent field is the development of out-of-equilibrium supramolecular polymers, where the polymerization process can be temporally controlled enabling access to highly adaptive materials.

@article{ellingford_self-healing_2020,
	title = {Self-{Healing} {Dielectric} {Elastomers} for {Damage}-{Tolerant} {Actuation} and {Energy} {Harvesting}},
	volume = {12},
	issn = {1944-8244},
	doi = {10.1021/acsami.9b21957},
	abstract = {The actuation and energy-harvesting performance of dielectric elastomers are strongly related to their intrinsic electrical and mechanical properties. For future resilient smart transducers, a fast actuation response, efficient energy-harvesting performance, and mechanical robustness are key requirements. In this work, we demonstrate that poly(styrene-butadiene-styrene) (SBS) can be converted into a self-healing dielectric elastomer with high permittivity and low dielectric loss, which can be deformed to large mechanical strains; these are key requirements for actuation and energy-harvesting applications. Using a one-step click reaction at room temperature for 20 min, methyl-3-mercaptopropionate (M3M) was grafted to SBS and reached 95.2\% of grafting ratios. The resultant M3M-SBS can be deformed to a high mechanical strain of 1000\%, with a relative permittivity of epsilon(r) = 7.5 and a low tan delta = 0.03. When used in a dielectric actuator, it can provide 9.2\% strain at an electric field of 39.5 MV m(-1) and can also generate an energy density of 11 mJ g(-1) from energy harvesting. After being subjected to mechanical damage, the self-healed elastomer can recover 44\% of its breakdown strength during energy harvesting. This work demonstrates a facile route to produce self-healing, high permittivity, and low dielectric loss elastomers for both actuation and energy harvesting, which is applicable to a wide range of diene elastomer systems.},
	number = {6},
	urldate = {2020-03-04},
	journal = {ACS APPLIED MATERIALS \& INTERFACES},
	author = {Ellingford, Christopher and Zhang, Runan and Wemyss, Alan M. and Zhang, Yan and Brown, Oliver B. and Zhou, Hongzhao and Keogh, Patrick and Bowen, Christopher and Wan, Chaoying},
	month = feb,
	year = {2020},
	pages = {7595--7604},
}

The actuation and energy-harvesting performance of dielectric elastomers are strongly related to their intrinsic electrical and mechanical properties. For future resilient smart transducers, a fast actuation response, efficient energy-harvesting performance, and mechanical robustness are key requirements. In this work, we demonstrate that poly(styrene-butadiene-styrene) (SBS) can be converted into a self-healing dielectric elastomer with high permittivity and low dielectric loss, which can be deformed to large mechanical strains; these are key requirements for actuation and energy-harvesting applications. Using a one-step click reaction at room temperature for 20 min, methyl-3-mercaptopropionate (M3M) was grafted to SBS and reached 95.2% of grafting ratios. The resultant M3M-SBS can be deformed to a high mechanical strain of 1000%, with a relative permittivity of epsilon(r) = 7.5 and a low tan delta = 0.03. When used in a dielectric actuator, it can provide 9.2% strain at an electric field of 39.5 MV m(-1) and can also generate an energy density of 11 mJ g(-1) from energy harvesting. After being subjected to mechanical damage, the self-healed elastomer can recover 44% of its breakdown strength during energy harvesting. This work demonstrates a facile route to produce self-healing, high permittivity, and low dielectric loss elastomers for both actuation and energy harvesting, which is applicable to a wide range of diene elastomer systems.

@article{town_automatic_2020,
	title = {Automatic peak assignment and visualisation of copolymer mass spectrometry data using the 'genetic algorithm'},
	volume = {34},
	issn = {0951-4198},
	doi = {10.1002/rcm.8654},
	abstract = {Copolymer analysis is vitally important as the materials have a wide variety of applications due to their tunable properties. Processing mass spectrometry data for copolymer samples can be very complex due to the increase in the number of species when the polymer chains are formed by two or more monomeric units. In this paper, we describe the use of the genetic algorithm for automated peak assignment of copolymers synthesised by a variety of polymerisation methods. We find that in using this method we are able to easily assign copolymer spectra in a few minutes and visualise them into heat maps. These heat maps allow us to look qualitatively at the distribution of the chains, by showing how they alter with different polymerisation techniques, and by changing the initial copolymer composition. This methodology is simple to use and requires little user input, which makes it well suited for use by less expert users. The data outputted by the automatic assignment may also allow for more complex data processing in the future.},
	urldate = {2020-02-25},
	journal = {RAPID COMMUNICATIONS IN MASS SPECTROMETRY},
	author = {Town, James S. and Gao, Yuqui and Hancox, Ellis and Liarou, Evelina and Shegiwal, Ataulla and Atkins, Christophe J. and Haddleton, David},
	month = aug,
	year = {2020},
}

