Plasma brominated polymer particles as grafting substrate for thiol‐terminated telomers

Abstract

A combined surface activation and "grafting to" strategy was developed to convert divinylbenzene particles into weak cation exchangers suitable for protein separation. The initial activation step was based on plasma modification with bromoform, which rendered the particles amenable to further reaction with nucleophiles by introducing Br to a surface content of 11.2 atom-%, as determined by X-ray photoelectron spectroscopy. Grafting of thiol-terminated glydicyl methacrylate telomers to freshly plasma activated surfaces was accomplished without the use of added initiator, and the grafting was verified both by reduction in bromine content and the appearance of sulfur-carbon linkages, showing that the surface grafts were covalently bonded. Following grafting the attached glydicyl methacrylate telomer tentacles were further modified by a two-step procedure involving hydrolysis to 2,3-hydroxypropyl groups and conversion of hydroxyl groups to carboxylate functionality by succinic anhydride. The final material was capable of baseline separating four model proteins in 3 min by gradient cation exchange chromatography in a fully aqueous eluent.

Surface Engineering of Bromine-Based Plasma Polymer Films: A Step toward High Thiol Density Containing Organic Coatings

“…In view of incorporating −SH functions in the material taking advantage of the reactivity of the C–Br bond, a chemical reaction is induced between Br-PPF and propanedithiol. The choice of the grafting reaction is inspired from the study of Byström et al investigating the nucleophilic reaction between the C–Br bond and a thiol-terminated glycidyl methacrylate telomers . It has been demonstrated that the reaction proceeds through the nucleophilic attack on the C–Br bond of the thiol-terminal group of the grafting molecule resulting, in fine, in the formation of the thioether bond (i.e., C–S–C) and the removing of bromine atom in the form of HBr.…”

“…The choice of the grafting reaction is inspired from the study of Bystrom et al investigating the nucleophilic reaction between the C−Br bond and a thiol-terminated glycidyl methacrylate telomers. 39 It has been demonstrated that the reaction proceeds through the nucleophilic attack on the C−Br bond of the thiolterminal group of the grafting molecule resulting, in fine, in the formation of the thioether bond (i.e., C−S−C) and the removing of bromine atom in the form of HBr. Because, in this work, the objective is to incorporate −SH terminated groups at the interface, in comparison with the strategy employed by Bystrom et al, a molecule containing an −SH function at each extremity is consequently employed.…”

“…For incorporating −SH functions in the Br-PPF, the coatings were immersed in ethanol solution containing 10 −1 M of propanedithiol and triethylamine acting as the catalyst and thus favoring the occurrence of the reaction. 39 The reaction was carried out at 60 °C, and the duration varied from 1 to 48 h. After immersion, the PPF was rinsed in ethanol solution to eliminate the unreacted molecules and dried under nitrogen flow before analysis.…”

Preparation of poly(glycidylmethacrylate‐divinylbenzene) weak acid cation exchange stationary phases with succinic anhydride, phthalic anhydride, and maleic anhydride for ion chromatography

“…Maleic acid has been applied in the preparation of weak acid cation exchange stationary phase by Schomburg . In this work, carboxylic acid anhydride was selected as the carboxylation reagent to prepare the carboxylic acid‐based cation exchanger .…”