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\n \n\n \n \n \n \n \n \n On the Fate of Lithium Ions in Sol–Gel Derived Zinc Oxide Nanocrystals.\n \n \n \n \n\n\n \n Olejnik‐Fehér, N.; Jędrzejewska, M.; Wolska‐Pietkiewicz, M.; Lee, D.; Paëpe, G. D.; and Lewiński, J.\n\n\n \n\n\n\n Small,2309984. March 2024.\n \n\n\n\n
\n\n\n\n \n \n $\"On$ Paper\n \n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n \n \n \n \n \n \n \n \n \n \n\n\n\n

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@article{olejnikfeher_fate_2024,\n\ttitle = {On the {Fate} of {Lithium} {Ions} in {Sol}–{Gel} {Derived} {Zinc} {Oxide} {Nanocrystals}},\n\tissn = {1613-6810, 1613-6829},\n\turl = {https://onlinelibrary.wiley.com/doi/10.1002/smll.202309984},\n\tdoi = {10.1002/smll.202309984},\n\tabstract = {Abstract\n            \n              Among diverse chemical synthetic approaches to zinc oxide nanocrystals (ZnO NCs), ubiquitous inorganic sol–gel methodology proved crucial for advancements in ZnO‐based nanoscience. Strikingly, unlike the exquisite level of control over morphology and size dispersity achieved in ZnO NC syntheses, the purity of the crystalline phase, as well as the understanding of the surface structure and the character of the inorganic–organic interface, have been limited to vague descriptors until very recently. Herein, ZnO NCs applying the standard sol–gel synthetic protocol are synthesized with zinc acetate and lithium hydroxide and tracked the integration of lithium (Li) cations into the interior and exterior of nanoparticles by combining various techniques, including advanced solid‐state NMR methods. In contrast to common views, it is demonstrated that Li\n              +\n              ions remain kinetically trapped in the inorganic core, enter into a shallow subsurface layer, and generate “swelling” of the surface and interface regions. Thus, this work enabled both the determination of the NCs’ structural imperfections and an in‐depth understanding of the unappreciated role of the Li\n              +\n              ions in impacting the doping and the passivation of sol–gel‐derived ZnO nanomaterials.},\n\tlanguage = {en},\n\turldate = {2024-04-08},\n\tjournal = {Small},\n\tauthor = {Olejnik‐Fehér, Natalia and Jędrzejewska, Maria and Wolska‐Pietkiewicz, Małgorzata and Lee, Daniel and Paëpe, Gaël De and Lewiński, Janusz},\n\tmonth = mar,\n\tyear = {2024},\n\tkeywords = {lithium, nanocrystals, solid-state NMR, sol–gel, zinc oxide},\n\tpages = {2309984},\n}\n\n

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\n \n\n \n \n \n \n \n \n AsymPol-TEKs as efficient polarizing agents for MAS-DNP in glass matrices of non-aqueous solvents.\n \n \n \n \n\n\n \n Harrabi, R.; Halbritter, T.; Alarab, S.; Chatterjee, S.; Wolska-Pietkiewicz, M.; Damodaran, K. K.; Van Tol, J.; Lee, D.; Paul, S.; Hediger, S.; Sigurdsson, S. T.; Mentink-Vigier, F.; and De Paëpe, G.\n\n\n \n\n\n\n Physical Chemistry Chemical Physics, 26(6): 5669–5682. 2024.\n \n\n\n\n
\n\n\n\n \n \n $\"AsymPol-TEKs$ Paper\n \n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

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@article{harrabi_asympol-teks_2024,\n\ttitle = {{AsymPol}-{TEKs} as efficient polarizing agents for {MAS}-{DNP} in glass matrices of non-aqueous solvents},\n\tvolume = {26},\n\tissn = {1463-9076, 1463-9084},\n\turl = {http://xlink.rsc.org/?DOI=D3CP04271E},\n\tdoi = {10.1039/D3CP04271E},\n\tabstract = {Two polarizing agents from the AsymPol family, AsymPol-TEK and cAsymPol-TEK (methyl-free version) are introduced for MAS-DNP applications in non-aqueous solvents.\n          , \n            \n              Two polarizing agents from the AsymPol family, AsymPol-TEK and cAsymPol-TEK (methyl-free version) are introduced for MAS-DNP applications in non-aqueous solvents. The performance of these new biradicals is rationalized in detail using a combination of electron paramagnetic resonance spectroscopy, density functional theory, molecular dynamics and quantitative MAS-DNP spin dynamics simulations. By slightly modifying the experimental protocol to keep the sample temperature low at insertion, we are able to obtain reproducable DNP-NMR data with 1,1,2,2-tetrachloroethane (TCE) at 100 K, which facilitates optimization and comparison of different polarizing agents. At intermediate magnetic fields, AsymPol-TEK and cAsymPol-TEK provide 1.5 to 3-fold improvement in sensitivity compared to TEKPol, one of the most widely used polarizing agents for organic solvents, with significantly shorter DNP build-up times of ∼1 s and ∼2 s at 9.4 and 14.1 T respectively. In the course of the work, we also isolated and characterized two diastereoisomers that can form during the synthesis of AsymPol-TEK; their difference in performance is described and discussed. Finally, the advantages of the AsymPol-TEKs are demonstrated by recording 2D\n              13\n              C–\n              13\n              C correlation experiments at natural\n              13\n              C-abundance of proton-dense microcrystals and by polarizing the surface of ZnO nanocrystals (NCs) coated with diphenyl phosphate ligands. For those experiments, cAsymPol-TEK yielded a three-fold increase in sensitivity compared to TEKPol, corresponding to a nine-fold time saving.},\n\tlanguage = {en},\n\tnumber = {6},\n\turldate = {2024-04-08},\n\tjournal = {Physical Chemistry Chemical Physics},\n\tauthor = {Harrabi, Rania and Halbritter, Thomas and Alarab, Shadi and Chatterjee, Satyaki and Wolska-Pietkiewicz, Malgorzata and Damodaran, Krishna K. and Van Tol, Johan and Lee, Daniel and Paul, Subhradip and Hediger, Sabine and Sigurdsson, Snorri Th. and Mentink-Vigier, Frederic and De Paëpe, Gaël},\n\tyear = {2024},\n\tpages = {5669--5682},\n}\n\n

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\n \n\n \n \n \n \n \n \n Sustainable and cost-effective MAS DNP-NMR at 30 K with cryogenic sample exchange.\n \n \n \n \n\n\n \n Paul, S.; Bouleau, E.; Reynard-Feytis, Q.; Arnaud, J.; Bancel, F.; Rollet, B.; Dalban-Moreynas, P.; Reiter, C.; Purea, A.; Engelke, F.; Hediger, S.; and De Paëpe, G.\n\n\n \n\n\n\n Journal of Magnetic Resonance, 356: 107561. November 2023.\n \n\n\n\n
\n\n\n\n \n \n $\"Sustainable$ Paper\n \n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n\n \n \n \n 11 downloads\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n \n \n\n\n\n

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@article{paul_sustainable_2023,\n\ttitle = {Sustainable and cost-effective {MAS} {DNP}-{NMR} at 30 {K} with cryogenic sample exchange},\n\tvolume = {356},\n\tcopyright = {All rights reserved},\n\tissn = {10907807},\n\turl = {https://linkinghub.elsevier.com/retrieve/pii/S1090780723001969},\n\tdoi = {10.1016/j.jmr.2023.107561},\n\tlanguage = {en},\n\turldate = {2023-10-18},\n\tjournal = {Journal of Magnetic Resonance},\n\tauthor = {Paul, Subhradip and Bouleau, Eric and Reynard-Feytis, Quentin and Arnaud, Jean-Pierre and Bancel, Florian and Rollet, Bertrand and Dalban-Moreynas, Pierre and Reiter, Christian and Purea, Armin and Engelke, Frank and Hediger, Sabine and De Paëpe, Gaël},\n\tmonth = nov,\n\tyear = {2023},\n\tkeywords = {\\#nosource},\n\tpages = {107561},\n}\n\n

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\n \n\n \n \n \n \n \n \n PyrroTriPol: a semi-rigid trityl-nitroxide for high field dynamic nuclear polarization.\n \n \n \n \n\n\n \n Halbritter, T.; Harrabi, R.; Paul, S.; Van Tol, J.; Lee, D.; Hediger, S.; Sigurdsson, S. T.; Mentink-Vigier, F.; and De Paëpe, G.\n\n\n \n\n\n\n Chemical Science, 14(14): 3852–3864. 2023.\n \n\n\n\n
\n\n\n\n \n \n $\"PyrroTriPol:$ Paper\n \n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n \n \n \n \n \n \n \n \n\n\n\n

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@article{halbritter_pyrrotripol_2023,\n\ttitle = {{PyrroTriPol}: a semi-rigid trityl-nitroxide for high field dynamic nuclear polarization},\n\tvolume = {14},\n\tissn = {2041-6520, 2041-6539},\n\tshorttitle = {{PyrroTriPol}},\n\turl = {http://xlink.rsc.org/?DOI=D2SC05880D},\n\tdoi = {10.1039/D2SC05880D},\n\tabstract = {A semi-rigid trityl-nitroxide polarizing agent is introduced for magic angle spinning (MAS) dynamic nuclear polarization (DNP), which significantly broadened the scope of solid-state NMR to study biomolecular systems and materials.\n          , \n            \n              Magic angle spinning (MAS) dynamic nuclear polarization (DNP) has significantly broadened the scope of solid-state NMR to study biomolecular systems and materials. In recent years, the advent of very high field DNP combined with fast MAS has brought new challenges in the design of polarizing agents (PA) used to enhance nuclear spin polarization. Here, we present a trityl-nitroxide PA family based on a piperazine linker, named PyrroTriPol, for both aqueous and organic solutions. These new radicals have similar properties to that of TEMTriPol-I and can be readily synthesized, and purified in large quantities thereby ensuring widespread application. The family relies on a rigid bridge connecting the trityl and the nitroxide offering a better control of the electron spin–spin interactions thus providing improved performance across a broad range of magnetic fields and MAS frequencies while requiring reduced microwave power compared to bis-nitroxides. We demonstrate the efficiency of the PyrroTriPol family under a magnetic field of 9.4, 14.1 and 18.8 T with respect to TEMTriPol-I. In particular, the superiority of PyrroTriPol was demonstrated on γ-Al\n              2\n              O\n              3\n              nanoparticles which enabled the acquisition of a high signal-to-noise surface-selective\n              27\n              Al multiple-quantum MAS experiment at 18.8 T and 40 kHz MAS frequency.},\n\tlanguage = {en},\n\tnumber = {14},\n\turldate = {2023-06-14},\n\tjournal = {Chemical Science},\n\tauthor = {Halbritter, Thomas and Harrabi, Rania and Paul, Subhradip and Van Tol, Johan and Lee, Daniel and Hediger, Sabine and Sigurdsson, Snorri Th. and Mentink-Vigier, Frédéric and De Paëpe, Gaël},\n\tyear = {2023},\n\tkeywords = {DNP, NMR, PyrroTriPol, biradical},\n\tpages = {3852--3864},\n}\n\n

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\n \n\n \n \n \n \n \n \n Fast magic angle spinning for the characterization of milligram quantities of organic and biological solids at natural isotopic abundance by 13C–13C correlation DNP-enhanced NMR.\n \n \n \n \n\n\n \n Smith, A. N.; Harrabi, R.; Halbritter, T.; Lee, D.; Aussenac, F.; Van Der Wel, P. C.; Hediger, S.; Sigurdsson, S. T.; and De Paëpe, G.\n\n\n \n\n\n\n Solid State Nuclear Magnetic Resonance, 123: 101850. February 2023.\n \n\n\n\n
\n\n\n\n \n \n $\"Fast$ Paper\n \n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n\n \n \n \n 1 download\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n \n \n \n \n \n \n \n \n \n \n \n \n \n \n \n \n \n \n\n\n\n