Copolymer analysis is vitally important as the materials have a wide variety of applications due to their tunable properties. Processing mass spectrometry data for copolymer samples can be very complex due to the increase in the number of species when the polymer chains are formed by two or more monomeric units. In this paper, we describe the use of the genetic algorithm for automated peak assignment of copolymers synthesised by a variety of polymerisation methods. We find that in using this method we are able to easily assign copolymer spectra in a few minutes and visualise them into heat maps. These heat maps allow us to look qualitatively at the distribution of the chains, by showing how they alter with different polymerisation techniques, and by changing the initial copolymer composition. This methodology is simple to use and requires little user input, which makes it well suited for use by less expert users. The data outputted by the automatic assignment may also allow for more complex data processing in the future.

@article{aksakal_nitroxide-mediated_2020,
	title = {Nitroxide-mediated polymerisation of thioacrylates and their transformation into poly(acrylamide)s},
	volume = {11},
	issn = {1759-9954},
	doi = {10.1039/c9py01129c},
	abstract = {One long-standing challenge in polymer science is the development of transformation reactions, in which the conversion of a specific functional group to another is targeted. For this purpose, a thioester polymer consisting of thioacrylate monomers has been prepared via nitroxide-mediated polymerization and its kinetics has been studied for the first time. The copolymerization behavior of butyl thioacrylate with PFS was investigated in detail and compared to the copolymerization of butyl acrylate and PFS. Finally, a series of modification reactions were carried out using different amines and alcohols, in an attempt to transform the thioacrylate monomer into an acrylamide or acrylate, respectively. The established conditions allowed one to obtain poly(acrylamide)s via post polymerization functionalization in a versatile and efficient way, which is why this process is believed to be widely used by polymer chemists.},
	number = {5},
	urldate = {2020-03-16},
	journal = {POLYMER CHEMISTRY},
	author = {Aksakal, Suzan and Liu, Renjie and Aksakal, Resat and Becer, C. Remzi},
	month = feb,
	year = {2020},
	pages = {982--989},
}

One long-standing challenge in polymer science is the development of transformation reactions, in which the conversion of a specific functional group to another is targeted. For this purpose, a thioester polymer consisting of thioacrylate monomers has been prepared via nitroxide-mediated polymerization and its kinetics has been studied for the first time. The copolymerization behavior of butyl thioacrylate with PFS was investigated in detail and compared to the copolymerization of butyl acrylate and PFS. Finally, a series of modification reactions were carried out using different amines and alcohols, in an attempt to transform the thioacrylate monomer into an acrylamide or acrylate, respectively. The established conditions allowed one to obtain poly(acrylamide)s via post polymerization functionalization in a versatile and efficient way, which is why this process is believed to be widely used by polymer chemists.

