Polymethacrylate monoliths with immobilized poly-3-mercaptopropyl methylsiloxane film for high-coverage surface functionalization by thiol-ene click reaction

• Published in: Journal of Chromatography A 2014-11, Vol.1367, p.123-130
• Main Authors: Carrasco-Correa, Enrique Javier, Ramis-Ramos, Guillermo, Herrero-Martínez, José Manuel, Lämmerhofer, Michael
• Format: Article
• Language: English
• Subjects: Analytical chemistry; Capillary column; Chemistry; Chromatographic methods and physical methods associated with chromatography; Exact sciences and technology; O-9-tert-butylcarbamoyl quinine; Other chromatographic methods; Poly-3-mercaptopropyl methylsiloxane; Reactive monolith; Thiol-covered surfaces; Thiol-ene click reaction
• ISSN: 0021-9673
• DOI: 10.1016/j.chroma.2014.09.066

•Poly-3-mercaptopropyl-methylsiloxane film was coated onto methacrylate monolith.•Functional polysiloxane film was then chemically crosslinked to the surface.•Resultant composite materials allow clickable high-density surface functionalization.•Concept was demonstrated by thiol-ene click reaction with quinine carbamate.•Resultant chiral monoliths were tested for enantiomer separation by CEC. 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.