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@article{smith_fast_2023,\n\ttitle = {Fast magic angle spinning for the characterization of milligram quantities of organic and biological solids at natural isotopic abundance by {13C}–{13C} correlation {DNP}-enhanced {NMR}},\n\tvolume = {123},\n\tissn = {09262040},\n\turl = {https://linkinghub.elsevier.com/retrieve/pii/S0926204022000790},\n\tdoi = {10.1016/j.ssnmr.2022.101850},\n\tlanguage = {en},\n\turldate = {2023-06-14},\n\tjournal = {Solid State Nuclear Magnetic Resonance},\n\tauthor = {Smith, Adam N. and Harrabi, Rania and Halbritter, Thomas and Lee, Daniel and Aussenac, Fabien and Van Der Wel, Patrick C.A. and Hediger, Sabine and Sigurdsson, Snorri Th. and De Paëpe, Gaël},\n\tmonth = feb,\n\tyear = {2023},\n\tkeywords = {Dynamic nuclear polarization, Fast MAS, MAS-DNP, Nuclear magnetic resonance, Pharmaceuticals, adam, fast magic angle spinning, rania, review},\n\tpages = {101850},\n}\n\n

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\n \n\n \n \n \n \n \n \n Optimizing chemistry at the surface of prodrug-loaded cellulose nanofibrils with MAS-DNP.\n \n \n \n \n\n\n \n Kumar, A.; Watbled, B.; Baussanne, I.; Hediger, S.; Demeunynck, M.; and De Paëpe, G.\n\n\n \n\n\n\n Communications Chemistry, 6(1): 58. March 2023.\n \n\n\n\n
\n\n\n\n \n \n $\"Optimizing$ Paper\n \n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 3 downloads\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n \n \n \n \n \n \n\n\n\n

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@article{kumar_optimizing_2023,\n\ttitle = {Optimizing chemistry at the surface of prodrug-loaded cellulose nanofibrils with {MAS}-{DNP}},\n\tvolume = {6},\n\tissn = {2399-3669},\n\turl = {https://www.nature.com/articles/s42004-023-00852-2},\n\tdoi = {10.1038/s42004-023-00852-2},\n\tabstract = {Abstract\n            \n              Studying the surface chemistry of functionalized cellulose nanofibrils at atomic scale is an ongoing challenge, mainly because FT-IR, NMR, XPS and RAMAN spectroscopy are limited in sensitivity or resolution. Herein, we show that dynamic nuclear polarization (DNP) enhanced\n              13\n              C and\n              15\n              N solid-state NMR is a uniquely suited technique to optimize the drug loading on nanocellulose using aqueous heterogenous chemistry. We compare the efficiency of two conventional coupling agents (DMTMM vs EDC/NHS) to bind a complex prodrug of ciprofloxacin designed for controlled drug release. Besides quantifying the drug grafting, we also evidence the challenge to control the concurrent prodrug adsorption and to optimize washing procedures. We notably highlight the presence of an unexpected prodrug cleavage mechanism triggered by carboxylates at the surface of the cellulose nanofibrils.},\n\tlanguage = {en},\n\tnumber = {1},\n\turldate = {2023-06-14},\n\tjournal = {Communications Chemistry},\n\tauthor = {Kumar, Akshay and Watbled, Bastien and Baussanne, Isabelle and Hediger, Sabine and Demeunynck, Martine and De Paëpe, Gaël},\n\tmonth = mar,\n\tyear = {2023},\n\tkeywords = {Drug delivery, Solid-state NMR, Surface spectroscopy},\n\tpages = {58},\n}\n\n

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\n \n\n \n \n \n \n \n \n Solvent-derived defects suppress adsorption in MOF-74.\n \n \n \n \n\n\n \n Fu, Y.; Yao, Y.; Forse, A. C.; Li, J.; Mochizuki, K.; Long, J. R.; Reimer, J. A.; De Paëpe, G.; and Kong, X.\n\n\n \n\n\n\n Nature Communications, 14(1): 2386. April 2023.\n Number: 1 Publisher: Nature Publishing Group\n\n\n\n
\n\n\n\n \n \n $\"Solvent-derived$ Paper\n \n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n \n \n \n \n \n \n \n \n \n \n\n\n\n

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@article{fu_solvent-derived_2023,\n\ttitle = {Solvent-derived defects suppress adsorption in {MOF}-74},\n\tvolume = {14},\n\tcopyright = {2023 The Author(s)},\n\tissn = {2041-1723},\n\turl = {https://www.nature.com/articles/s41467-023-38155-8},\n\tdoi = {10.1038/s41467-023-38155-8},\n\tabstract = {Defects in metal-organic frameworks (MOFs) have great impact on their nano-scale structure and physiochemical properties. However, isolated defects are easily concealed when the frameworks are interrogated by typical characterization methods. In this work, we unveil the presence of solvent-derived formate defects in MOF-74, an important class of MOFs with open metal sites. With multi-dimensional solid-state nuclear magnetic resonance (NMR) investigations, we uncover the ligand substitution role of formate and its chemical origin from decomposed N,N-dimethylformamide (DMF) solvent. The placement and coordination structure of formate defects are determined by 13C NMR and density functional theory (DFT) calculations. The extra metal-oxygen bonds with formates partially eliminate open metal sites and lead to a quantitative decrease of N2 and CO2 adsorption with respect to the defect concentration. In-situ NMR analysis and molecular simulations of CO2 dynamics elaborate the adsorption mechanisms in defective MOF-74. Our study establishes comprehensive strategies to search, elucidate and manipulate defects in MOFs.},\n\tlanguage = {en},\n\tnumber = {1},\n\turldate = {2023-06-07},\n\tjournal = {Nature Communications},\n\tauthor = {Fu, Yao and Yao, Yifeng and Forse, Alexander C. and Li, Jianhua and Mochizuki, Kenji and Long, Jeffrey R. and Reimer, Jeffrey A. and De Paëpe, Gaël and Kong, Xueqian},\n\tmonth = apr,\n\tyear = {2023},\n\tnote = {Number: 1\nPublisher: Nature Publishing Group},\n\tkeywords = {Lab Pubs, MOF, Organic–inorganic nanostructures, Solid-state NMR, Yao},\n\tpages = {2386},\n}\n\n

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\n \n\n \n \n \n \n \n \n Revealing Electrolytic Ion Sorption in Layered Graphene Galleries through Low-Temperature Solid-State NMR.\n \n \n \n \n\n\n \n Lee, D.; Banda, H.; Périé, S.; Marcucci, C.; Chenavier, Y.; Dubois, L.; Taberna, P.; Simon, P.; De Paëpe, G.; and Duclairoir, F.\n\n\n \n\n\n\n Chemistry of Materials, 35(10): 3841–3848. May 2023.\n \n\n\n\n
\n\n\n\n \n \n $\"Revealing$ Paper\n \n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

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@article{lee_revealing_2023,\n\ttitle = {Revealing {Electrolytic} {Ion} {Sorption} in {Layered} {Graphene} {Galleries} through {Low}-{Temperature} {Solid}-{State} {NMR}},\n\tvolume = {35},\n\tissn = {0897-4756, 1520-5002},\n\turl = {https://pubs.acs.org/doi/10.1021/acs.chemmater.2c03502},\n\tdoi = {10.1021/acs.chemmater.2c03502},\n\tlanguage = {en},\n\tnumber = {10},\n\turldate = {2023-06-13},\n\tjournal = {Chemistry of Materials},\n\tauthor = {Lee, Daniel and Banda, Harish and Périé, Sandy and Marcucci, Coralie and Chenavier, Yves and Dubois, Lionel and Taberna, Pierre-Louis and Simon, Patrice and De Paëpe, Gaël and Duclairoir, Florence},\n\tmonth = may,\n\tyear = {2023},\n\tpages = {3841--3848},\n}\n\n

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\n \n\n \n \n \n \n \n \n Highly Efficient Polarizing Agents for MAS‐DNP of Proton‐Dense Molecular Solids.\n \n \n \n \n\n\n \n Harrabi, R.; Halbritter, T.; Aussenac, F.; Dakhlaoui, O.; Van Tol, J.; Damodaran, K. K.; Lee, D.; Paul, S.; Hediger, S.; Mentink‐Vigier, F.; Sigurdsson, S. T.; and De Paëpe, G.\n\n\n \n\n\n\n Angewandte Chemie International Edition, 61(12): e202114103. March 2022.\n Publisher: John Wiley & Sons, Ltd\n\n\n\n
\n\n\n\n \n \n $\"Highly$ Paper\n \n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n \n \n \n \n \n \n \n \n \n \n\n\n\n

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@article{Harrabi2022,\n\ttitle = {Highly {Efficient} {Polarizing} {Agents} for {MAS}‐{DNP} of {Proton}‐{Dense} {Molecular} {Solids}},\n\tvolume = {61},\n\tissn = {1433-7851, 1521-3773},\n\turl = {https://onlinelibrary.wiley.com/doi/10.1002/anie.202114103},\n\tdoi = {10.1002/anie.202114103},\n\tabstract = {Efficiently hyperpolarizing proton-dense molecular solids through Dynamic Nuclear Polarization (DNP) solid-state NMR is still an unmet challenge. Polarizing agents (PAs) developed so far do not perform well on proton-rich systems, such as organic microcrystals and biomolecular assemblies. Herein we introduce a new PA, cAsymPol-POK, and report outstanding hyperpolarization efficiency on 12.76 kDa U-13 C, 15 N-labeled LecA protein and pharmaceutical drugs at high magnetic fields (up to 18.8 T) and fast MAS frequencies (up to 40 kHz). The performance of cAsymPol-POK is rationalized by MAS-DNP simulations combined with Electron Paramagnetic Resonance (EPR), Density Functional Theory (DFT) and Molecular Dynamics (MD). This work shows that this new biradical is compatible with challenging biomolecular applications and unlocks the rapid acquisition of 13 C-13 C and 15 N-13 C correlations of pharmaceutical drugs at natural isotopic abundance, which are key experiments for structure determination.},\n\tnumber = {12},\n\turldate = {2022-01-12},\n\tjournal = {Angewandte Chemie International Edition},\n\tauthor = {Harrabi, Rania and Halbritter, Thomas and Aussenac, Fabien and Dakhlaoui, Ons and Van Tol, Johan and Damodaran, Krishna K. and Lee, Daniel and Paul, Subhradip and Hediger, Sabine and Mentink‐Vigier, Frederic and Sigurdsson, Snorri Th. and De Paëpe, Gaël},\n\tmonth = mar,\n\tyear = {2022},\n\tnote = {Publisher: John Wiley \\& Sons, Ltd},\n\tkeywords = {Biomolecules, Polarizing Agents, dynamic nuclear polarization, nuclear magnetic resonance, pharmaceuticals},\n\tpages = {e202114103},\n}\n\n

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\n \n\n \n \n \n \n \n \n Biomolecular and Biological Applications of Solid-State NMR with Dynamic Nuclear Polarization Enhancement.\n \n \n \n \n\n\n \n Chow, W. Y.; De Paëpe, G.; and Hediger, S.\n\n\n \n\n\n\n Chemical Reviews, 122(10): 9795–9847. May 2022.\n \n\n\n\n
\n\n\n\n \n \n $\"Biomolecular$ Paper\n \n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n\n \n \n \n 1 download\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

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@article{chow_biomolecular_2022,\n\ttitle = {Biomolecular and {Biological} {Applications} of {Solid}-{State} {NMR} with {Dynamic} {Nuclear} {Polarization} {Enhancement}},\n\tvolume = {122},\n\tissn = {0009-2665, 1520-6890},\n\turl = {https://pubs.acs.org/doi/10.1021/acs.chemrev.1c01043},\n\tdoi = {10.1021/acs.chemrev.1c01043},\n\tlanguage = {en},\n\tnumber = {10},\n\turldate = {2023-06-14},\n\tjournal = {Chemical Reviews},\n\tauthor = {Chow, Wing Ying and De Paëpe, Gaël and Hediger, Sabine},\n\tmonth = may,\n\tyear = {2022},\n\tpages = {9795--9847},\n}\n\n

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\n \n\n \n \n \n \n \n \n Sonocrystallization of CMONS Needles and Nanocubes: Mechanistic Studies and Advanced Crystallinity Characterization by Combining X-ray and Electron Diffractions with DNP-Enhanced NMR.\n \n \n \n \n\n\n \n Cattoën, X.; Kumar, A.; Dubois, F.; Vaillant, C.; Matta-Seclén, M.; Leynaud, O.; Kodjikian, S.; Hediger, S.; De Paëpe, G.; and Ibanez, A.\n\n\n \n\n\n\n Crystal Growth & Design, 22(4): 2181–2191. April 2022.\n \n\n\n\n
\n\n\n\n \n \n $\"Sonocrystallization$ Paper\n \n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

