Click Chemistry For Preparation Of Monolithic Capillary Columns And Their Application

In recent years,monolithic columns have been rapidly developed in the aspect of the analysis of chromatography and preparation techniques.Aiming at the shortcomings in the polymeric column monolith and hybrid monolith,several novel approaches were developed for the preparation of monolithic columns.Click reaction,which features simplicity,regioselectivity and under mild conditions,has become a versatile tool in the applications of polymer science,surface modification and organic synthesis.However,there were still few reports about click polymerization for direct construction of monolithic columns.1.A facile approach was exploited for fast preparation of polymeric monoliths via"one-pot" thiol-acrylate polymerization reaction.During this process,the crosslinker(DPEPA)not only self-polymerized,but also coupled with the thiol-containing monomer.Due to the addition of thiol,the major obstacle of oxygen inhibition was essentially eliminated.The resulting poly(ODT-co-DPEPA)monolithic columns exhibited strong ability for small molecules(highest ca.75,000 N/m).Moreover,we made the first attempt to identify the proteins extracted from Amygdalus pedunculata Pall.seeds by cLC-MS/MS,which demonstrated its potential in the analysis of biological samples.2.A macroporous hydrophilic organic-silica hybrid monolith was successfully fabricated through two steps of thiol-ene click reaction.1-Thioglycerol-modified vinylPOSS was synthesized to improve its solubility and then exploited as the precursor to further synthesize hybrid monoliths.The resulting hybrid monolithic columns exhibited homogeneous macroporous structure,well permeability and good separation ability for neutral polar compounds in HILIC.In addition,the hybrid monolith was successfully turned into a kind of hydrazine material for glycopeptides enrichment.This successful application implied the hydrophilic hybrid monolith would be taken as a promising material for the pretreatment of sample.3.One-step alkaline-catalyzed thiol-maleimide polymerization reaction was firstly adopted for direct preparation of polymeric monoliths.The polymerization could be performed within 3 h,which was much faster than thermal-initiated free radical polymerization reaction.Satisfactory chromatographic separation performance was gained for analysis of alkylbenzenes,EPA 610 and phenols.Compared to the previously reported organic monoliths and organic-inorganic monoliths,this work demonstrated excellent column efficiency(180,000 N/m)on the premise of fast chromatographic separations.Finally,as a practical application,53 and 2184 unique peptides from the tryptic digests of BSA and HeLa cell proteins were positively identified with poly(BMI-co-3SH)monolith in cLC-MS,respectively.