{"_id":"Q6eDirwuPZnRQS93j","bibbaseid":"anonymous-polymethacrylatemonolithswithimmobilizedpoly3mercaptopropylmethylsiloxanefilmforhighcoveragesurfacefunctionalizationbythioleneclickreaction-2014","bibdata":{"bibtype":"article","type":"article","author":[{"propositions":[],"lastnames":["Carrasco-Correa"],"firstnames":["E.J."],"suffixes":[]},{"propositions":[],"lastnames":["Ramis-Ramos"],"firstnames":["G."],"suffixes":[]},{"propositions":[],"lastnames":["Herrero-Martínez"],"firstnames":["J.M."],"suffixes":[]},{"propositions":[],"lastnames":["Lämmerhofer"],"firstnames":["M."],"suffixes":[]}],"title":"Polymethacrylate monoliths with immobilized poly-3-mercaptopropyl methylsiloxane film for high-coverage surface functionalization by thiol-ene click reaction","journal":"Journal of Chromatography A","year":"2014","volume":"1367","pages":"123-130","doi":"10.1016/j.chroma.2014.09.066","note":"cited By 29","url":"https://www.scopus.com/inward/record.uri?eid=2-s2.0-84908220761&doi=10.1016%2fj.chroma.2014.09.066&partnerID=40&md5=af7e3b45fc08aa1abd2a17be92df2147","affiliation":"Department de Química Analítica, Universitat de València, Dr. Moliner 50, Burjassot, Valencia, 46100, Spain; Institute of Pharmaceutical Sciences, University of Tübingen, Tübingen, 72076, Germany","abstract":"In this work, new polythiol-functionalized macroporous monolithic polymethacrylate-polysiloxane composite materials are presented which can be useful substrates for highly efficient immobilization of (chiral) catalysts, chromatographic ligands, and other functional moieties by thiol-ene click reaction. Poly(glycidyl methacrylate-. co-ethylene dimethacrylate) (poly(GMA-. co-EDMA)) monoliths were coated with a poly-3-mercaptopropyl methylsiloxane (PMPMS) film and subsequently the polymer was covalently immobilized by formation of crosslinks via nucleophilic substitution reaction with pendent 2,3-epoxypropyl groups on the monolith surface. This monolith, though, showed similar levels of surface coverage as a reference monolith obtained by opening of the epoxide groups with sodium hydrogen sulfide. However, a 3-step functionalization by amination of the epoxy monolith, followed by its vinylation with allylglycidyl ether and subsequent thiolation by coating of a thin polythiol (PMPMS) film and crosslinking by click reaction furnished a monolith with more than 2-fold elevated thiol coverage. Its further functionalization with a clickable chiral quinine carbamate selector clearly documented the benefit of highly dense thiol surfaces for such reactions and synthesis of functional materials with proper ligand loadings. The new monoliths were chromatographically tested in capillary electrochromatography mode using N-3,5-dinitrobenzoyl-leucine as chiral probe and the capillary column with the monolith having the highest selector coverage, produced from the precursor with the most thiols on the surface, showed the largest separation factor. By performic acid oxidation the surface characteristic could be tuned and strongly altered due to a delicate balance of enantioselective and non-specific interactions. © 2014 Elsevier B.V.","author_keywords":"Capillary column; O-9-tert-butylcarbamoyl quinine; Poly-3-mercaptopropyl methylsiloxane; Reactive monolith; Thiol-covered surfaces; Thiol-ene click reaction","keywords":"Acrylic monomers; Amines; Chelation; Chromatography; Crosslinking; Ethylene; Functional materials; Gas metal arc welding; Ligands; Silicones; Sodium sulfide; Substitution reactions; Sulfur compounds, Capillary columns; Capillary electrochromatography; Methylsiloxane; Non-specific interactions; Nucleophilic substitution reactions; Reactive monolith; Surface Functionalization; Thiol-ene click reactions, Surface reactions, cross linking reagent; ethylene glycol dimethacrylate; glycidyl methacrylate; hydrogen sulfide; monomer; o 9 tert butylcarbamoyl quinine; poly 3 mercaptopropyl methylsiloxane; poly(methyl methacrylate); quinine derivative; sodium hydrogen sulfide; unclassified drug; GMA-EDMA; methacrylic acid methyl ester; polymethacrylic acid; polymethacrylic acid derivative; siloxane; thiol derivative, amination; Article; capillary electrochromatography; catalyst; chemical binding; chemical reaction; chemical structure; controlled study; cross linking; immobilization; oxidation; reaction time; substitution reaction; synthesis; thiol ene click reaction; vinylation; chemistry; devices; heat; liquid