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@article{Cattoen2022a,\n\ttitle = {Sonocrystallization of {CMONS} {Needles} and {Nanocubes}: {Mechanistic} {Studies} and {Advanced} {Crystallinity} {Characterization} by {Combining} {X}-ray and {Electron} {Diffractions} with {DNP}-{Enhanced} {NMR}},\n\tvolume = {22},\n\tissn = {1528-7483},\n\turl = {https://pubs.acs.org/doi/10.1021/acs.cgd.1c01246},\n\tdoi = {10.1021/acs.cgd.1c01246},\n\tnumber = {4},\n\turldate = {2022-03-07},\n\tjournal = {Crystal Growth \\& Design},\n\tauthor = {Cattoën, Xavier and Kumar, Akshay and Dubois, Fabien and Vaillant, Carole and Matta-Seclén, Mauricio and Leynaud, Olivier and Kodjikian, Stéphanie and Hediger, Sabine and De Paëpe, Gaël and Ibanez, Alain},\n\tmonth = apr,\n\tyear = {2022},\n\tpages = {2181--2191},\n}\n\n

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\n \n 2021\n \n \n (2)\n \n \n

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\n \n\n \n \n \n \n \n \n ZnO Nanoplatelets with Controlled Thickness: Atomic Insight into Facet‐Specific Bimodal Ligand Binding Using DNP NMR.\n \n \n \n \n\n\n \n Terlecki, M.; Badoni, S.; Leszczyński, M. K.; Gierlotka, S.; Justyniak, I.; Okuno, H.; Wolska‐Pietkiewicz, M.; Lee, D.; De Paëpe, G.; and Lewiński, J.\n\n\n \n\n\n\n Advanced Functional Materials, 31(49): 2105318. December 2021.\n \n\n\n\n
\n\n\n\n \n \n $\"ZnO$ Paper\n \n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n\n \n \n \n 3 downloads\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@article{terlecki_zno_2021,\n\ttitle = {{ZnO} {Nanoplatelets} with {Controlled} {Thickness}: {Atomic} {Insight} into {Facet}‐{Specific} {Bimodal} {Ligand} {Binding} {Using} {DNP} {NMR}},\n\tvolume = {31},\n\tissn = {1616-301X, 1616-3028},\n\tshorttitle = {{ZnO} {Nanoplatelets} with {Controlled} {Thickness}},\n\turl = {https://onlinelibrary.wiley.com/doi/10.1002/adfm.202105318},\n\tdoi = {10.1002/adfm.202105318},\n\tlanguage = {en},\n\tnumber = {49},\n\turldate = {2023-06-14},\n\tjournal = {Advanced Functional Materials},\n\tauthor = {Terlecki, Michał and Badoni, Saumya and Leszczyński, Michał K. and Gierlotka, Stanisław and Justyniak, Iwona and Okuno, Hanako and Wolska‐Pietkiewicz, Małgorzata and Lee, Daniel and De Paëpe, Gaël and Lewiński, Janusz},\n\tmonth = dec,\n\tyear = {2021},\n\tpages = {2105318},\n}\n\n

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\n \n\n \n \n \n \n \n On the use of radio-frequency offsets for improving double-quantum homonuclear dipolar recoupling of half-integer-spin quadrupolar nuclei.\n \n \n \n\n\n \n Duong, N.; Lee, D.; Mentink-Vigier, F.; Lafon, O.; and De Paëpe, G.\n\n\n \n\n\n\n Magnetic Resonance in Chemistry, 59(9-10): 991–1008. 2021.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

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@article{duong_use_2021,\n\ttitle = {On the use of radio-frequency offsets for improving double-quantum homonuclear dipolar recoupling of half-integer-spin quadrupolar nuclei},\n\tvolume = {59},\n\tdoi = {10.1002/mrc.5142},\n\tabstract = {Detecting proximities between nuclei is crucial for atomic-scale structure determination with nuclear magnetic resonance (NMR) spectroscopy. Different from spin-1/2 nuclei, the methodology for quadrupolar nuclei is limited for solids due to the complex spin dynamics under simultaneous magic-angle spinning (MAS) and radio-frequency irradiation. Herein, the performances of several homonuclear rotary recoupling (HORROR)-based homonuclear dipolar recoupling sequences are evaluated for 27Al (spin-5/2). It is shown numerically and experimentally on mesoporous alumina that (Formula presented.) outperforms the supercycled S3 sequence and its pure double-quantum (DQ) (bracketed) version, [S3], both in terms of DQ transfer efficiency and bandwidth. This result is surprising since the S3 sequence is among the best low-power recoupling schemes for spin-1/2. The superiority of (Formula presented.) is thoroughly explained, and the crucial role of radio-frequency offsets during its spin dynamics is highlighted. The analytical approximation of (Formula presented.), derived in an offset-toggling frame, clarifies the interplay between offset and DQ efficiency, namely, the benefits of off-resonance irradiation and the trough in DQ efficiency for (Formula presented.) when the irradiation is central between two resonances, both for spin-1/2 and half-integer-spin quadrupolar nuclei. Additionally, density matrix propagations show that the (Formula presented.) sequence, applied to quadrupolar nuclei subject to quadrupolar interaction much larger than radio-frequency frequency field, can create single- and multiple-quantum coherences for near on-resonance irradiation. This significantly perturbs the creation of DQ coherences between central transitions of neighboring quadrupolar nuclei. This effect explains the DQ efficiency trough for near on-resonance irradiation, in the case of both cross-correlation and autocorrelation peaks. Overall, this work aids experimental acquisition of homonuclear dipolar correlation spectra of half-integer-spin quadrupolar nuclei and provides theoretical insights towards improving recoupling schemes at high magnetic field and fast MAS.},\n\tnumber = {9-10},\n\tjournal = {Magnetic Resonance in Chemistry},\n\tauthor = {Duong, N.T. and Lee, D. and Mentink-Vigier, F. and Lafon, O. and De Paëpe, G.},\n\tyear = {2021},\n\tpages = {991--1008},\n}\n\n

\n

\n\n\n

\n Detecting proximities between nuclei is crucial for atomic-scale structure determination with nuclear magnetic resonance (NMR) spectroscopy. Different from spin-1/2 nuclei, the methodology for quadrupolar nuclei is limited for solids due to the complex spin dynamics under simultaneous magic-angle spinning (MAS) and radio-frequency irradiation. Herein, the performances of several homonuclear rotary recoupling (HORROR)-based homonuclear dipolar recoupling sequences are evaluated for 27Al (spin-5/2). It is shown numerically and experimentally on mesoporous alumina that (Formula presented.) outperforms the supercycled S3 sequence and its pure double-quantum (DQ) (bracketed) version, [S3], both in terms of DQ transfer efficiency and bandwidth. This result is surprising since the S3 sequence is among the best low-power recoupling schemes for spin-1/2. The superiority of (Formula presented.) is thoroughly explained, and the crucial role of radio-frequency offsets during its spin dynamics is highlighted. The analytical approximation of (Formula presented.), derived in an offset-toggling frame, clarifies the interplay between offset and DQ efficiency, namely, the benefits of off-resonance irradiation and the trough in DQ efficiency for (Formula presented.) when the irradiation is central between two resonances, both for spin-1/2 and half-integer-spin quadrupolar nuclei. Additionally, density matrix propagations show that the (Formula presented.) sequence, applied to quadrupolar nuclei subject to quadrupolar interaction much larger than radio-frequency frequency field, can create single- and multiple-quantum coherences for near on-resonance irradiation. This significantly perturbs the creation of DQ coherences between central transitions of neighboring quadrupolar nuclei. This effect explains the DQ efficiency trough for near on-resonance irradiation, in the case of both cross-correlation and autocorrelation peaks. Overall, this work aids experimental acquisition of homonuclear dipolar correlation spectra of half-integer-spin quadrupolar nuclei and provides theoretical insights towards improving recoupling schemes at high magnetic field and fast MAS.\n

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\n \n 2020\n \n \n (1)\n \n \n

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\n \n\n \n \n \n \n \n \n The surface chemistry of a nanocellulose drug carrier unravelled by MAS-DNP.\n \n \n \n \n\n\n \n Kumar, A.; Durand, H.; Zeno, E.; Balsollier, C.; Watbled, B.; Sillard, C.; Fort, S.; Baussanne, I.; Belgacem, N.; Lee, D.; Bras, J.; De Paëpe, G.; Hediger, S.; Demeunynck, M.; Bras, J.; and De Paëpe, G.\n\n\n \n\n\n\n Chemical Science, 11(15): 3868–3877. April 2020.\n Publisher: Royal Society of Chemistry\n\n\n\n
\n\n\n\n \n \n $\"The$ Paper\n \n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

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@article{kumar_surface_2020,\n\ttitle = {The surface chemistry of a nanocellulose drug carrier unravelled by {MAS}-{DNP}},\n\tvolume = {11},\n\tissn = {20416539},\n\turl = {https://pubs.rsc.org/en/content/articlehtml/2020/sc/c9sc06312a https://pubs.rsc.org/en/content/articlelanding/2020/sc/c9sc06312a},\n\tdoi = {10.1039/c9sc06312a},\n\tabstract = {Cellulose nanofibrils (CNF) are renewable bio-based materials with high specific area, which makes them ideal candidates for multiple emerging applications including for instance on-demand drug release. However, in-depth chemical and structural characterization of the CNF surface chemistry is still an open challenge, especially for low weight percentage of functionalization. This currently prevents the development of efficient, cost-effective and reproducible green synthetic routes and thus the widespread development of targeted and responsive drug-delivery CNF carriers. We show in this work how we use dynamic nuclear polarization (DNP) to overcome the sensitivity limitation of conventional solid-state NMR and gain insight into the surface chemistry of drug-functionalized TEMPO-oxidized cellulose nanofibrils. The DNP enhanced-NMR data can report unambiguously on the presence of trace amounts of TEMPO moieties and depolymerized cellulosic units in the starting material, as well as coupling agents on the CNFs surface (used in the heterogeneous reaction). This enables a precise estimation of the drug loading while differentiating adsorption from covalent bonding (∼1 wt\\% in our case) as opposed to other analytical techniques such as elemental analysis and conductometric titration that can neither detect the presence of coupling agents, nor differentiate unambiguously between adsorption and grafting. The approach, which does not rely on the use of 13C/15N enriched compounds, will be key to further develop efficient surface chemistry routes and has direct implication for the development of drug delivery applications both in terms of safety and dosage.},\n\tnumber = {15},\n\tjournal = {Chemical Science},\n\tauthor = {Kumar, Akshay and Durand, Hippolyte and Zeno, Elisa and Balsollier, Cyril and Watbled, Bastien and Sillard, Cecile and Fort, Sébastien and Baussanne, Isabelle and Belgacem, Naceur and Lee, Daniel and Bras, Julien and De Paëpe, Gaël and Hediger, Sabine and Demeunynck, Martine and Bras, Julien and De Paëpe, Gaël},\n\tmonth = apr,\n\tyear = {2020},\n\tnote = {Publisher: Royal Society of Chemistry},\n\tpages = {3868--3877},\n}\n\n

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\n \n 2019\n \n \n (5)\n \n \n

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\n \n\n \n \n \n \n \n \n De novo prediction of cross-effect efficiency for magic angle spinning dynamic nuclear polarization.\n \n \n \n \n\n\n \n Mentink Vigier, F.; Barra, A.; van Tol, J.; Hediger, S.; Lee, D.; and De Paëpe, G.\n\n\n \n\n\n\n Physical Chemistry Chemical Physics, 18: 1–636. 2019.\n \n\n\n\n
\n\n\n\n \n \n $\"De$ Paper\n \n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n \n \n \n \n \n \n \n \n \n \n \n \n \n \n \n \n \n \n\n\n\n

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@article{MentinkVigier2019,\n\ttitle = {De novo prediction of cross-effect efficiency for magic angle spinning dynamic nuclear polarization},\n\tvolume = {18},\n\tissn = {1463-9076},\n\turl = {www.rsc.org/pccp},\n\tdoi = {10.1039/C8CP06819D},\n\tabstract = {Magic angle spinning dynamic nuclear polarization (MAS-DNP) has become a key approach to boost the intrinsic low sensitivity of NMR in solids. This method relies on the use of both...},\n\tjournal = {Physical Chemistry Chemical Physics},\n\tauthor = {Mentink Vigier, Frederic and Barra, Anne-Laure and van Tol, Johan and Hediger, Sabine and Lee, Daniel and De Paëpe, Gaël},\n\tyear = {2019},\n\tkeywords = {Biradicals, DFT, Dynamic Nuclear Polarization, High-Field EPR, MAS-DNP, Nitroxides, Theory, depolarization, solid-state NMR},\n\tpages = {1--636},\n}\n\n