@article{merritt_gas_2020,
	title = {Gas {Barrier} {Polymer} {Nanocomposite} {Films} {Prepared} by {Graphene} {Oxide} {Encapsulated} {Polystyrene} {Microparticles}},
	volume = {2},
	issn = {2637-6105},
	doi = {10.1021/acsapm.9b01041},
	abstract = {The dispersion and orientation of two-dimensional (2D) inorganic nanoplatelets in polymers are technical challenges faced in polymer nanocomposite manufacturing. This work demonstrates an effective way to facilitate the dispersion and orientation of graphene oxide (GO) nanoplatelets in a polymer matrix through encapsulating the polymer within a nanoplatelet shell. Briefly, few-layered GO nanoplatelets encapsulated polystyrene (PS) microparticles were synthesized by a Pickering suspension polymerization method. The synthesis conditions, morphologies, and barrier properties of the GO encapsulated PS spheres and the melt-compressed films are characterized. The addition of salt induces flocculation of GO onto the surface of the styrene monomer droplet, resulting in the formation of a multilayered GO shell as well as the sedimenting of the PS/GO particles during polymerization. The obtained GO encapsulated PS microspheres were purified, dried, and melt-compressed to form composite films. The oxygen permeability (expressed as transmission rate) of the PS/GO composite film containing 2 wt \% GO was 526.02 +/- 55.78 cm(3) m(-2) 24 h(-1)-a reduction of 96\% relative to the PS control film and 34\% lower than the solution mixed PS/GO composite film. This indicates that the encapsulated PS spheres act as an effective carrier to facilitate the dispersion of GO. The orientation was realized by the following meltcompression process, which creates tortuous pathways hindering the permeation of gases through the PS matrix.},
	number = {2},
	urldate = {2020-03-12},
	journal = {ACS APPLIED POLYMER MATERIALS},
	author = {Merritt, Steven M. J. and Wemyss, Alan M. and Farris, Stefano and Patole, Samson and Patias, Georgios and Haddleton, David M. and Shollock, Barbara and Wan, Chaoying},
	month = feb,
	year = {2020},
	note = {TATA Steel Res \& Dev},
	pages = {725--731},
}

The dispersion and orientation of two-dimensional (2D) inorganic nanoplatelets in polymers are technical challenges faced in polymer nanocomposite manufacturing. This work demonstrates an effective way to facilitate the dispersion and orientation of graphene oxide (GO) nanoplatelets in a polymer matrix through encapsulating the polymer within a nanoplatelet shell. Briefly, few-layered GO nanoplatelets encapsulated polystyrene (PS) microparticles were synthesized by a Pickering suspension polymerization method. The synthesis conditions, morphologies, and barrier properties of the GO encapsulated PS spheres and the melt-compressed films are characterized. The addition of salt induces flocculation of GO onto the surface of the styrene monomer droplet, resulting in the formation of a multilayered GO shell as well as the sedimenting of the PS/GO particles during polymerization. The obtained GO encapsulated PS microspheres were purified, dried, and melt-compressed to form composite films. The oxygen permeability (expressed as transmission rate) of the PS/GO composite film containing 2 wt % GO was 526.02 +/- 55.78 cm(3) m(-2) 24 h(-1)-a reduction of 96% relative to the PS control film and 34% lower than the solution mixed PS/GO composite film. This indicates that the encapsulated PS spheres act as an effective carrier to facilitate the dispersion of GO. The orientation was realized by the following meltcompression process, which creates tortuous pathways hindering the permeation of gases through the PS matrix.

@article{rogalski_study_2020,
	title = {A study of rheological limitations in rotary jet spinning of polymer nanofibers through modeling and experimentation},
	volume = {137},
	issn = {0021-8995},
	doi = {10.1002/app.48963},
	abstract = {The recently popularized method of rotary jet spinning (RJS) or centrifugal spinning is investigated to evaluate the rheological limitations of polymer solutions and melts to optimal spinnability. The influence of Newtonian or non-Newtonian behavior of the polymer on spinnability is discussed. We observe that highly viscous polymers tend to block the die channels within a rotary jet spinneret and therefore suggest the use of relatively low Newtonian viscosities of between 1 and 10 Pa s for optimal fiber production. Computational fluid dynamics simulations are used in conjunction with experimental data to establish important processing parameters, such as typical shear rates in the device and optimal polymer melt or solution viscosities. A theoretical model for RJS is compared to measured fiber diameters. The comparison shows that although fiber diameters can be estimated very roughly in the case of polymer solutions, the prediction of fiber diameter in the case of polymer melts require further modeling work. (c) 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48963.},
	number = {33},
	urldate = {2020-01-28},
	journal = {JOURNAL OF APPLIED POLYMER SCIENCE},
	author = {Rogalski, James J. and Botto, Lorenzo and Bastiaansen, Cees W. M. and Peijs, Ton},
	month = sep,
	year = {2020},
}

