【作者】 乔凤霞；

【导师】 孙汉文；

【作者基本信息】 河北大学 ， 分析化学， 2008， 博士

【摘要】 分子印迹整体柱和水兼容性印迹聚合物的研究是分子印迹研究中最关注的焦点之一。本文以喹诺酮类抗生素药物和嘌呤碱类药物为研究对象,研究了茶碱分子印迹整体柱的制备、特性及分子识别机理。以茶碱为模板、丙烯酰胺为功能单体,EDMA作交联剂采用原位聚合热引发方式制备了孔径均匀的分子印迹整体柱,避免了耗时的粉碎、研磨、过筛的步骤,提高了烙印聚合物的特异选择性。同时对其色谱特性、结合容量、吸附特性、形态表征、热力学性质及分子识别机理进行了探讨,并成功的应用于不同品种绿茶中咖啡因与茶碱的选择性分离分析。合成了水兼容性印迹聚合物并成功地应用于分子印迹-固相萃取中。分别以氧氟沙星和恩诺沙星为模板,在甲醇-水体系中合成了对喹诺酮类药物具有特异选择性的印迹聚合物,并对印迹聚合物的聚合条件、键合容量、色谱行为等进行了考察。结果表明,在实际生物和环境水溶液分离分析中该印迹聚合物对喹诺酮类药物具有较高的识别能力和亲和能力。以这些喹诺酮印迹聚合物作固相吸附剂,可以在选择性萃取富集待测药物的同时可以有效的去除复杂的生物及环境基体干扰。同时,用HyperChem V6.0.1软件、PM3半经验主义计算模型对水兼容性氧氟沙星印迹聚合物的识别机理模型进行了分子模拟和理论预测,并通过UV、IR,和1HNMR进行了验证和确认。建立了分子印迹-基质固相分散技术萃取分离复杂生物样品喹诺酮类抗生素和嘌呤碱类药物的新方法。考察了印迹聚合物用做基质固相分散剂对生物样品中喹诺酮和茶碱的最佳萃取分离条件及选择性,并成功应用于牛奶、蜂蜜、血清、鸡肉等样品中痕量喹诺酮类药物残留分离监测。由于基质固相萃取不要求额外的样品净化步骤及分子印迹功能材料的高选择性,样品中大量的蜂蜡、蛋白质等基体在萃取样品的同时亦得到很大程度的分离,因此在减少样品用量和有机溶剂的消耗的同时提高了基质固相分散技术的选择性。分子印迹-基质固相分散技术有着潜在的应用前景。更多还原

【Abstract】 Synthesis imprinted monolithic column and water-compatible imprinted polymers is the most active hotspot of molecular imprinted technique(MIT). Fluoroquinolones and alkaloids were selected as the research object with the suppot of MIT.Synthesis, characteristics, and recognition menchnism of the theophylline imprinted monolithic column were investigated Theophylline imprinted monolithic columns were designed by an in-situ thermal-initiated copolymerization technique. The chromatographic conditions, binding capacity, morphological characteristics and thermodynamic characteristic were evaluated. The present monolithic MIP columns were successfully applied for the quantitative determination of caffeine and theophylline in different kinds of green tea.Water-compatible imprinted polymers were Synthesized and be successfully applied to solid-phase extraction. Water-compatible imprinted polymers with high selectivity to quinolones in polar condition were prepared in methanol-water system using ofloxacin and enrofloxcin as template respectively. The effect of polymerization conditions and characteristics of the MIPs such as binding capacity and chromatography characteristics were evaluated. These polymers show high affinity to quinolones in aqueous environment and were successfully applied as special sorbents for selective solid-phase extraction of quinolones from environmental and biological samples. Furthermore, the matrix interferences origing from complex samples could be effectively eliminated while the analytes were selectively extrated and enriched. The molecular recognition mechanisms of the obtained MIPs were investigated by the molecular simulation using HyperChem V6.0.1 software and PM3 semi-experimentalism compute model, and then were experimental validation with UV and infrared spectrogram as well as 1H NMR.A new selective sample cleanup procedure, molecularly-imprinted matrix solid-phase dispersion (MI-MSPD) was developed for the extraction of fluoroquinolones from different biological samples. By using C18 and MIPs as different dispersants, the extraction and separation conditions of quinolones in biological samples were investigated and optimized. The MIPs applied as the selective dispersant of MSPD could selectively extracted fluoroquinolones from complicated sample matrix, while interferences originated from biological matrices were eliminated simultaneously. The proposed MIP-MSPD method only requires a small amount of sample (0.1mL) and uses aqueous solutions for clean-up step, which significant reduction in both sample size and solvent consumption. The extracts were clean enough to inject directly into HPLC for further chromatographic analysis. The developed method is simple and sensitive, and can be used as an alternative tool to the existing HPLC methods for analyzing the residues of fluoroquinolones in biological samples. Furthermore, to improve the affinity and recognization in water solution, the preparation conditions of the MIP in aqeous environment was further investigated. The technique of MIP-MSPD have potential application to many fileds.更多还原