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\n \n\n \n \n \n \n \n Selective high-resolution DNP-enhanced NMR of biomolecular binding sites.\n \n \n \n\n\n \n Marin-Montesinos, I.; Goyard, D.; Gillon, E.; Renaudet, O.; Imberty, A.; Hediger, S.; and De Paëpe, G.\n\n\n \n\n\n\n Chemical Science, 10(11): 3366–3374. 2019.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

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@article{marin-montesinos_selective_2019,\n\ttitle = {Selective high-resolution {DNP}-enhanced {NMR} of biomolecular binding sites},\n\tvolume = {10},\n\tdoi = {10.1039/C8SC05696J},\n\tabstract = {Locating binding sites in biomolecular assemblies and solving their structures are of the utmost importance to unravel functional aspects of the system and provide experimental data that can be used for structure-based drug design. This often still remains a challenge, both in terms of selectivity and sensitivity for X-ray crystallography, cryo-electron microscopy and NMR. In this work, we introduce a novel method called Selective Dynamic Nuclear Polarization (Sel-DNP) that allows selective highlighting and identification of residues present in the binding site. This powerful site-directed approach relies on the use of localized paramagnetic relaxation enhancement induced by a ligand-functionalized paramagnetic construct combined with difference spectroscopy to recover high-resolution and high-sensitivity information from binding sites. The identification of residues involved in the binding is performed using spectral fingerprints obtained from a set of high-resolution multidimensional spectra with varying selectivities. The methodology is demonstrated on the galactophilic lectin LecA, for which we report well-resolved DNP-enhanced spectra with linewidths between 0.5 and 1 ppm, which enable the de novo assignment of the binding interface residues, without using previous knowledge of the binding site location. Since this approach produces clean and resolved difference spectra containing a limited number of residues, resonance assignment can be performed without any limitation with respect to the size of the biomolecular system and only requires the production of one protein sample (e.g.13C,15N-labeled protein).},\n\tnumber = {11},\n\tjournal = {Chemical Science},\n\tauthor = {Marin-Montesinos, I. and Goyard, D. and Gillon, E. and Renaudet, O. and Imberty, A. and Hediger, S. and De Paëpe, G.},\n\tyear = {2019},\n\tpages = {3366--3374},\n}\n\n

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\n \n\n \n \n \n \n \n Disclosing Interfaces of ZnO Nanocrystals Using Dynamic Nuclear Polarization: Sol-Gel versus Organometallic Approach.\n \n \n \n\n\n \n Lee, D.; Wolska-Pietkiewicz, M.; Badoni, S.; Grala, A.; Lewiński, J.; and De Paëpe, G.\n\n\n \n\n\n\n Angewandte Chemie - International Edition, 58(48): 17163–17168. 2019.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n \n \n \n \n \n \n \n \n \n \n\n\n\n

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@article{lee_disclosing_2019,\n\ttitle = {Disclosing {Interfaces} of {ZnO} {Nanocrystals} {Using} {Dynamic} {Nuclear} {Polarization}: {Sol}-{Gel} versus {Organometallic} {Approach}},\n\tvolume = {58},\n\tdoi = {10.1002/anie.201906726},\n\tabstract = {The unambiguous characterization of the coordination chemistry of nanocrystal surfaces produced by wet-chemical synthesis presently remains highly challenging. Here, zinc oxide nanocrystals (ZnO NCs) coated by monoanionic diphenyl phosphate (DPP) ligands were derived by a sol-gel process and a one-pot self-supporting organometallic (OSSOM) procedure. Atomic-scale characterization through dynamic nuclear polarization (DNP-)enhanced solid-state NMR (ssNMR) spectroscopy has notably enabled resolving their vastly different surface-ligand interfaces. For the OSSOM-derived NCs, DPP moieties form stable and strongly-anchored μ2- and μ3-bridging-ligand pairs that are resistant to competitive ligand exchange. The sol-gel-derived NCs contain a wide variety of coordination modes of DPP ligands and a ligand exchange process takes place between DPP and glycerol molecules. This highlights the power of DNP-enhanced ssNMR for detailed NC surface analysis and of the OSSOM approach for the preparation of ZnO NCs.},\n\tnumber = {48},\n\tjournal = {Angewandte Chemie - International Edition},\n\tauthor = {Lee, D. and Wolska-Pietkiewicz, M. and Badoni, S. and Grala, A. and Lewiński, J. and De Paëpe, G.},\n\tyear = {2019},\n\tkeywords = {Organometallic Chemistry, Sol Gel chemistry, ZnO nanocrystals, dynamic nuclear polarization, nuclear magnetic resonance},\n\tpages = {17163--17168},\n}\n\n

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\n \n\n \n \n \n \n \n \n Natural Isotopic Abundance 13 C and 15 N Multidimensional Solid-State NMR Enabled by Dynamic Nuclear Polarization.\n \n \n \n \n\n\n \n Smith, A. N.; Märker, K.; Hediger, S.; and De Paëpe, G.\n\n\n \n\n\n\n The Journal of Physical Chemistry Letters, 10(16): 4652–4662. August 2019.\n \n\n\n\n
\n\n\n\n \n \n $\"Natural$ Paper\n \n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

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@article{Smith2019,\n\ttitle = {Natural {Isotopic} {Abundance} 13 {C} and 15 {N} {Multidimensional} {Solid}-{State} {NMR} {Enabled} by {Dynamic} {Nuclear} {Polarization}},\n\tvolume = {10},\n\tissn = {1948-7185},\n\turl = {https://pubs.acs.org/sharingguidelines},\n\tdoi = {10.1021/acs.jpclett.8b03874},\n\tabstract = {Dynamic nuclear polarization (DNP) has made feasible solid-state NMR experiments that were previously thought impractical due to sensitivity limitations. One such class of experiments is the structural characterization of organic and biological samples at natural isotopic abundance (NA). Herein, we describe the many advantages of DNP-enabled ssNMR at NA, including the extraction of long-range distance constraints using dipolar recoupling pulse sequences without the deleterious effects of dipolar truncation. In addition to the theoretical underpinnings in the analysis of these types of experiments, numerous applications of DNP-enabled ssNMR at NA are discussed.},\n\tnumber = {16},\n\turldate = {2020-01-28},\n\tjournal = {The Journal of Physical Chemistry Letters},\n\tauthor = {Smith, Adam N. and Märker, Katharina and Hediger, Sabine and De Paëpe, Gaël},\n\tmonth = aug,\n\tyear = {2019},\n\tpmid = {31361489},\n\tpages = {4652--4662},\n}\n\n

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\n \n\n \n \n \n \n \n Sparsely Pillared Graphene Materials for High-Performance Supercapacitors: Improving Ion Transport and Storage Capacity.\n \n \n \n\n\n \n Banda, H.; Périé, S.; Daffos, B.; Taberna, P.; Dubois, L.; Crosnier, O.; Simon, P.; Lee, D.; De Paëpe, G.; and Duclairoir, F.\n\n\n \n\n\n\n ACS Nano, 13(2): 1443–1453. 2019.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

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@article{banda_sparsely_2019,\n\ttitle = {Sparsely {Pillared} {Graphene} {Materials} for {High}-{Performance} {Supercapacitors}: {Improving} {Ion} {Transport} and {Storage} {Capacity}},\n\tvolume = {13},\n\tdoi = {10.1021/acsnano.8b07102},\n\tabstract = {Graphene-based materials are extensively studied as promising candidates for supercapacitors (SCs) owing to the high surface area, electrical conductivity, and mechanical flexibility of graphene. Reduced graphene oxide (RGO), a close graphene-like material studied for SCs, offers limited specific capacitances (100 F·g-1) as the reduced graphene sheets partially restack through I-πinteractions. This paper presents pillared graphene materials designed to minimize such graphitic restacking by cross-linking the graphene sheets with a bifunctional pillar molecule. Solid-state NMR, X-ray diffraction, and electrochemical analyses reveal that the synthesized materials possess covalently cross-linked graphene galleries that offer additional sites for ion sorption in SCs. Indeed, high specific capacitances in SCs are observed for the graphene materials synthesized with an optimized number of pillars. Specifically, the straightforward synthesis of a graphene hydrogel containing pillared structures and an interconnected porous network delivered a material with gravimetric capacitances two times greater than that of RGO (200 F·g-1 vs 107 F·g-1) and volumetric capacitances that are nearly four times larger (210 F·cm-3 vs 54 F·cm-3). Additionally, despite the presence of pillars inside the graphene galleries, the optimized materials show efficient ion transport characteristics. This work therefore brings perspectives for the next generation of high-performance SCs.},\n\tnumber = {2},\n\tjournal = {ACS Nano},\n\tauthor = {Banda, H. and Périé, S. and Daffos, B. and Taberna, P.-L. and Dubois, L. and Crosnier, O. and Simon, P. and Lee, D. and De Paëpe, G. and Duclairoir, F.},\n\tyear = {2019},\n\tpages = {1443--1453},\n}\n

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\n \n 2018\n \n \n (2)\n \n \n

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\n \n\n \n \n \n \n \n \n MAS-DNP Enhancements: Hyperpolarization, Depolarization, and Absolute Sensitivity.\n \n \n \n \n\n\n \n Hediger, S.; Lee, D.; Mentink-Vigier, F.; and De Paëpe, G.\n\n\n \n\n\n\n eMagRes, 7(4): 105–116. 2018.\n ISBN: 9780470034590\n\n\n\n
\n\n\n\n \n \n $\"MAS-DNP$ Paper\n \n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 1 download\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n \n \n \n \n \n \n \n \n \n \n \n \n \n \n\n\n\n

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@article{hediger_mas-dnp_2018,\n\ttitle = {{MAS}-{DNP} {Enhancements}: {Hyperpolarization}, {Depolarization}, and {Absolute} {Sensitivity}},\n\tvolume = {7},\n\turl = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/9780470034590.emrstm1559},\n\tdoi = {10.1002/9780470034590.emrstm1559},\n\tabstract = {Dynamic nuclear polarization at high magnetic fields has made significant progress over the last decades, and this hyperpolarizing technique is currently revolutionizing the impact of solid-state NMR for the study of complex systems in chemistry, material science, and biology. In this article, we emphasize the importance and difficulty in quantifying sensitivity from DNP under magic-angle spinning. To this end, we provide insight into the cross effect, the current main MAS-DNP mechanism. This includes a description of the microwave-induced hyperpolarization phenomenon but also of the reduction of the NMR signal prior to microwave irradiation for samples doped with polarizing agents (bleaching and depolarization effects). We highlight the importance of the nuclear hyperpolarization buildup time in the evaluation of MAS-DNP efficiency. Finally, we discuss other experimental parameters affecting sensitivity in DNP-enhanced spectra and propose a guideline for its proper characterization depending on the type of investigation.},\n\tnumber = {4},\n\tjournal = {eMagRes},\n\tauthor = {Hediger, Sabine and Lee, Daniel and Mentink-Vigier, Frédéric and De Paëpe, Gaël},\n\tyear = {2018},\n\tnote = {ISBN: 9780470034590},\n\tkeywords = {\\#nosource, MAS-DNP, absolute sensitivity, cross effect, depolarization, enhancement, hyperpolarization},\n\tpages = {105--116},\n}\n\n

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\n \n\n \n \n \n \n \n Structural Fingerprinting of Protein Aggregates by Dynamic Nuclear Polarization-Enhanced Solid-State NMR at Natural Isotopic Abundance.\n \n \n \n\n\n \n Smith, A.; Märker, K.; Piretra, T.; Boatz, J.; Matlahov, I.; Kodali, R.; Hediger, S.; Van Der Wel, P.; and De Paëpe, G.\n\n\n \n\n\n\n Journal of the American Chemical Society, 140(44): 14576–14580. 2018.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 1 download\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

