Ternary thiol-ene photopolymerization for facile preparation of ionic liquid-functionalized hybrid monolithic columns based on polyhedral oligomeric silsesquioxanes.

A simple thiol-ene photopolymerization approach was developed for the rapid preparation of ionic liquid-functionalized hybrid monolithic column based on polyhedral oligomeric silsesquioxane (POSS). "One-pot" polymerization was realized in the UV-transparent fused-silica capillary by using octanethiol, 1-allyl-3-methylimidazolium hexafluorophosphate as functional monomers and methacryl-substituted POSS as a crosslinker. The thiol-vinyl-methacrylate ternary system uniquely exhibits a mixed step-chain growth polymerization regime that combining the thiol-ene reaction and free-radical reaction mechanisms, which provides a simple route to prepare novel POSS-based functionalized hybrid monoliths. The pore property, permeability, and electroosmotic flow (EOF) of the hybrid monoliths can be tailored by proper adjustment of the feeding composition and initiation condition. Morphologic and spectroscopic characterizations of monolithic columns clearly indicate that utilization of the photo-initiated approach in thiol-vinyl polymerization can generate a more homogeneous porous structure, smaller domain size and higher column efficiency (53,800-60,300 plates/m for alkylbenzenes) than the thermally-initiated one (32,800-49,300 plates/m). Significant improvements in mechanical stability, anti-swelling property and tailorability of hybrid polymer were achieved in a simple manner, owing to the photopolymerization of rigid nanoscale POSS units and imidazolium-based ionic liquids in ternary thiol-vinyl system for the first time. The resulting hybrid monolith possessed controllable EOFs at pH values from 2 to 10, and showed a multimode separation mechanism in capillary electrochromatography, including π-π interaction, ion exchange, electrophoretic migration, electrostatic and hydrophobic interaction. Satisfactory separation ability was achieved for the analysis of different types of small molecules.