Design and fabrication of fluorous monoliths with tunable surface property for capillary liquid chromatography

Hierarchically porous monoliths with satisfactory properties have been employed in diverse fields, especially separation. In this study, pentafluorophenyl acrylate (PFPA), pentaerythritol tetraacrylate (PETA) and trimethylolpropane tris(3-mercaptopropionate) (TTMP) were selected as precursors to fabricate a novel monolithic column by thermally initiated polymerization in the presence of a binary porogenic system containing tetrahydrofuran and 1-propanol. The fabricated poly(PFPA- co -PETA- co -TTMP) monolithic column revealed excellent permeability and mechanical stability. Additionally, baseline separation of the mixture of small molecules can be achieved, involving alkylbenzene and fluorobenzene in chromatographic assessment, and the theoretical plate number is up to 60,500 plates/m for butylbenzene with a linear velocity of 0.14 mm/s. Tryptic digest of HeLa as an analyte was used to investigate the possibility of the poly(PFPA- co -PETA- co -TTMP) monolith in biological separation by cLC-MS/MS. Moreover, benefiting from the existence of pentafluorophenyl groups, the cucurbit[8]uril (CB[8]) could be modified on the prepared poly(PFPA- co -PETA- co -TTMP) monolith through host-guest interaction to obtain poly(PFPA- co -PETA- co -TTMP)-CB[8] monolith. It could be observed that significant changes in retention behavior of analytes appeared after immobilizing CB[8] on the monolith. It offered an innovative approach by utilizing host-guest interaction to fabricate monolithic columns with different chromatographic behaviors.