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@article{smith_structural_2018,\n\ttitle = {Structural {Fingerprinting} of {Protein} {Aggregates} by {Dynamic} {Nuclear} {Polarization}-{Enhanced} {Solid}-{State} {NMR} at {Natural} {Isotopic} {Abundance}},\n\tvolume = {140},\n\tdoi = {10.1021/jacs.8b09002},\n\tabstract = {A pathological hallmark of Huntington's disease (HD) is the formation of neuronal protein deposits containing mutant huntingtin fragments with expanded polyglutamine (polyQ) domains. Prior studies have shown the strengths of solid-state NMR (ssNMR) to probe the atomic structure of such aggregates, but have required in vitro isotopic labeling. Herein, we present an approach for the structural fingerprinting of fibrils through ssNMR at natural isotopic abundance (NA). These methods will enable the spectroscopic fingerprinting of unlabeled (e.g., ex vivo) protein aggregates and the extraction of valuable new long-range 13C-13C distance constraints.},\n\tnumber = {44},\n\tjournal = {Journal of the American Chemical Society},\n\tauthor = {Smith, A.N. and Märker, K. and Piretra, T. and Boatz, J.C. and Matlahov, I. and Kodali, R. and Hediger, S. and Van Der Wel, P.C.A. and De Paëpe, G.},\n\tyear = {2018},\n\tpages = {14576--14580},\n}\n\n

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\n \n 2017\n \n \n (6)\n \n \n

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\n \n\n \n \n \n \n \n At the very beginning of life on earth: The thiol-rich peptide (TRP) world hypothesis.\n \n \n \n\n\n \n Vallee, Y.; Shalayel, I.; Ly, K.; Raghavendra Rao, K.; De Paëpe, G.; Märker, K.; and Milet, A.\n\n\n \n\n\n\n International Journal of Developmental Biology, 61(8-9): 471–478. 2017.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n \n \n\n\n\n

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@article{vallee_at_2017,\n\ttitle = {At the very beginning of life on earth: {The} thiol-rich peptide ({TRP}) world hypothesis},\n\tvolume = {61},\n\tdoi = {10.1387/ijdb.170028yv},\n\tabstract = {Life developed on Earth probably about 3.8 billion years ago, on a planet that was already largely covered by oceans and where the atmosphere was very humid. The reactions, which may have led to the formation of the first polymers, particularly to the first peptides and nucleic acids, must have been compatible with these conditions. This is the case of the reaction of nitriles with aminothiols, such as cysteine and homocysteine. Since aminonitriles are the probable precursors of amino acids, this condensation reaction has been able to rapidly yield dipeptides, tripeptides, oligomers and even true polymers, each containing thiol functions. These thiol-rich peptides (TRP's) would then have assumed the various catalytic roles that the peptides containing cysteine residues play today. They allowed a rapid bloom of life in the primitive ocean. In this scenario, RNA's are not the first polymers, but have been synthesized, like DNA's, thanks to the catalytic properties of thiols in a mostly TRP world. In this world, due to its ability to form a thiolactone, homocysteine may have played the leading role in enabling the previously formed oligomers to be stappled together, thus accelerating the formation of long peptide chains. ility to form a thiolactone, homocysteine may have played the leading role in enabling the previously formed oligomers to be stappled together, thus accelerating the formation of long peptide chains.},\n\tnumber = {8-9},\n\tjournal = {International Journal of Developmental Biology},\n\tauthor = {Vallee, Y. and Shalayel, I. and Ly, K.-D. and Raghavendra Rao, K.V. and De Paëpe, G. and Märker, K. and Milet, A.},\n\tyear = {2017},\n\tkeywords = {\\#nosource},\n\tpages = {471--478},\n}\n\n

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\n \n\n \n \n \n \n \n \n Solvent signal suppression for high-resolution MAS-DNP.\n \n \n \n \n\n\n \n Lee, D.; Chaudhari, S. R.; and De Paëpe, G.\n\n\n \n\n\n\n Journal of Magnetic Resonance, 278: 60–66. May 2017.\n \n\n\n\n
\n\n\n\n \n \n $\"Solvent$ Paper\n \n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

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@article{lee_solvent_2017,\n\ttitle = {Solvent signal suppression for high-resolution {MAS}-{DNP}},\n\tvolume = {278},\n\tissn = {10907807},\n\turl = {https://linkinghub.elsevier.com/retrieve/pii/S1090780717300733},\n\tdoi = {10.1016/j.jmr.2017.03.012},\n\tlanguage = {en},\n\turldate = {2023-06-14},\n\tjournal = {Journal of Magnetic Resonance},\n\tauthor = {Lee, Daniel and Chaudhari, Sachin R. and De Paëpe, Gaël},\n\tmonth = may,\n\tyear = {2017},\n\tpages = {60--66},\n}\n\n

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\n \n\n \n \n \n \n \n Efficient 2D double-quantum solid-state NMR spectroscopy with large spectral widths.\n \n \n \n\n\n \n Märker, K.; Hediger, S.; and De Paëpe, G.\n\n\n \n\n\n\n Chemical Communications, 53(65): 9155–9158. 2017.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 1 download\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

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@article{marker_efficient_2017,\n\ttitle = {Efficient {2D} double-quantum solid-state {NMR} spectroscopy with large spectral widths},\n\tvolume = {53},\n\tdoi = {10.1039/c7cc04890d},\n\tabstract = {2D double-quantum single-quantum correlation spectra with arbitrary spectral widths can be recorded with SR26 and related supercycled recoupling sequences when applying Supercycle-Timing-Compensation (STiC) phase shifts. This concept widely extends the applicability of supercycled sequences, most importantly for obtaining long-range distance constraints for structure determination with solid-state NMR.},\n\tnumber = {65},\n\tjournal = {Chemical Communications},\n\tauthor = {Märker, K. and Hediger, S. and De Paëpe, G.},\n\tyear = {2017},\n\tpages = {9155--9158},\n}\n\n

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\n \n\n \n \n \n \n \n \n Fast and accurate MAS–DNP simulations of large spin ensembles.\n \n \n \n \n\n\n \n Mentink-Vigier, F.; Vega, S.; and De Paëpe, G.\n\n\n \n\n\n\n Physical Chemistry Chemical Physics, 19(5): 3506–3522. 2017.\n Publisher: The Royal Society of Chemistry\n\n\n\n
\n\n\n\n \n \n $\"Fast$ Paper\n \n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

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@article{mentink-vigier_fast_2017,\n\ttitle = {Fast and accurate {MAS}–{DNP} simulations of large spin ensembles},\n\tvolume = {19},\n\tissn = {1463-9076},\n\turl = {http://xlink.rsc.org/?DOI=C6CP07881H},\n\tdoi = {10.1039/C6CP07881H},\n\tabstract = {A deeper understanding of parameters affecting Magic Angle Spinning Dynamic Nuclear Polarization (MAS–DNP), an emerging nuclear magnetic resonance hyperpolarization method, is crucial for the development of new polarizing agents and the successful implementation of the technique at higher magnetic fields ({\\textgreater}10 T).},\n\tnumber = {5},\n\tjournal = {Physical Chemistry Chemical Physics},\n\tauthor = {Mentink-Vigier, Frédéric and Vega, Shimon and De Paëpe, Gaël},\n\tyear = {2017},\n\tnote = {Publisher: The Royal Society of Chemistry},\n\tpages = {3506--3522},\n}\n\n

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\n \n\n \n \n \n \n \n \n Interfacial Ca2+ environments in nanocrystalline apatites revealed by dynamic nuclear polarization enhanced 43Ca NMR spectroscopy.\n \n \n \n \n\n\n \n Lee, D.; Leroy, C.; Crevant, C.; Bonhomme-Coury, L.; Babonneau, F.; Laurencin, D.; Bonhomme, C.; and De Paëpe, G.\n\n\n \n\n\n\n Nature Communications, 8(1): 14104. April 2017.\n Publisher: Nature Publishing Group\n\n\n\n
\n\n\n\n \n \n $\"Interfacial$ Paper\n \n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n \n \n \n \n \n \n \n \n \n \n\n\n\n

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@article{Lee2017,\n\ttitle = {Interfacial {Ca2}+ environments in nanocrystalline apatites revealed by dynamic nuclear polarization enhanced {43Ca} {NMR} spectroscopy},\n\tvolume = {8},\n\tissn = {2041-1723},\n\turl = {http://www.nature.com/doifinder/10.1038/ncomms14104},\n\tdoi = {10.1038/ncomms14104},\n\tabstract = {Solid-state NMR can in principle be used to study calcium environments in biomaterials such as bones/teeth, but 43Ca lacks receptivity. Here the authors present an approach to acquire 43Ca data for hydroxyapatite at its natural isotopic abundance, di…},\n\tnumber = {1},\n\tjournal = {Nature Communications},\n\tauthor = {Lee, Daniel and Leroy, César and Crevant, Charlène and Bonhomme-Coury, Laure and Babonneau, Florence and Laurencin, Danielle and Bonhomme, Christian and De Paëpe, Gaël},\n\tmonth = apr,\n\tyear = {2017},\n\tnote = {Publisher: Nature Publishing Group},\n\tkeywords = {Bioinspired materials, Characterization and analytical techniques, Solid, Surface spectroscopy, state NMR},\n\tpages = {14104},\n}\n\n

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\n \n\n \n \n \n \n \n Welcoming natural isotopic abundance in solid-state NMR: probing π-stacking and supramolecular structure of organic nanoassemblies using DNP.\n \n \n \n\n\n \n Märker, K.; Paul, S.; Fernández-De-Alba, C.; Lee, D.; Mouesca, J.; Hediger, S.; and De Paëpe, G.\n\n\n \n\n\n\n Chemical Science, 8(2): 974–987. 2017.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 1 download\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

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@article{marker_welcoming_2017,\n\ttitle = {Welcoming natural isotopic abundance in solid-state {NMR}: probing π-stacking and supramolecular structure of organic nanoassemblies using {DNP}},\n\tvolume = {8},\n\tdoi = {10.1039/c6sc02709a},\n\tabstract = {The self-assembly of small organic molecules is an intriguing phenomenon, which provides nanoscale structures for applications in numerous fields from medicine to molecular electronics. Detailed knowledge of their structure, in particular on the supramolecular level, is a prerequisite for the rational design of improved self-assembled systems. In this work, we prove the feasibility of a novel concept of NMR-based 3D structure determination of such assemblies in the solid state. The key point of this concept is the deliberate use of samples that contain 13C at its natural isotopic abundance (NA, 1.1\\%), while exploiting magic-angle spinning dynamic nuclear polarization (MAS-DNP) to compensate for the reduced sensitivity. Since dipolar truncation effects are suppressed to a large extent in NA samples, unique and highly informative spectra can be recorded which are impossible to obtain on an isotopically labeled system. On the self-assembled cyclic diphenylalanine peptide, we demonstrate the detection of long-range internuclear distances up to ∼7 Å, allowing us to observe π-stacking through 13C-13C correlation spectra, providing a powerful tool for the analysis of one of the most important non-covalent interactions. Furthermore, experimental polarization transfer curves are in remarkable agreement with numerical simulations based on the crystallographic structure, and can be fully rationalized as the superposition of intra- and intermolecular contributions. This new approach to NMR crystallography provides access to rich and precise structural information, opening up a new avenue to de novo crystal structure determination by NMR.},\n\tnumber = {2},\n\tjournal = {Chemical Science},\n\tauthor = {Märker, K. and Paul, S. and Fernández-De-Alba, C. and Lee, D. and Mouesca, J.-M. and Hediger, S. and De Paëpe, G.},\n\tyear = {2017},\n\tpages = {974--987},\n}\n\n

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\n \n 2016\n \n \n (1)\n \n \n

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\n \n\n \n \n \n \n \n Ultra-low temperature MAS-DNP.\n \n \n \n\n\n \n Lee, D.; Bouleau, E.; Saint-Bonnet, P.; Hediger, S.; and De Paëpe, G.\n\n\n \n\n\n\n Journal of Magnetic Resonance, 264: 116–124. 2016.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

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@article{lee_ultra-low_2016,\n\ttitle = {Ultra-low temperature {MAS}-{DNP}},\n\tvolume = {264},\n\tdoi = {10.1016/j.jmr.2015.12.010},\n\tabstract = {Since the infancy of NMR spectroscopy, sensitivity and resolution have been the limiting factors of the technique. Regular essential developments on this front have led to the widely applicable, versatile, and powerful spectroscopy that we know today. However, the Holy Grail of ultimate sensitivity and resolution is not yet reached, and technical improvements are still ongoing. Hence, high-field dynamic nuclear polarization (DNP) making use of high-frequency, high-power microwave irradiation of electron spins has become very promising in combination with magic angle sample spinning (MAS) solid-state NMR experiments. This is because it leads to a transfer of the much larger polarization of these electron spins under suitable irradiation to surrounding nuclei, greatly increasing NMR sensitivity. Currently, this boom in MAS-DNP is mainly performed at minimum sample temperatures of about 100 K, using cold nitrogen gas to pneumatically spin and cool the sample. This Perspective deals with the desire to improve further the sensitivity and resolution by providing "ultra"-low temperatures for MAS-DNP, using cryogenic helium gas. Different designs on how this technological challenge has been overcome are described. It is shown that stable and fast spinning can be attained for sample temperatures down to 30 K using a large cryostat developed in our laboratory. Using this cryostat to cool a closed-loop of helium gas brings the additional advantage of sample spinning frequencies that can greatly surpass those achievable with nitrogen gas, due to the differing fluidic properties of these two gases. It is shown that using ultra-low temperatures for MAS-DNP results in substantial experimental sensitivity enhancements and according time-savings. Access to this temperature range is demonstrated to be both viable and highly pertinent.},\n\tjournal = {Journal of Magnetic Resonance},\n\tauthor = {Lee, D. and Bouleau, E. and Saint-Bonnet, P. and Hediger, S. and De Paëpe, G.},\n\tyear = {2016},\n\tpages = {116--124},\n}\n\n