The recently popularized method of rotary jet spinning (RJS) or centrifugal spinning is investigated to evaluate the rheological limitations of polymer solutions and melts to optimal spinnability. The influence of Newtonian or non-Newtonian behavior of the polymer on spinnability is discussed. We observe that highly viscous polymers tend to block the die channels within a rotary jet spinneret and therefore suggest the use of relatively low Newtonian viscosities of between 1 and 10 Pa s for optimal fiber production. Computational fluid dynamics simulations are used in conjunction with experimental data to establish important processing parameters, such as typical shear rates in the device and optimal polymer melt or solution viscosities. A theoretical model for RJS is compared to measured fiber diameters. The comparison shows that although fiber diameters can be estimated very roughly in the case of polymer solutions, the prediction of fiber diameter in the case of polymer melts require further modeling work. (c) 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48963.

@article{liarou_uv_2020,
	title = {{UV} irradiation of {Cu}-based complexes with aliphatic amine ligands as used in living radical polymerization},
	volume = {123},
	issn = {0014-3057},
	doi = {10.1016/j.eurpolymj.2019.109388},
	abstract = {The effect UV irradiation on Cu(II)-based complexes with aliphatic amine ligands is investigated. Four aliphatic amines are used as ligands and Cu(II)Br-2 as the metal source for the formation of catalyst complexes that can be used for the photoinduced Cu-RDRP of methyl acrylate. Different characterization techniques such as transient electronic absorption spectroscopy (TEAS), ultraviolet-visible (UV-Vis) spectroscopy, electrospray ionization time of flight mass spectrometry (ESI-ToF-MS) and cyclic voltammetry (CV) are applied in order to provide insights into the catalyst behaviour upon photo-irradiation. The excited-state dynamics, the electrochemical behaviour of the Cu(II)/Cu(I) redox couples and the detection of different species upon complexation of the ligand to the metal center (before and after UV irradiation) are further depicted in the quality of the obtained polymers.},
	urldate = {2020-02-18},
	journal = {EUROPEAN POLYMER JOURNAL},
	author = {Liarou, Evelina and Staniforth, Michael and Town, James S. and Marathianos, Arkadios and Grypioti, Maria and Li, Yongguang and Chang, Yujing and Efstathiou, Spyridon and Hancox, Ellis and Wemyss, Alan M. and Wilson, Paul and Jones, Bryn A. and Aljuaid, Mohammed and Stavros, Vasilios G. and Haddleton, David M.},
	month = jan,
	year = {2020},
}

The effect UV irradiation on Cu(II)-based complexes with aliphatic amine ligands is investigated. Four aliphatic amines are used as ligands and Cu(II)Br-2 as the metal source for the formation of catalyst complexes that can be used for the photoinduced Cu-RDRP of methyl acrylate. Different characterization techniques such as transient electronic absorption spectroscopy (TEAS), ultraviolet-visible (UV-Vis) spectroscopy, electrospray ionization time of flight mass spectrometry (ESI-ToF-MS) and cyclic voltammetry (CV) are applied in order to provide insights into the catalyst behaviour upon photo-irradiation. The excited-state dynamics, the electrochemical behaviour of the Cu(II)/Cu(I) redox couples and the detection of different species upon complexation of the ligand to the metal center (before and after UV irradiation) are further depicted in the quality of the obtained polymers.

