“One-Pot” Process for Fabrication of Organic-Silica Hybrid Monolithic Capillary Columns Using Organic Monomer and Alkoxysilane

Abstract

A "one-pot" process for the preparation of organic-silica hybrid capillary monolithic columns by concurrently using organic monomers and alkoxysilanes was described. In this process, the hydrolyzed alkoxysilanes of tetramethoxysilane (TMOS) and vinyltrimethoxysilane (VTMS) as precursors for the synthesis of a silica-based monolith using the sol-gel method and the organic monomer (allyldimethyldodecylammonium bromide (ADDAB) or acrylamide (AA)) with vinyl groups for free radical polymerization along with the initiator of azobisisobutyronitrile (AIBN) were concurrently introduced into a pretreated capillary; after that, the polycondensation of alkoxysilanes and the copolymerization of organic monomers and as-precondensed siloxanes were subsequently carried out within the confines of a capillary at the proper reaction conditions. Two types of organic-silica hybrid capillary monolithic columns with hydrophobic and hydrophilic properties have been fabricated, respectively, by this "one-pot" process using two different organic monomers of ADDAB and AA. The morphologies of the synthesized organic-silica hybrid monolithic columns were characterized by scanning electron microscopy (SEM). The performances of these organic-silica monolithic columns were investigated by capillary electrochromatography (CEC). The retention behaviors of the neutral and polar compounds on the resulting hydrophobic and hydrophilic organic-silica hybrid monolithic columns confirmed the successful incorporation of organic monomers in the silica monolithic matrix. In addition, the ADDA-silica hybrid capillary monolithic column was also applied in the analysis of tryptic digests of bovine serum albumin (BSA) and mouse liver extract by microliquid chromatography-tandem mass spectrometry (microLC-MS/MS) for demonstrating its potential in proteome analysis.

Synthesis of boronate-silica hybrid affinity monolith via a one-pot process for specific capture of glycoproteins at neutral conditions

“…The AAPBA-silica hybrid affinity monolith was synthesized via a one-pot procedure, which mainly involved two major steps as mentioned in the literatures [26][27][28][29]: the polycondensation between the hydrolyzed alkoxysilanes TMOS and VTMS to form vinyl-silica hybrid monolithic matrix at a relatively low temperature, and the copolymerization of vinyl functional groups on the vinyl-silica hybrid monolithic matrix and the organic monomer AAPBA at a proper higher temperature. The synthetic scheme of the AAPBA-silica hybrid affinity monolith is shown in Fig.…”

“…In this process, the polycondensation and copolymerization of the organic and inorganic monomers were carried out orderly by controlling at proper temperatures. The "one-pot" synthesis method is simple, convenient and time-saving, and it has been used to fabricate a series of organic-silica hybrid monolith with different organic monomers for the chromatographic analysis [26][27][28][29]. These researches provided a facile approach for covalent incorporation of different organic moieties into the silica monolith to prepare various organic-silica hybrid monoliths.…”

Recent advances in preparation and application of hybrid organic‐silica monolithic capillary columns

“…As a result, the "one-pot" process can not only introduce the desirable functional groups into the silica monolith by combining the merits of the meso-and macroporous structure of silica monolith and the great availability of functional chemicals, but also address the limitation and difficulty of using or synthesizing the alkyltrialkoxysilanes to prepare the hybrid monoliths but using various organic monomer or other functionalities. Besides the monomers of allyldimethyldodecylammonium bromide and acrylamide being used to fabricate hybrid monoliths with "one-pot" process [72], the monomer of [3-(methacryloylamino) propyl]trimethylammonium chloride was also used to prepare strong anion exchange hybrid column via this ''one-pot'' approach. The resulting hybrid column was coupled with MALDI-TOF MS for the enrichment and detection of phosphopeptides from protein digest with excellent sensitivity.…”

Recent advances in monolithic columns for protein and peptide separation by capillary liquid chromatography

“…Recently, a novel "one-pot" preparation approach has been developed by the group of Zou [44][45][46][47] to prepare organic-silica hybrid monoliths via the polycondensation of hydrolyzed alkoxysilanes of tetramethoxysilane and vinyltrimethoxysilane at a relatively low temperature and then the copolymerization of organic monomers with the vinyl-silica matrix formed at a relatively high temperature, as shown in Fig. 2.…”

“…Various kinds of monolithic capillary columns have been synthesized for RPLC separation of proteins and peptides, such as poly(styrene-co-divinylbenzene) monoliths [53][54][55][56], poly(butyl methacrylate-co-ethylene dimethacrylate) monoliths [57], poly(lauryl methacrylateco-ethylene dimethacrylate) monoliths [58,59], monoliths derived from ring-opening metathesis polymerization [60], C 18 -modified silica monoliths [61][62][63][64][65][66], dimethyldodecylammonium-silica hybrid monoliths [44], POSS-based hybrid monoliths [49], and phenyl-silica hybrid monoliths [47]. The detailed applications are shown in Table 1.…”