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\n \n 2015\n \n \n (6)\n \n \n

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\n \n\n \n \n \n \n \n \n Nuclear depolarization and absolute sensitivity in magic-angle spinning cross effect dynamic nuclear polarization.\n \n \n \n \n\n\n \n Mentink-Vigier, F.; Paul, S.; Lee, D.; Feintuch, A.; Hediger, S.; Vega, S.; and De Paëpe, G.\n\n\n \n\n\n\n Physical Chemistry Chemical Physics, 17(34): 21824–21836. 2015.\n \n\n\n\n
\n\n\n\n \n \n $\"Nuclear$ Paper\n \n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n \n \n\n\n\n

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@article{mentink-vigier_nuclear_2015,\n\ttitle = {Nuclear depolarization and absolute sensitivity in magic-angle spinning cross effect dynamic nuclear polarization},\n\tvolume = {17},\n\tissn = {1463-9076},\n\turl = {http://xlink.rsc.org/?DOI=C5CP03457D},\n\tdoi = {10.1039/C5CP03457D},\n\tabstract = {Biradicals' performance in MAS-DNP experiments should be revised to account for substantial field-dependent nuclear polarization losses that depend on experimental conditions and biradical properties.},\n\tnumber = {34},\n\tjournal = {Physical Chemistry Chemical Physics},\n\tauthor = {Mentink-Vigier, Frédéric and Paul, Subhradip and Lee, Daniel and Feintuch, Akiva and Hediger, Sabine and Vega, Shimon and De Paëpe, Gaël},\n\tyear = {2015},\n\tkeywords = {\\#nosource},\n\tpages = {21824--21836},\n}\n\n

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\n \n\n \n \n \n \n \n Solid-State NMR and DFT Combined for the Surface Study of Functionalized Silicon Nanoparticles.\n \n \n \n\n\n \n Lee, D.; Kaushik, M.; Coustel, R.; Chenavier, Y.; Chanal, M.; Bardet, M.; Dubois, L.; Okuno, H.; Rochat, N.; Duclairoir, F.; Mouesca, J.; and De Paëpe, G.\n\n\n \n\n\n\n Chemistry - A European Journal, 21(45): 16047–16058. 2015.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n \n \n\n\n\n

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@article{lee_solid-state_2015,\n\ttitle = {Solid-{State} {NMR} and {DFT} {Combined} for the {Surface} {Study} of {Functionalized} {Silicon} {Nanoparticles}},\n\tvolume = {21},\n\tdoi = {10.1002/chem.201502687},\n\tabstract = {Silicon nanoparticles (NPs) serve a wide range of optical, electronic, and biological applications. Chemical grafting of various molecules to Si NPs can help to passivate their reactive surfaces, "fine-tune" their properties, or even give them further interesting features. In this work, 1H, 13C, and 29Si solid-state NMR spectroscopy has been combined with density functional theory calculations to study the surface chemistry of hydride-terminated and alkyl-functionalized Si NPs. This combination of techniques yields assignments for the observed chemical shifts, including the contributions resulting from different surface planes, and highlights the presence of physisorbed water. Resonances from near-surface 13C nuclei were shown to be substantially broadened due to surface disorder and it is demonstrated that in an ambient environment hydride-terminated Si NPs undergo fast back-bond oxidation, whereas long-chain alkyl-functionalized Si NPs undergo slow oxidation. Furthermore, the combination of NMR spectroscopy and DFT calculations showed that the employed hydrosilylation reaction involves anti-Markovnikov addition of the 1-alkene to the surface of the Si NPs.},\n\tnumber = {45},\n\tjournal = {Chemistry - A European Journal},\n\tauthor = {Lee, D. and Kaushik, M. and Coustel, R. and Chenavier, Y. and Chanal, M. and Bardet, M. and Dubois, L. and Okuno, H. and Rochat, N. and Duclairoir, F. and Mouesca, J.-M. and De Paëpe, G.},\n\tyear = {2015},\n\tkeywords = {\\#nosource},\n\tpages = {16047--16058},\n}\n\n

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\n \n\n \n \n \n \n \n \n Is solid-state NMR enhanced by dynamic nuclear polarization?.\n \n \n \n \n\n\n \n Lee, D.; Hediger, S.; and De Paëpe, G.\n\n\n \n\n\n\n Solid State Nuclear Magnetic Resonance, 66-67: 6–20. April 2015.\n \n\n\n\n
\n\n\n\n \n \n $\"Is$ Paper\n \n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n \n \n \n \n \n \n \n \n\n\n\n

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@article{lee_is_2015,\n\ttitle = {Is solid-state {NMR} enhanced by dynamic nuclear polarization?},\n\tvolume = {66-67},\n\tissn = {09262040},\n\turl = {http://www.sciencedirect.com/science/article/pii/S0926204015000041 http://linkinghub.elsevier.com/retrieve/pii/S0926204015000041 https://linkinghub.elsevier.com/retrieve/pii/S0926204015000041},\n\tdoi = {10.1016/j.ssnmr.2015.01.003},\n\tabstract = {The recent trend of high-field (∼5–20T), low-temperature (∼100K) ssNMR combined with dynamic nuclear polarization (DNP) under magic angle spinning (MAS) conditions is analyzed. A brief overview of the current theory of hyperpolarization for so-called MAS-DNP experiments is given, along with various reasons why the DNP-enhancement, the ratio of the NMR signal intensities obtained in the presence and absence of microwave irradiation suitable for hyperpolarization, should not be used alone to gauge the value of performing MAS-DNP experiments relative to conventional ssNMR. This is demonstrated through a dissection of the current conditions required for MAS-DNP with particular attention to resulting absolute sensitivities and spectral resolution. Consequently, sample preparation methods specifically avoiding the surplus of glass-forming solvents so as to improve the absolute sensitivity and resolution are discussed, as are samples that are intrinsically pertinent for MAS-DNP studies (high surface area, amorphous, and porous). Owing to their pertinence, examples of recent applications on these types of samples where chemically-relevant information has been obtained that would have been impossible without the sensitivity increases bestowed by MAS-DNP are also detailed. Additionally, a promising further implementation for MAS-DNP is exampled, whereby the sensitivity improvements shown for (correlation) spectroscopy of nuclei at low natural isotopic abundance, facilitate internuclear distance measurements, especially for long distances (absence of dipolar truncation). Finally, we give some speculative perspectives for MAS-DNP.},\n\tjournal = {Solid State Nuclear Magnetic Resonance},\n\tauthor = {Lee, Daniel and Hediger, Sabine and De Paëpe, Gaël},\n\tmonth = apr,\n\tyear = {2015},\n\tkeywords = {\\#nosource, Dynamic nuclear polarization, Magic angle spinning, Solid-state NMR},\n\tpages = {6--20},\n}\n\n

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\n \n\n \n \n \n \n \n Matrix-Free DNP-Enhanced NMR Spectroscopy of Liposomes Using a Lipid-Anchored Biradical.\n \n \n \n\n\n \n Fernández-de-Alba, C.; Takahashi, H.; Richard, A.; Chenavier, Y.; Dubois, L.; Maurel, V.; Lee, D.; Hediger, S.; and De Paëpe, G.\n\n\n \n\n\n\n Chemistry - A European Journal, 21(12): 4512–4517. 2015.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n \n \n \n \n \n \n \n \n \n \n \n \n\n\n\n

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@article{fernandez-de-alba_matrix-free_2015,\n\ttitle = {Matrix-{Free} {DNP}-{Enhanced} {NMR} {Spectroscopy} of {Liposomes} {Using} a {Lipid}-{Anchored} {Biradical}},\n\tvolume = {21},\n\tdoi = {10.1002/chem.201404588},\n\tabstract = {Magic-angle spinning dynamic nuclear polarization (MAS-DNP) has been proven to be a powerful technique to enhance the sensitivity of solid-state NMR (SSNMR) in a wide range of systems. Here, we show that DNP can be used to polarize lipids using a lipid-anchored polarizing agent. More specifically, we introduce a C16-functionalized biradical, which allows localization of the polarizing agents in the lipid bilayer and DNP experiments to be performed in the absence of excess cryo-protectant molecules (glycerol, dimethyl sulfoxide, etc.). This constitutes another original example of the matrix-free DNP approach that we recently introduced.},\n\tnumber = {12},\n\tjournal = {Chemistry - A European Journal},\n\tauthor = {Fernández-de-Alba, C. and Takahashi, H. and Richard, A. and Chenavier, Y. and Dubois, L. and Maurel, V. and Lee, D. and Hediger, S. and De Paëpe, G.},\n\tyear = {2015},\n\tkeywords = {\\#nosource, NMR spectroscopy, dynamic nuclear polarization, membranes, phospholipids, solid-state NMR spectroscopy},\n\tpages = {4512--4517},\n}\n\n

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\n \n\n \n \n \n \n \n \n A New Tool for NMR Crystallography: Complete $^{\\textrm{13}}$ C/ $^{\\textrm{15}}$ N Assignment of Organic Molecules at Natural Isotopic Abundance Using DNP-Enhanced Solid-State NMR.\n \n \n \n \n\n\n \n Märker, K.; Pingret, M.; Mouesca, J.; Gasparutto, D.; Hediger, S.; and De Paëpe, G.\n\n\n \n\n\n\n Journal of the American Chemical Society, 137(43): 13796–13799. November 2015.\n Publisher: American Chemical Society ISBN: 10.1021/jacs.5b09964\n\n\n\n
\n\n\n\n \n \n $\"A$ Paper\n \n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 1 download\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n \n \n\n\n\n

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@article{Marker2015,\n\ttitle = {A {New} {Tool} for {NMR} {Crystallography}: {Complete} $^{\\textrm{13}}$ {C}/ $^{\\textrm{15}}$ {N} {Assignment} of {Organic} {Molecules} at {Natural} {Isotopic} {Abundance} {Using} {DNP}-{Enhanced} {Solid}-{State} {NMR}},\n\tvolume = {137},\n\tissn = {0002-7863, 1520-5126},\n\turl = {https://pubs.acs.org/doi/10.1021/jacs.5b09964},\n\tdoi = {10.1021/jacs.5b09964},\n\tabstract = {NMR crystallography of organic molecules at natural isotopic abundance (NA) strongly relies on the comparison of assigned experimental and computed NMR chemical shifts. However, a broad applicability of this approach is often hampered by the still limited (1)H resolution and/or difficulties in assigning (13)C and (15)N resonances without the use of structure-based chemical shift calculations. As shown here, such difficulties can be overcome by (13)C-(13)C and for the first time (15)N-(13)C correlation experiments, recorded with the help of dynamic nuclear polarization. We present the complete de novo (13)C and (15)N resonance assignment at NA of a self-assembled 2'-deoxyguanosine derivative presenting two different molecules in the asymmetric crystallographic unit cell. This de novo assignment method is exclusively based on aforementioned correlation spectra and is an important addition to the NMR crystallography approach, rendering firstly (1)H assignment straightforward, and being secondly a prerequisite for distance measurements with solid-state NMR.},\n\tnumber = {43},\n\tjournal = {Journal of the American Chemical Society},\n\tauthor = {Märker, Katharina and Pingret, Morgane and Mouesca, Jean-Marie and Gasparutto, Didier and Hediger, Sabine and De Paëpe, Gaël},\n\tmonth = nov,\n\tyear = {2015},\n\tpmid = {26485326},\n\tnote = {Publisher: American Chemical Society\nISBN: 10.1021/jacs.5b09964},\n\tkeywords = {Classic Paper},\n\tpages = {13796--13799},\n}\n\n