@article{georgiou_tuning_2020,
	title = {"{Tuning} aggregative versus non-aggregative lectin binding with glycosylated nanoparticles by the nature of the polymer ligand"},
	volume = {8},
	issn = {2050-750X},
	doi = {10.1039/c9tb02004g},
	abstract = {Glycan-lectin interactions drive a diverse range of biological signaling and recognition processes. The display of glycans in multivalent format enables their intrinsically weak binding affinity to lectins to be overcome by the cluster glycoside effect, which results in a non-linear increase in binding affinity. As many lectins have multiple binding sites, upon interaction with glycosylated nanomaterials either aggregation or surface binding without aggregation can occur. Depending on the application area, either one of these responses are desirable (or undesirable) but methods to tune the aggregation state, independently from the overall extent/affinity of binding are currently missing. Herein, we use gold nanoparticles decorated with galactose-terminated polymer ligands, obtained by photo-initiated RAFT polymerization to ensure high end-group fidelity, to show the dramatic impact on agglutination behaviour due to the chemistry of the polymer linker. Poly(N-hydroxyethyl acrylamide) (PHEA)-coated gold nanoparticles, a polymer widely used as a non-ionic stabilizer, showed preference for aggregation with lectins compared to poly(N-(2-hydroxypropyl)methacrylamide) (PHPMA)-coated nanoparticles which retained colloidal stability, across a wide range of polymer lengths and particle core sizes. Using biolayer interferometry, it was observed that both coatings gave rise to similar binding affinity and hence provided conclusive evidence that aggregation rate alone cannot be used to measure affinity between nanoparticle systems with different stabilizing linkers. This is significant, as turbidimetry is widely used to demonstrate glycomaterial activity, although this work shows the most aggregating may not be the most avid, when comparing different polymer backbones/coating. Overall, our findings underline the potential of PHPMA as the coating of choice for applications where aggregation upon lectin binding would be problematic, such as in vivo imaging or drug delivery.},
	number = {1},
	urldate = {2020-01-06},
	journal = {JOURNAL OF MATERIALS CHEMISTRY B},
	author = {Georgiou, Panagiotis G. and Baker, Alexander N. and Richards, Sarah-Jane and Laezza, Antonio and Walker, Marc and Gibson, I, Matthew},
	month = jan,
	year = {2020},
	pages = {136--145},
}

Glycan-lectin interactions drive a diverse range of biological signaling and recognition processes. The display of glycans in multivalent format enables their intrinsically weak binding affinity to lectins to be overcome by the cluster glycoside effect, which results in a non-linear increase in binding affinity. As many lectins have multiple binding sites, upon interaction with glycosylated nanomaterials either aggregation or surface binding without aggregation can occur. Depending on the application area, either one of these responses are desirable (or undesirable) but methods to tune the aggregation state, independently from the overall extent/affinity of binding are currently missing. Herein, we use gold nanoparticles decorated with galactose-terminated polymer ligands, obtained by photo-initiated RAFT polymerization to ensure high end-group fidelity, to show the dramatic impact on agglutination behaviour due to the chemistry of the polymer linker. Poly(N-hydroxyethyl acrylamide) (PHEA)-coated gold nanoparticles, a polymer widely used as a non-ionic stabilizer, showed preference for aggregation with lectins compared to poly(N-(2-hydroxypropyl)methacrylamide) (PHPMA)-coated nanoparticles which retained colloidal stability, across a wide range of polymer lengths and particle core sizes. Using biolayer interferometry, it was observed that both coatings gave rise to similar binding affinity and hence provided conclusive evidence that aggregation rate alone cannot be used to measure affinity between nanoparticle systems with different stabilizing linkers. This is significant, as turbidimetry is widely used to demonstrate glycomaterial activity, although this work shows the most aggregating may not be the most avid, when comparing different polymer backbones/coating. Overall, our findings underline the potential of PHPMA as the coating of choice for applications where aggregation upon lectin binding would be problematic, such as in vivo imaging or drug delivery.

@article{cook_branched_2020,
	title = {Branched and {Dendritic} {Polymer} {Architectures}: {Functional} {Nanomaterials} for {Therapeutic} {Delivery}},
	volume = {30},
	issn = {1616-301X},
	doi = {10.1002/adfm.201901001},
	abstract = {Barriers to therapeutic transport in biological systems can prevent accumulation of drugs at the intended site, thus limiting the therapeutic effect against various diseases. Advances in synthetic chemistry techniques have recently increased the accessibility of complex polymer architectures for drug delivery systems, including branched polymer architectures. This article first outlines drug delivery concepts, and then defines and illustrates all forms of branched polymers including highly branched polymers, hyperbranched polymers, dendrimers, and branched-linear hybrid polymers. Many new types of branched and dendritic polymers continue to be reported; however, there is often confusion about how to accurately describe these complex polymer architectures, particularly in the interdisciplinary field of nanomedicine where not all researchers have in-depth polymer chemistry backgrounds. In this context, the present review describes and compares different branched polymer architectures and their application in therapeutic delivery in a simple and easy-to-understand way, with the aim of appealing to a multidisciplinary audience.},
	number = {2},
	urldate = {2020-01-01},
	journal = {ADVANCED FUNCTIONAL MATERIALS},
	author = {Cook, Alexander B. and Perrier, Sebastien},
	month = jan,
	year = {2020},
}

