基于POSS的可逆加成—断裂链转移聚合法制备分子印迹整体柱

发布时间：2018-04-25 09:42

本文选题：分子印迹聚合物 + 多面体低聚倍半硅氧烷　；参考：《天津医科大学》2017年硕士论文

【摘要】：分子印迹(molecular imprinting)是一种强大的工具用于制备与模板分子特异性结合的人工受体。分子印迹聚合物(MIPs)是在模板分子存在下,由印迹分子和一种或几种功能单体混合形成模板-单体复合物,然后通过功能单体和交联剂共聚形成的固体聚合物,将印迹分子去除后,所得的印迹聚合物能够形成对模板具有“记忆”的识别位点。MIPs具有特异性识别性、廉价和高物理化学稳定性等优点,已发现广泛应用于特异性结合领域。可逆加成断裂链转移聚合(RAFT)方法是活性/可控自由基聚合法(CRP)其中的一种,RAFT聚合法因其温和的反应条件,可被应用于多种单体、引发剂和聚合条件当中,通过对聚合体系中活性链自由基的浓度进行控制,使其始终保持在较低的水平,双分子偶合或歧化终止等副反应很少,得到的聚合物结构更加均匀,因而选择性和特异性更好。POSS(Polyhedral oligomeric silsesquioxane)是一类纳米复合材料,具有无机-有机笼型结构,常见分子式为(RSiO_(1.5))n。由于POSS具有多重活性功能基和纳米级结构,可通过共聚作用、嫁接或混合法将其混合到传统的聚合物里。本文首次成功使用可逆加成-断裂链转移法制备了基于POSS的分子印迹整体柱。此分子印迹整体柱以酮洛芬(KET)为模板,混合RAFT试剂,POSS功能单体(MA0702),4-乙烯基吡啶(4-VP),二甲基丙烯酸乙二醇酯(EDMA)制备而得。我们研究了RAFT试剂、POSS单体的含量以及KET与4-VP的比例、4-VP与EDMA的比例对聚合物的保留因子和印迹效果产生的影响。得到,基于POSS的以RAFT法制备的印迹整体柱的最佳印迹因子为15.2,比不存在RAFT试剂的印迹整体柱高出1.5倍。我们通过渗透性,表观形态和孔径分布的表征,对加入RAFT试剂和不加RAFT试剂的POSS印迹整体柱进行了对比。将最佳的MIP用于酮洛芬药片中酮洛芬的选择性萃取。在基于POSS的以RAFT法制备的印迹整体柱上,酮洛芬的平均回收率为85.2%,相对标准偏差(RSD)为2.6%。
[Abstract]:Molecular imprinting is a powerful tool for the preparation of artificial receptors specifically bound to template molecules. Molecularly imprinted polymer (MIPs) is a solid polymer, which is composed of imprinted molecules and one or more functional monomers in the presence of template molecules, and then copolymerizes with functional monomers and crosslinkers to form a template monomer complex. After the imprinting molecule is removed, the imprinted polymer can form the recognition site. MIPs with "memory" for template have the advantages of specificity recognition, low cost and high physicochemical stability, which have been widely used in the field of specific binding. Reversible addition chain transfer Polymerization (RAFT) is one of the active / controllable radical polymerization methods (CRP), which can be used in many kinds of monomers, initiators and polymerization conditions because of its mild reaction conditions. By controlling the concentration of active chain free radicals in the polymerization system, the polymer was kept at a relatively low level, the side reactions such as bimolecular coupling or disproportionation were rare, and the structure of the polymer was more uniform. Therefore, the selectivity and specificity of the polymer polyhedral oligomeric silsesquioxane) is a kind of nanocomposites with inorganic and organic cage structure. Because POSS has multiple active functional groups and nanoscale structures, it can be mixed into traditional polymers by copolymerization, grafting or mixing. In this paper, the molecular imprinted monolithic column based on POSS has been successfully prepared by reversible addition-break chain transfer method for the first time. The molecularly imprinted monolithic column was prepared by using ketoprofen Ket as template, RAFT reagents were mixed with POSS functional monomer, MA0702 and 4-vinylpyridine 4-VPX, and ethylene glycol dimethacrylate (EDMA) was prepared. The effects of the content of POSS monomer of RAFT reagent and the ratio of KET to 4-VP, 4-VP to EDMA, on the retention factor and imprinting effect of the polymer were studied. The optimum imprinting factor of the imprinted monolithic column prepared by RAFT method based on POSS was 15.2, which was 1.5 times higher than that of the imprinted monolithic column without RAFT reagent. Through the characterization of permeability, apparent morphology and pore size distribution, we compared the POSS imprinted monolithic column with and without RAFT reagent. The best MIP was used for selective extraction of ketoprofen from ketoprofen tablets. The average recovery of ketoprofen was 85.2 and the relative standard deviation (RSD) was 2.6 on the imprinted monolithic column prepared by RAFT method based on POSS.
【学位授予单位】：天津医科大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ316.3

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