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\n \n\n \n \n \n \n \n Pushing NMR sensitivity limits using dynamic nuclear polarization with closed-loop cryogenic helium sample spinning.\n \n \n \n\n\n \n Bouleau, E.; Saint-Bonnet, P.; Mentink-Vigier, F.; Takahashi, H.; Jacquot, J.; Bardet, M.; Aussenac, F.; Purea, A.; Engelke, F.; Hediger, S.; Lee, D.; and De Paëpe, G.\n\n\n \n\n\n\n Chemical Science, 6(12): 6806–6812. 2015.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

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@article{bouleau_pushing_2015,\n\ttitle = {Pushing {NMR} sensitivity limits using dynamic nuclear polarization with closed-loop cryogenic helium sample spinning},\n\tvolume = {6},\n\tdoi = {10.1039/c5sc02819a},\n\tabstract = {We report a strategy to push the limits of solid-state NMR sensitivity far beyond its current state-of-the-art. The approach relies on the use of dynamic nuclear polarization and demonstrates unprecedented DNP enhancement factors for experiments performed at sample temperatures much lower than 100 K, and can translate into 6 orders of magnitude of experimental time-savings. This leap-forward was made possible thanks to the employment of cryogenic helium as the gas to power magic angle sample spinning (MAS) for dynamic nuclear polarization (DNP) enhanced NMR experiments. These experimental conditions far exceed what is currently possible and allows currently reaching sample temperatures down to 30 K while conducting experiments with improved resolution (thanks to faster spinning frequencies, up to 25 kHz) and highly polarized nuclear spins. The impressive associated gains were used to hyperpolarize the surface of an industrial catalyst as well as to hyperpolarize organic nano-assemblies (self-assembling peptides in our case), for whom structures cannot be solved using diffraction techniques. Sustainable cryogenic helium sample spinning significantly enlarges the realm and possibilities of the MAS-DNP technique and is the route to transform NMR into a versatile but also sensitive atomic-level characterization tool.},\n\tnumber = {12},\n\tjournal = {Chemical Science},\n\tauthor = {Bouleau, E. and Saint-Bonnet, P. and Mentink-Vigier, F. and Takahashi, H. and Jacquot, J.-F. and Bardet, M. and Aussenac, F. and Purea, A. and Engelke, F. and Hediger, S. and Lee, D. and De Paëpe, G.},\n\tyear = {2015},\n\tpages = {6806--6812},\n}\n\n

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\n \n 2014\n \n \n (3)\n \n \n

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\n \n\n \n \n \n \n \n \n Optimization of an absolute sensitivity in a glassy matrix during DNP-enhanced multidimensional solid-state NMR experiments.\n \n \n \n \n\n\n \n Takahashi, H.; Fernández-De-Alba, C.; Lee, D.; Maurel, V.; Gambarelli, S.; Bardet, M.; Hediger, S.; Barra, A. L. A.; and De Paëpe, G.\n\n\n \n\n\n\n Journal of Magnetic Resonance, 239: 91–99. February 2014.\n \n\n\n\n
\n\n\n\n \n \n $\"Optimization$ Paper\n \n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 1 download\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n \n \n \n \n \n \n \n \n \n \n \n \n \n \n\n\n\n

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@article{takahashi_optimization_2014,\n\ttitle = {Optimization of an absolute sensitivity in a glassy matrix during {DNP}-enhanced multidimensional solid-state {NMR} experiments},\n\tvolume = {239},\n\tissn = {10907807},\n\turl = {http://www.mendeley.com/catalog/optimization-absolute-sensitivity-glassy-matrix-during-dnpenhanced-multidimensional-solidstate-nmr-e/},\n\tdoi = {10.1016/j.jmr.2013.12.005},\n\tabstract = {Thanks to instrumental and theoretical development, notably the access to high-power and high-frequency microwave sources, high-field dynamic nuclear polarization (DNP) on solid-state NMR currently appears as a promising solution to enhance nuclear magnetization in many different types of systems. In magic-angle-spinning DNP experiments, systems of interest are usually dissolved or suspended in glass-forming matrices doped with polarizing agents and measured at low temperature (down to ∼100 K). In this work, we discuss the influence of sample conditions (radical concentration, sample temperature, etc.) on DNP enhancements and various nuclear relaxation times which affect the absolute sensitivity of DNP spectra, especially in multidimensional experiments. Furthermore, DNP-enhanced solid-state NMR experiments performed at 9.4 T are complemented by high-field CW EPR measurements performed at the same magnetic field. Microwave absorption by the DNP glassy matrix is observed even below the glass transition temperature caused by softening of the glass. Shortening of electron relaxation times due to glass softening and its impact in terms of DNP sensitivity is discussed. ©2014 Published by Elsevier Inc.},\n\tjournal = {Journal of Magnetic Resonance},\n\tauthor = {Takahashi, Hiroki and Fernández-De-Alba, Carlos and Lee, Daniel and Maurel, Vincent and Gambarelli, Serge and Bardet, Michel and Hediger, Sabine and Barra, Anne-Laure Laure A.-L. and De Paëpe, Gaël},\n\tmonth = feb,\n\tyear = {2014},\n\tpmid = {24480716},\n\tkeywords = {\\#nosource, Absolute sensitivity ratio, Dynamic nuclear polarization, Glassy solution, High-field EPR, Microwave absorption, Solid-state NMR},\n\tpages = {91--99},\n}\n\n

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\n \n\n \n \n \n \n \n \n Dynamic nuclear polarization NMR of low-$γ$ nuclei: Structural insights into hydrated yttrium-doped BaZrO3.\n \n \n \n \n\n\n \n Blanc, F.; Sperrin, L.; Lee, D.; Dervişoǧlu, R.; Yamazaki, Y.; Haile, S. M; De Paëpe, G.; and Grey, C. P\n\n\n \n\n\n\n Journal of Physical Chemistry Letters, 5(14): 2431–2436. July 2014.\n Publisher: American Chemical Society\n\n\n\n
\n\n\n\n \n \n $\"Dynamic$ Paper\n \n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n \n \n \n \n \n \n \n \n \n \n\n\n\n

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@article{Blanc2014,\n\ttitle = {Dynamic nuclear polarization {NMR} of low-\\$γ\\$ nuclei: {Structural} insights into hydrated yttrium-doped {BaZrO3}},\n\tvolume = {5},\n\tissn = {19487185},\n\turl = {http://www.scopus.com/inward/record.url?eid=2-s2.0-84904597815&partnerID=tZOtx3y1},\n\tdoi = {10.1021/jz5007669},\n\tabstract = {We demonstrate that solid-state NMR spectra of challenging nuclei with a low gyromagnetic ratio such as yttrium-89 can be acquired quickly with indirect dynamic nuclear polarization (DNP) methods. Proton to 89Y cross polarization (CP) magic angle spinning (MAS) spectra of Y3+ in a frozen aqueous solution were acquired in minutes using the AMUPol biradical as a polarizing agent. Subsequently, the detection of the 89Y and 1H NMR signals from technologically important hydrated yttrium-doped zirconate ceramics, in combination with DFT calculations, allows the local yttrium and proton environments present in these protonic conductors to be detected and assigned to different hydrogen-bonded environments. We demonstrate that solid-state NMR spectra of challenging nuclei with a low gyromagnetic ratio such as yttrium-89 can be acquired quickly with indirect dynamic nuclear polarization (DNP) methods. Proton to 89Y cross polarization (CP) magic angle spinning (MAS) spectra of Y3+ in a frozen aqueous solution were acquired in minutes using the AMUPol biradical as a polarizing agent. Subsequently, the detection of the 89Y and 1H NMR signals from technologically important hydrated yttrium-doped zirconate ceramics, in combination with DFT calculations, allows the local yttrium and proton environments present in these protonic conductors to be detected and assigned to different hydrogen-bonded environments.},\n\tnumber = {14},\n\tjournal = {Journal of Physical Chemistry Letters},\n\tauthor = {Blanc, Frédéric and Sperrin, Luke and Lee, Daniel and Dervişoǧlu, Riza and Yamazaki, Yoshihiro and Haile, Sossina M and De Paëpe, Gaël and Grey, Clare P},\n\tmonth = jul,\n\tyear = {2014},\n\tnote = {Publisher: American Chemical Society},\n\tkeywords = {\\#nosource, dynamic nuclear polarization, hydrated yttrium-doped barium zirconate, solid-state nuclear magnetic resonance, yttrium-89},\n\tpages = {2431--2436},\n}\n\n

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\n \n\n \n \n \n \n \n Untangling the condensation network of organosiloxanes on nanoparticles using 2D 29Si-29Si solid-state NMR enhanced by dynamic nuclear polarization.\n \n \n \n\n\n \n Lee, D.; Monin, G.; Duong, N.; Lopez, I.; Bardet, M.; Mareau, V.; Gonon, L.; and De Paëpe, G.\n\n\n \n\n\n\n Journal of the American Chemical Society, 136(39): 13781–13788. 2014.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

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@article{lee_untangling_2014,\n\ttitle = {Untangling the condensation network of organosiloxanes on nanoparticles using {2D} {29Si}-{29Si} solid-state {NMR} enhanced by dynamic nuclear polarization},\n\tvolume = {136},\n\tdoi = {10.1021/ja506688m},\n\tabstract = {Silica (SiO2) nanoparticles (NPs) were functionalized by silanization to produce a surface covered with organosiloxanes. Information about the surface coverage and the nature, if any, of organosiloxane polymerization, whether parallel or perpendicular to the surface, is highly desired. To this extent, two-dimensional homonuclear 29Si solid-state NMR could be employed. However, owing to the sensitivity limitations associated with the low natural abundance (4.7\\%) of 29Si and the difficulty and expense of isotopic labeling here, this technique would usually be deemed impracticable. Nevertheless, we show that recent developments in the field of dynamic nuclear polarization under magic angle spinning (MAS-DNP) could be used to dramatically increase the sensitivity of the NMR experiments, resulting in a timesaving factor of 625 compared to conventional solid-state NMR. This allowed the acquisition of previously infeasible data. Using both through-space and through-bond 2D 29Si-29Si correlation experiments, it is shown that the required reaction conditions favor lateral polymerization and domain growth. Moreover, the natural abundance correlation experiments permitted the estimation of 2JSi-O-Si-couplings (13.8 ± 1.4 Hz for surface silica) and interatomic distances (3.04 ± 0.08 Å for surface silica) since complications associated with many-spin systems and also sensitivity were avoided. The work detailed herein not only demonstrates the possibility of using MAS-DNP to greatly facilitate the acquisition of 2D 29Si-29Si correlation spectra but also shows that this technique can be used in a routine fashion to characterize surface grafting networks and gain structural constraints, which can be related to a system's chemical and physical properties.},\n\tnumber = {39},\n\tjournal = {Journal of the American Chemical Society},\n\tauthor = {Lee, D. and Monin, G. and Duong, N.T. and Lopez, I.Z. and Bardet, M. and Mareau, V. and Gonon, L. and De Paëpe, G.},\n\tyear = {2014},\n\tpages = {13781--13788},\n}\n\n

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\n \n\n \n \n \n \n \n Solid-state NMR on bacterial cells: Selective cell wall signal enhancement and resolution improvement using dynamic nuclear polarization.\n \n \n \n\n\n \n Takahashi, H.; Ayala, I.; Bardet, M.; De Paëpe, G.; Simorre, J.; and Hediger, S.\n\n\n \n\n\n\n Journal of the American Chemical Society, 135(13): 5105–5110. 2013.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 1 download\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n \n \n\n\n\n

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@article{takahashi_solid-state_2013,\n\ttitle = {Solid-state {NMR} on bacterial cells: {Selective} cell wall signal enhancement and resolution improvement using dynamic nuclear polarization},\n\tvolume = {135},\n\tdoi = {10.1021/ja312501d},\n\tabstract = {Dynamic nuclear polarization (DNP) enhanced solid-state nuclear magnetic resonance (NMR) has recently emerged as a powerful technique for the study of material surfaces. In this study, we demonstrate its potential to investigate cell surface in intact cells. Using Bacillus subtilis bacterial cells as an example, it is shown that the polarizing agent 1-(TEMPO-4-oxy)-3-(TEMPO-4-amino) propan-2-ol (TOTAPOL) has a strong binding affinity to cell wall polymers (peptidoglycan). This particular interaction is thoroughly investigated with a systematic study on extracted cell wall materials, disrupted cells, and entire cells, which proved that TOTAPOL is mainly accumulating in the cell wall. This property is used on one hand to selectively enhance or suppress cell wall signals by controlling radical concentrations and on the other hand to improve spectral resolution by means of a difference spectrum. Comparing DNP-enhanced and conventional solid-state NMR, an absolute sensitivity ratio of 24 was obtained on the entire cell sample. This important increase in sensitivity together with the possibility of enhancing specifically cell wall signals and improving resolution really opens new avenues for the use of DNP-enhanced solid-state NMR as an on-cell investigation tool. © 2013 American Chemical Society.},\n\tnumber = {13},\n\tjournal = {Journal of the American Chemical Society},\n\tauthor = {Takahashi, H. and Ayala, I. and Bardet, M. and De Paëpe, G. and Simorre, J.-P. and Hediger, S.},\n\tyear = {2013},\n\tkeywords = {\\#nosource},\n\tpages = {5105--5110},\n}\n\n