chromatography; procedures; reproducibility; surface property, Capillary Electrochromatography; Chromatography, Liquid; Hot Temperature; Methylmethacrylates; Polymethacrylic Acids; Reproducibility of Results; Siloxanes; Sulfhydryl Compounds; Surface Properties","chemicals_cas":"ethylene glycol dimethacrylate, 97-90-5; hydrogen sulfide, 15035-72-0, 7783-06-4; poly(methyl methacrylate), 39320-98-4, 9008-29-1; methacrylic acid methyl ester, 80-62-6; polymethacrylic acid, 25087-26-7; thiol derivative, 13940-21-1; GMA-EDMA; Methylmethacrylates; polymethacrylic acid; Polymethacrylic Acids; Siloxanes; Sulfhydryl Compounds","funding_details":"European Regional Development FundEuropean Regional Development Fund, FEDER","key":"Carrasco-Correa2014123","id":"Carrasco-Correa2014123","bibbaseid":"anonymous-polymethacrylatemonolithswithimmobilizedpoly3mercaptopropylmethylsiloxanefilmforhighcoveragesurfacefunctionalizationbythioleneclickreaction-2014","role":"author","urls":{"Paper":"https://www.scopus.com/inward/record.uri?eid=2-s2.0-84908220761&doi=10.1016%2fj.chroma.2014.09.066&partnerID=40&md5=af7e3b45fc08aa1abd2a17be92df2147"},"keyword":["Acrylic monomers; Amines; Chelation; Chromatography; Crosslinking; Ethylene; Functional materials; Gas metal arc welding; Ligands; Silicones; Sodium sulfide; Substitution reactions; Sulfur compounds","Capillary columns; Capillary electrochromatography; Methylsiloxane; Non-specific interactions; Nucleophilic substitution reactions; Reactive monolith; Surface Functionalization; Thiol-ene click reactions","Surface reactions","cross linking reagent; ethylene glycol dimethacrylate; glycidyl methacrylate; hydrogen sulfide; monomer; o 9 tert butylcarbamoyl quinine; poly 3 mercaptopropyl methylsiloxane; poly(methyl methacrylate); quinine derivative; sodium hydrogen sulfide; unclassified drug; GMA-EDMA; methacrylic acid methyl ester; polymethacrylic acid; polymethacrylic acid derivative; siloxane; thiol derivative","amination; Article; capillary electrochromatography; catalyst; chemical binding; chemical reaction; chemical structure; controlled study; cross linking; immobilization; oxidation; reaction time; substitution reaction; synthesis; thiol ene click reaction; vinylation; chemistry; devices; heat; liquid chromatography; procedures; reproducibility; surface property","Capillary Electrochromatography; Chromatography","Liquid; Hot Temperature; Methylmethacrylates; Polymethacrylic Acids; Reproducibility of Results; Siloxanes; Sulfhydryl Compounds; Surface Properties"],"metadata":{"authorlinks":{}},"html":""},"bibtype":"article","biburl":"https://www.clecem.es/wp-content/uploads/2024/01/scopus.bib","dataSources":["z88YG74vvXjjYpRcn"],"keywords":["acrylic monomers; amines; chelation; chromatography; crosslinking; ethylene; functional materials; gas metal arc welding; ligands; silicones; sodium sulfide; substitution reactions; sulfur compounds","capillary columns; capillary electrochromatography; methylsiloxane; non-specific interactions; nucleophilic substitution reactions; reactive monolith; surface functionalization; thiol-ene click reactions","surface reactions","cross linking reagent; ethylene glycol dimethacrylate; glycidyl methacrylate; hydrogen sulfide; monomer; o 9 tert butylcarbamoyl quinine; poly 3 mercaptopropyl methylsiloxane; poly(methyl methacrylate); quinine derivative; sodium hydrogen sulfide; unclassified drug; gma-edma; methacrylic acid methyl ester; polymethacrylic acid; polymethacrylic acid derivative; siloxane; thiol derivative","amination; article; capillary electrochromatography; catalyst; chemical binding; chemical reaction; chemical structure; controlled study; cross linking; immobilization; oxidation; reaction time; substitution reaction; synthesis; thiol ene click reaction; vinylation; chemistry; devices; heat; liquid chromatography; procedures; reproducibility; surface property","capillary electrochromatography; chromatography","liquid; hot temperature; methylmethacrylates; polymethacrylic acids; reproducibility of results; siloxanes; sulfhydryl compounds; surface properties"],"search_terms":["polymethacrylate","monoliths","immobilized","poly","mercaptopropyl","methylsiloxane","film","high","coverage","surface","functionalization","thiol","ene","click","reaction"],"title":"Polymethacrylate monoliths with immobilized poly-3-mercaptopropyl methylsiloxane film for high-coverage surface functionalization by thiol-ene click reaction","year":2014}