Barriers to therapeutic transport in biological systems can prevent accumulation of drugs at the intended site, thus limiting the therapeutic effect against various diseases. Advances in synthetic chemistry techniques have recently increased the accessibility of complex polymer architectures for drug delivery systems, including branched polymer architectures. This article first outlines drug delivery concepts, and then defines and illustrates all forms of branched polymers including highly branched polymers, hyperbranched polymers, dendrimers, and branched-linear hybrid polymers. Many new types of branched and dendritic polymers continue to be reported; however, there is often confusion about how to accurately describe these complex polymer architectures, particularly in the interdisciplinary field of nanomedicine where not all researchers have in-depth polymer chemistry backgrounds. In this context, the present review describes and compares different branched polymer architectures and their application in therapeutic delivery in a simple and easy-to-understand way, with the aim of appealing to a multidisciplinary audience.

@article{zhao_fluorescent_2020,
	title = {Fluorescent {Supramolecular} {Polymersomes} {Based} on {Pillararene}/{Paraquat} {Molecular} {Recognition} for {pH}-controlled {Drug} {Release}},
	volume = {38},
	issn = {0256-7679},
	doi = {10.1007/s10118-019-2305-1},
	abstract = {Researchers have put significant efforts on developing versatile fluorescent polymeric systems due to their promising biological/biomedical labelling, tracking, monitoring, imaging, and diagnostic applications. However, complicated organic/polymeric synthesis or post-modification of these functionalized platforms is still a big obstacle for their further application and thereby provides clear motivation for exploring alternative strategies for the design and fabrication of easily available fluorescent systems. The marriage of supramolecular polymers and fluorescent imaging can provide a facile and dynamic manner instead of tedious and time-consuming synthesis due to the dynamic and reversible nature of noncovalent interactions. Herein, based on water-soluble pillararene/paraquat molecular recognition, we successfully prepare two amphiphilic polypseudorotaxanes which can self-assemble into supramolecular polymersomes in water. These polymersomes can be reversibly destroyed and reformed by tuning the solution pH. Attributed to the aggregation-induced emission of tetraphenylethylene groups, intense fluorescence can be introduced into the obtained supramolecular polymersomes. Furthermore, pH-triggered release of an encapsulated water-insoluble drug (doxorubicin) from the self-assembled fluorescent supramolecular polymersomes is also investigated.},
	number = {1},
	urldate = {2020-01-03},
	journal = {CHINESE JOURNAL OF POLYMER SCIENCE},
	author = {Zhao, Run and Zhou, Yu-Juan and Jia, Ke-Cheng and Yang, Jie and Perrier, Sebastien and Huang, Fei-He},
	month = jan,
	year = {2020},
	pages = {1--8},
}

Researchers have put significant efforts on developing versatile fluorescent polymeric systems due to their promising biological/biomedical labelling, tracking, monitoring, imaging, and diagnostic applications. However, complicated organic/polymeric synthesis or post-modification of these functionalized platforms is still a big obstacle for their further application and thereby provides clear motivation for exploring alternative strategies for the design and fabrication of easily available fluorescent systems. The marriage of supramolecular polymers and fluorescent imaging can provide a facile and dynamic manner instead of tedious and time-consuming synthesis due to the dynamic and reversible nature of noncovalent interactions. Herein, based on water-soluble pillararene/paraquat molecular recognition, we successfully prepare two amphiphilic polypseudorotaxanes which can self-assemble into supramolecular polymersomes in water. These polymersomes can be reversibly destroyed and reformed by tuning the solution pH. Attributed to the aggregation-induced emission of tetraphenylethylene groups, intense fluorescence can be introduced into the obtained supramolecular polymersomes. Furthermore, pH-triggered release of an encapsulated water-insoluble drug (doxorubicin) from the self-assembled fluorescent supramolecular polymersomes is also investigated.