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\n \n\n \n \n \n \n \n Application of 7Li NMR to characterize the evolution of intercalated and non-intercalated lithium in LiFePO4-based materials for Li-ion batteries.\n \n \n \n\n\n \n Buzlukov, A.; Gerbaud, G.; Bourbon, C.; Hediger, S.; De Paëpe, G.; Patoux, S.; and Bardet, M.\n\n\n \n\n\n\n Journal of Solid State Electrochemistry, 17(5): 1421–1427. 2013.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n \n \n\n\n\n

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@article{buzlukov_application_2013,\n\ttitle = {Application of {7Li} {NMR} to characterize the evolution of intercalated and non-intercalated lithium in {LiFePO4}-based materials for {Li}-ion batteries},\n\tvolume = {17},\n\tdoi = {10.1007/s10008-013-2011-9},\n\tabstract = {Different synthesis batches of LiFePO4/C materials were prepared, and their electrochemical properties as positive cathodes for lithium-ion batteries were evaluated. Using standard solid-state NMR conditions, such as a 7-mm magic-angle-spinning probe performing at low spinning rates, information on both intercalated and non-intercalated (stored on the grain boundaries) lithium was obtained. A sharp signal assigned to non-intercalated lithium could be observed by diluting the active material in silica. Correlations could be, thus, obtained between the amount of each type of lithium and the electrochemical history and state of the material, revealing that the relative amount of surface lithium in a pristine LiFePO4/C material is rather constant and cannot be used as a criterion for its further specification. However, a drastic increase of this surface lithium was observed in the cathode materials of out-of-order batteries. As the cathode material recovered from the batteries after electrochemical testing was carefully washed before analysis, we can conclude that the non-intercalated lithium is strongly bound to the active material probably inside the so-called solid electrolyte interface layer at the surfaces of LiFePO4 particles. This work illustrates that solid-state lithium NMR can allow rapid characterization and testing of LiFePO4/C cathode materials. © 2013 Springer-Verlag Berlin Heidelberg.},\n\tnumber = {5},\n\tjournal = {Journal of Solid State Electrochemistry},\n\tauthor = {Buzlukov, A. and Gerbaud, G. and Bourbon, C. and Hediger, S. and De Paëpe, G. and Patoux, S. and Bardet, M.},\n\tyear = {2013},\n\tkeywords = {\\#nosource},\n\tpages = {1421--1427},\n}\n\n

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\n \n\n \n \n \n \n \n \n Towards Structure Determination of Self-Assembled Peptides Using Dynamic Nuclear Polarization Enhanced Solid-State NMR Spectroscopy.\n \n \n \n \n\n\n \n Takahashi, H.; Viverge, B.; Lee, D.; Rannou, P.; and De Paëpe, G.\n\n\n \n\n\n\n Angewandte Chemie International Edition, 52(27): 6979–6982. July 2013.\n \n\n\n\n
\n\n\n\n \n \n $\"Towards$ Paper\n \n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n \n \n \n \n \n \n \n \n \n \n\n\n\n

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@article{takahashi_towards_2013,\n\ttitle = {Towards {Structure} {Determination} of {Self}-{Assembled} {Peptides} {Using} {Dynamic} {Nuclear} {Polarization} {Enhanced} {Solid}-{State} {NMR} {Spectroscopy}},\n\tvolume = {52},\n\tissn = {14337851},\n\turl = {https://onlinelibrary.wiley.com/doi/10.1002/anie.201210093},\n\tdoi = {10.1002/anie.201210093},\n\tabstract = {Supra-sensitivity: Dynamic nuclear polarization (DNP) enhanced solid-state NMR spectroscopy was performed on self-assembled peptide nanotubes. This approach yields significant experimental time savings (about five orders of magnitude; see picture) and was used to exemplify the feasibility of supramolecular structural studies of organic nanoassemblies at an atomic scale using DNP-enhanced solid-state NMR spectroscopy. Copyright © 2013 WILEY-VCH Verlag GmbH \\& Co. KGaA, Weinheim.},\n\tnumber = {27},\n\tjournal = {Angewandte Chemie International Edition},\n\tauthor = {Takahashi, Hiroki and Viverge, Bastien and Lee, Daniel and Rannou, Patrice and De Paëpe, Gaël},\n\tmonth = jul,\n\tyear = {2013},\n\tkeywords = {Magnetic Resonance Spectroscopy, Magnetic Resonance Spectroscopy: methods, Nanostructures, Peptides, Peptides: chemistry},\n\tpages = {6979--6982},\n}\n\n

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\n \n 2012\n \n \n (3)\n \n \n

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\n \n\n \n \n \n \n \n High field dynamic nuclear polarization and electron paramagnetic resonance \\textbar Polarisation dynamique nucléaire à haut champ magnétique et résonance paramagnétique électronique.\n \n \n \n\n\n \n De Paëpe, G.; and Gambarelli, S.\n\n\n \n\n\n\n Actualite Chimique, (364-365): 111–116. 2012.\n \n\n\n\n
\n\n\n\n \n\n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n \n \n\n\n\n

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@article{de_paepe_high_2012,\n\ttitle = {High field dynamic nuclear polarization and electron paramagnetic resonance {\\textbar} {Polarisation} dynamique nucléaire à haut champ magnétique et résonance paramagnétique électronique},\n\tabstract = {This article relates two recently developed magnetic spectroscopy methods. Both methods use the electron magnetic moment, which is significantly more intense than the more commonly used nuclear magnetic moment. This is because, at a given temperature and magnetic field, electrons are much more strongly polarised than nuclei. This property is used in dynamic nuclear polarisation (DNP) to increase the sensitivity of nuclear spin detection by several orders of magnitude. This article first describes how the recent development of high-frequency microwave sources and DNP probes compatible with pneumatic rotation of the sample ("magic angle spinning") have extended this hyperpolarisation technique to the most intense magnetic fields currently available ({\\textbackslash}textgreater 10 tesla). The second part shows how a strong electron magnetic moment allows to measure long distances in disordered systems by pulsed electron paramagnetic resonance. By measuring the dipolar interaction between two electron spins, using a sequence known as DEER, it becomes possible to measure distances up to 80 Å in disordered systems. This technique has many applications in chemistry and biology.},\n\tnumber = {364-365},\n\tjournal = {Actualite Chimique},\n\tauthor = {De Paëpe, G. and Gambarelli, S.},\n\tyear = {2012},\n\tkeywords = {\\#nosource},\n\tpages = {111--116},\n}\n\n

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\n \n\n \n \n \n \n \n Dynamics property recovery of archaeological-wood fibers treated with polyethylene glycol demonstrated by high-resolution solid-state NMR.\n \n \n \n\n\n \n Bardet, M.; Gerbaud, G.; Doan, C.; Giffard, M.; Hediger, S.; De Paëpe, G.; and Trân, Q.\n\n\n \n\n\n\n Cellulose, 19(5): 1537–1545. 2012.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n \n \n\n\n\n

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@article{bardet_dynamics_2012,\n\ttitle = {Dynamics property recovery of archaeological-wood fibers treated with polyethylene glycol demonstrated by high-resolution solid-state {NMR}},\n\tvolume = {19},\n\tdoi = {10.1007/s10570-012-9736-y},\n\tabstract = {We used high-resolution Solid-State 13C NMR to better understand and optimize the conservation process of archaeological waterlogged woods by polyethylene glycol (PEG) impregnation via the study of the molecular interactions between PEG and residual celluloses. By both deconvoluting NMR spectra and analyzing the behavior of 13C magnetization build-up under proton to carbon cross-polarization conditions, we were able to quantify PEG penetration and extract parameters sensitive to molecular dynamics such as proton spin lattice-relaxation-time constants in the rotating frame T 1ρH and the cross-relaxation time constant T CH. By exploring a large range of PEG concentrations for the impregnating solutions we show that the PEG penetrates inside the fibers and interacts at a molecular level with the cellulose fibrils thus restoring the dynamics properties of the damaged molecular cell wall network. At high PEG concentration, the polymer accumulates in the remaining free volume with more and looser molecular interactions with the residual wood components. This feature explains the facility for these hydroscopic materials to exude from the wood and led to deleterious consequences for the restored artefacts. © 2012 Springer Science+Business Media B.V.},\n\tnumber = {5},\n\tjournal = {Cellulose},\n\tauthor = {Bardet, M. and Gerbaud, G. and Doan, C. and Giffard, M. and Hediger, S. and De Paëpe, G. and Trân, Q.-K.},\n\tyear = {2012},\n\tkeywords = {\\#nosource},\n\tpages = {1537--1545},\n}\n\n

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\n \n\n \n \n \n \n \n \n Compensated second-order recoupling: application to third spin assisted recoupling.\n \n \n \n \n\n\n \n Giffard, M.; Hediger, S.; Lewandowski, J. R; Bardet, M.; Simorre, J.; Griffin, R. G; and De Paëpe, G.\n\n\n \n\n\n\n Physical chemistry chemical physics : PCCP, 14(20): 7246–7255. May 2012.\n Publisher: The Royal Society of Chemistry\n\n\n\n
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@article{Giffard2012,\n\ttitle = {Compensated second-order recoupling: application to third spin assisted recoupling.},\n\tvolume = {14},\n\tissn = {1463-9084},\n\turl = {http://pubs.rsc.org/en/content/articlehtml/2012/cp/c2cp40406k},\n\tdoi = {10.1039/c2cp40406k},\n\tabstract = {We consider the effect of phase shifts in the context of second-order recoupling techniques in solid-state NMR. Notably we highlight conditions leading to significant improvements for the Third Spin Assisted Recoupling (TSAR) mechanism and demonstrate the benefits of resulting techniques for detecting long-distance transfer in biomolecular systems. The modified pulse sequences of PAR and PAIN-CP, Phase-Shifted Proton Assisted Recoupling (AH-PS-PAR) and Phase-Shifted Proton-Assisted Insensitive Nuclei Cross Polarization (ABH-PS-PAIN-CP), still rely on cross terms between heteronuclear dipolar couplings involving assisting protons that mediate zero-quantum polarization transfer between low-\\$γ\\$ nuclei ((13)C-(13)C, (15)N-(15)N, (15)N-(13)C polarization transfer). Using Average Hamiltonian Theory we show that phase inversion compensates off-resonance contributions and yields improved polarization transfer as well as substantial broadening of the matching conditions. PS-TSAR greatly improves on the standard TSAR based methods because it alleviates their sensitivity to precise RF settings which significantly enhances robustness of the experiments. We demonstrate these new methods on a 19.6 kDa protein (U-[(15)N, (13)C]-YajG) at high magnetic fields (up to 900 MHz (1)H frequency) and fast sample spinning (up to 65 kHz MAS frequency).},\n\tnumber = {20},\n\tjournal = {Physical chemistry chemical physics : PCCP},\n\tauthor = {Giffard, Mathilde and Hediger, Sabine and Lewandowski, Józef R and Bardet, Michel and Simorre, Jean-Pierre and Griffin, Robert G and De Paëpe, Gaël},\n\tmonth = may,\n\tyear = {2012},\n\tpmid = {22513727},\n\tnote = {Publisher: The Royal Society of Chemistry},\n\tkeywords = {Alanine, Alanine: chemistry, Algorithms, Biomolecular, Biomolecular: methods, Carbon Isotopes, Carbon Isotopes: chemistry, Chemical, Computer Simulation, Models, Nitrogen Isotopes, Nitrogen Isotopes: chemistry, Nitrogen Radioisotopes, Nitrogen Radioisotopes: chemistry, Nuclear Magnetic Resonance, Proteins, Proteins: chemistry, Protons},\n\tpages = {7246--7255},\n}\n\n

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