基于POSS的可逆加成—斷裂鏈轉移聚合法制備分子印跡整體柱
發(fā)布時間:2018-04-25 09:42
本文選題:分子印跡聚合物 + 多面體低聚倍半硅氧烷; 參考:《天津醫(yī)科大學》2017年碩士論文
【摘要】:分子印跡(molecular imprinting)是一種強大的工具用于制備與模板分子特異性結合的人工受體。分子印跡聚合物(MIPs)是在模板分子存在下,由印跡分子和一種或幾種功能單體混合形成模板-單體復合物,然后通過功能單體和交聯(lián)劑共聚形成的固體聚合物,將印跡分子去除后,所得的印跡聚合物能夠形成對模板具有“記憶”的識別位點。MIPs具有特異性識別性、廉價和高物理化學穩(wěn)定性等優(yōu)點,已發(fā)現(xiàn)廣泛應用于特異性結合領域?赡婕映蓴嗔焰溵D移聚合(RAFT)方法是活性/可控自由基聚合法(CRP)其中的一種,RAFT聚合法因其溫和的反應條件,可被應用于多種單體、引發(fā)劑和聚合條件當中,通過對聚合體系中活性鏈自由基的濃度進行控制,使其始終保持在較低的水平,雙分子偶合或歧化終止等副反應很少,得到的聚合物結構更加均勻,因而選擇性和特異性更好。POSS(Polyhedral oligomeric silsesquioxane)是一類納米復合材料,具有無機-有機籠型結構,常見分子式為(RSiO_(1.5))n。由于POSS具有多重活性功能基和納米級結構,可通過共聚作用、嫁接或混合法將其混合到傳統(tǒng)的聚合物里。本文首次成功使用可逆加成-斷裂鏈轉移法制備了基于POSS的分子印跡整體柱。此分子印跡整體柱以酮洛芬(KET)為模板,混合RAFT試劑,POSS功能單體(MA0702),4-乙烯基吡啶(4-VP),二甲基丙烯酸乙二醇酯(EDMA)制備而得。我們研究了RAFT試劑、POSS單體的含量以及KET與4-VP的比例、4-VP與EDMA的比例對聚合物的保留因子和印跡效果產(chǎn)生的影響。得到,基于POSS的以RAFT法制備的印跡整體柱的最佳印跡因子為15.2,比不存在RAFT試劑的印跡整體柱高出1.5倍。我們通過滲透性,表觀形態(tài)和孔徑分布的表征,對加入RAFT試劑和不加RAFT試劑的POSS印跡整體柱進行了對比。將最佳的MIP用于酮洛芬藥片中酮洛芬的選擇性萃取。在基于POSS的以RAFT法制備的印跡整體柱上,酮洛芬的平均回收率為85.2%,相對標準偏差(RSD)為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.
【學位授予單位】:天津醫(yī)科大學
【學位級別】:碩士
【學位授予年份】:2017
【分類號】:TQ316.3
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,本文編號:1800818
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