【作者】 吕海霞；

【导师】 谢增鸿；

【作者基本信息】 福州大学 ， 分析化学， 2006， 博士

【摘要】 从毛细管电色谱的发展历程和研究进展,可以看到毛细管电色谱作为一种新兴的微分离技术,发展迅速、潜力巨大是当今分析化学领域的研究热点。虽然毛细管电色谱的应用很广泛,但是碱性化合物的分离仍然是电色谱需要解决的难题。这是因为硅胶基质的固定相仍然是现在电色谱应用的主要分离基质,碱性药物可能与固定相上的硅羟基发生强烈的非选择性吸附,形成色谱峰不对称和拖尾。针对电色谱中碱性化合物分离的问题:(1)我们制备了新型聚(甲基丙烯酸异丁酯-乙二醇二甲基丙烯酸-N-烯丙基二甲胺)毛细管电色谱整体柱,由这种整体柱带有正电荷,避免了碱性化合物与固定相之间的静电吸引作用,从而避免碱性化合物的峰拖尾或不出峰等现象(第二章)。(2)我们制备了聚(甲基丙烯酸异丁酯-乙二醇二甲基丙烯酸-甲基丙烯酸)毛细管电色谱整体柱,并在碱性的条件下采用“离子抑制”模式成功的分离了碱性化合物,一方面避免了碱性化合物的峰拖尾现象;另一方面避免了采用固定相表面带正电荷的毛细管电色谱柱分离性化合物带来的样品分子的电泳方向和电渗流方向相反的问题(第三章)。由于整体固定相具有渗透性好,传质速度快等优点,可实现大黄酸、芦荟大黄素、大黄素、大黄酚和大黄甲醚五种蒽醌类化合物(第四章)以及马拉硫磷、二嗪农、甲基对硫磷、杀幎硫磷、倍硫磷、甲基毒死蜱和毒死蜱7种有机磷农药残留(第五章)的快速分离检测。采用原位聚合的方法,制备了新型聚(甲基丙烯酸异丁酯-乙二醇二甲基丙烯酸酯-甲基丙烯酸-N-烯丙基二甲胺)两性电荷型毛细管电色谱整体柱。该毛细管电色谱整体柱电渗流的大小和方向可以方便地通过改变缓冲液的pH值来调控(第六章)。更多还原

【Abstract】 Capillary electrochromatography (CEC) has been considered as a very promising analytical technique that combines the efficiency of capillary zone electrophoresis and the selectivity of liquid chromatography with the use of stationary phases.As we know, the analysis of strongly basic analytes is still an analytical challenge for many years because traditional bonded stationary phases exhibit a high density of silanol groups, which results in secondary interactions, severe peak tailing and increased retention. In second chapter, a monolithic stationary phase was prepared in a single step by the in situ copolymerization of iso-butyl methacrylate, ethylene dimethacrylate and N, N-dimethylallylamine in the presence of porogens. The amino groups on the stationary phases are meant to support the electroosmotic flow (EOF) from cathode to anode necessary for moving the mobile phase through the monolithic capillary. Basic compounds such as aniline was well separated on the monolithic columns in the‘counter-directional mode’to avoid the electrostatic adsorption between basic analytes and the charged groups on the surface of the stationary phases. In third chapter, monolithic columns with in situ polymerization of iso-butyl methacrylate, ethylene dimethacrylate and methacrylic acid were prepared. Peak tailing of basic compounds such as anilines was likely to avoid by using ion-suppressed mode of CEC.The possibility of rapid separation resulted from the unique pore structure with high permeability and favorable mass transfer characteristics of the monolithic stationary phase. In fourth chapter, five anthraquinones including emodin,更多还原