Allyl-silica Hybrid Monoliths For Chromatographic Application.

摘要

Column technology continues to be the most investigated topics in the separation world, since the column is the place where the chromatographic separation happens, making it the heart of the separation system. Allyl-silica hybrid monolithic material has been exploited as support material and potential stationary phases for liquid chromatography; the stationary phase anchored to the silica surface by Si-C bond, which is more pH stable than traditional stationary phase.;First, nuclear magnetic resonance spectroscopy has been used to study the sol in the synthesis of allyl-silica hybrid monoliths. Allyl-trimethoxysilane (allyl-TrMOS), dimethyldimethoxysilane (DMDMOS) and tetramethoxysilane (TMOS) have been served as co-precursors in the sol-gel synthesis of organo-silica hybrid monolithic columns for liquid chromatography (LC). 29Si nuclear magnetic resonance (NMR) and 1H NMR spectroscopy were employed to monitor reaction profiles for the acid-catalyzed hydrolysis and initial condensation reactions of the individual precursor and the hybrid system. 29Si-NMR has also been used to identify different silane species formed during the reactions. The overall hydrolysis rate has been found to follow the trend DMDMOS > allyl-TrMOS > TMOS, if each precursor is reacted individually (homo-polymerization). Precursors show different hydrolysis rate when reacted together in the hybrid system than they are reacted individually. Cross-condensation products of TMOS and DMDMOS (QD) arise about 10 minutes of initiation of the reaction.;The allyl-silica monolithic columns for capillary liquid chromatography can only be prepared in capillaries with 50 im internal diameter with acceptable performance. One of the most prominent problems related to the synthesis of silica monolithic structures is the volume shrinkage. The synthesis of allylfunctionalized silica hybrid monolithic structures has been studied in an attempt to reduce the volume shrinkage during aging, drying and heat treatment procedure. Important parameters that influence the morphology of the allyl-silica hybrid material, such as the type and monomer ratio of silanes, the amount of porogenic material, the hydrolysis reaction time, the gelation temperature, the water to silicon ratio has been optimized. In addition, factors that affect the volume shrinkage including the fourth precursor, capillary filling temperature, the aging temperature and aging time and the fine tuning of PEG amount have been discussed in details. The pH stability of allyl-silica hybrid (III) monolithic column has been compared with that of TMOS monolithic column and allyl-silica hybrid (I) monolithic column. Details of the preparation, characterization and the initial chromatographic performance of the allyl-silica hybrid monolith are reported. Good peak asymmetry is obtained for the separation of basic analytes.;Allyl-functionalized silica hybrid monolithic structures have also been synthesized for use in CEC, nano-LC and HPLC. The monolithic material is synthesized in a "one pot" reaction approach that provides the functionalized silica support material containing accessible allyl organic groups. The allyl and methyl moieties at the surface with significantly hydrophobic characteristics, can be used as stationary phase directly and provide chromatographic selectivity. Capillary liquid chromatography (CLC) and capillary electrochromatography (CEC) were used to demonstrate the chromatographic kinetics of the hybrid monolith. Evaluation of the stationary phase for HPLC was performed using alkylbenzene as model compounds.