Preparation Of Stellated Silica Nanoparticles Hybrid And Hydrophilic Boronate Affinity Monolithic Columns

Capillary monolithic columns prepared by in situ polymerization or solidification exhibit good permeability,fast transfer kinetics,excellent reproducibility and easy modification.Capillary electrochromatography?capillary electrochromatography,CEC?is a rapid and efficient micro-separation technique with reliable chromatographic performance and good separation performance.It combines high selectivity of high performance liquid chromatography?HPLC?with high separation ability of capillary electrophoresis?CE?.Meanwhile,CEC which has much kind of stationary phases has been extensively applied in a wide range of fields,such as proteomics,metabolomics,and medicine and so on.Polymer monolith microextraction?PMME?is a type of solid-phase microextraction?SPME?technique methods using polymer monolithic column as extraction materials.PMME has large specific surface area,fast mass transfer rate and fast analysis speed,which can effectively enrich and purify the target analytes.In this paper,two types of novel capillary monolithic columns were prepared,and their preparations and applications were systematically described.In the first part of thesis,a novel inorganic-organic hybrid monolith incorporated with stellated mesoporous silica nanoparticles?SMSNs?was prepared,using RTILs and DESs as binary porogen.SMSNs after silylation modification were dispersed successfully in pre-polymerization mixture in order to obtain column wih highly homogeneous.The optimized monoliths were characterized by field emission scanning electron microscopy?FESEM?,transmission electron microscopy?TEM?,area scanning energy dispersive spectrometry,and nitrogen adsorption.Column performance was tested in CEC mode,baseline separation of alkylbenzenes was obtained with the highest column efficiency?266,000 plates/m?.The performance of the resulting monolith was further investigated in detail by separating mixtures of anilines,naphthalenes,phenols and polycyclic aromatic hydrocarbons?PAHs?.Compared with the corresponding SMSNs-free monolithic coulumn,the CEC performance was improved by about five times.Successful extraction of PAHs was also performed using this capillary monolithic column.Improved extraction efficiency?20.2%?for complex samples,lake water,was also found when this novel material was applied to microextraction of fluoranthene.In the second part of thesis,a novel hydrophily boronate affinity capillary monolithic column was prepared by in-situ polymerization and successfully applied in the microextraction of glycoproteins.Using functional monomer 3-?acrylamido?phenylboronic acid?AAPBA?and hydrophilic macromonomer oligo?ethylene glycol?methyl ether methacrylate?OEG?,crosslinking monomer ethylene glycol dimethacrylate?EDMA?and binary porogens of n-propanol and 1,4-butanediol,poly?AAPBA-co-OEG-co-EDMA?monolith was prepared with uniform structure with good column permeability.The optimized OEG-incorporated boronic monolithic column was characterized with infrared absorption spectroscopy,field emission scanning electron microscopy?FESEM?and N₂ adsorption experiment.In this study,extraction performance was tested by extraction of horseradish peroxidase?HRP?and ovalbumin?OVA?in the mode of PMME.Compared with the corresponding OEG-free boronate monolith,the recovery of HRP and OVA was significantly improved to 97.51%and 93.97%?RSD<5.0%?,respectively,improved over 30.0%.Moreover,the newly monolith was further applied for extraction of the egg white samples spiked with standard HRP and OVA,and the recovery of them was above96.10%and 92.24%?RSD<7.5%?,respectively.These results suggested that the introduction of hydrophilic macromonomer into boronic affinity monolithic column can improve the affinity of BAC with glycoproteins,and it is an effective method for purification and enrichment of glycoproteins with high extraction efficiency.