【作者】 何天稀；

【导师】 侯经国；

【作者基本信息】 西北师范大学 ， 分析化学， 2003， 硕士

【摘要】 手性是人类赖以生存的自然界的本质属性之一。手性化合物在药物、生物、农业化学等领域具有十分重要的地位。随着分离与不对称合成技术的发展，特别是对于对映体不同的药理活性、代谢过程、药物动力学情况的深入研究，以单一对映异构体供药的问题引起了各方面高度重视。因此开发新的高效、高灵敏度的手性物质分离方法对于对映体的立体选择性合成、药理研究、手性物质纯度检测和环境监测具有十分重要的意义。 气相色谱（GC）和高效液相色谱（HPLC）已成功的运用于很多对映体的分离，但该方法受到手性固定相等因素的限制，也就是说GC存在消旋化问题，HPLC耗费较大。近年来毛细管电泳（CE）因其高效、快速、低耗、方法灵活可变、应用范围广等优点而得到迅速发展，已经大量用于手性药物的分离领域。 介孔材料是一种新型的无机功能材料，自1992年首次报道以来已成为多相催化、无机化学以及材料科学等相关领域的研究热点。由于介孔材料具有比表面积大，孔径分布均匀，热稳定性良好等优点，因此它的研究对催化作用、各类载体和吸附剂、离子交换剂、膜分离技术等方面具有显著意义。随着研究的深入，介孔材料的应用业已扩大到光电材料、新型电池、敏感元件、药物载体、色谱分离和分子工程等高科技领域。 本论文共分为两大部分，共计六章。 第一章：综述了以大环抗生素为手性选择剂的毛细管电泳的进展情况。 第二章：重点研究了以大环内酯类抗生素—红霉素为手性选择剂对酸性手性药物的分离。考察了溶液中手性选择剂的浓度、缓冲溶液的种类及浓度、溶液的pH值，有机添加剂的含量、电压等条件对分离的影响，建立了最佳分离条件。 初步探讨了大环抗生素—乙酰螺旋霉素作为手性选择剂的手性分离。 第三章：综述了近年来介孔材料的合成方法、机理及其应用。 第四章：在碱性条件合成了具有不同钛含量的钛硅介孔分子筛Ti-MCM-41，采用XRD、TEM、SEM、IR、TG-DTA、N₂吸附解吸等技术对其结构进行了表征，考察了以H₂O₂与TBHP为催化剂，氧化乙苯的催化性能。 第五章：在酸性条件下制备了不同Si／Ti的Ti-MCM-41催化剂并进行了结构表征，考察了它们在液相温和条件中催化氧化苯胺的反应。 第六章：分别以溴代十六烷基吡啶、Triton-X-100为模板剂，合成了Co-MCM-41、Co-MSU、Cd-MCM-41和纯TiO₂介孔材料，为催化应用和进一步研究提供了参考数据。更多还原

【Abstract】 Chirality is a phenomenon that pervades the universe and keeps in closely contact with human life. Enantiomers play an important role in pharmaceuticals, biochemistry and agrochemicals, and so on. Chiral separations comprise one of the more attractive tasks of modem chemistry because of their quintessential nature of life. Before the use of a new chiral drug, the pharmacological effects and metabolic pathways for each enantiomer must be examined. Separation techniques have taken an essential role in all stages of the process because enantiomeric separation at analytical scale is required for monitoring the enantiomeric purity of chiral drug and for performing drug metabolism, phannacokinetic and clinical studies. Furthermore, as certain enantiomers represent illicit or banned substances, chiral discrimination represents also an important topic in forensic analysis and doping control. Thus the demand for analytical methods possessing high efficiency and high-resolution capability for enantiomers separation at low cost and short analysis time is increasing.So far the methods used for the analysis of chiral compounds include high-performance liquid chromatography (HPLC), gas chromatography (GC) and recently capillary electrophoresis (CE). Chiral separation is widely accomplished via the use of chromatographic methods (HPLC and GC), which required rather expensive chiral stationary phases. CE is a modern separation technique that provides rapid analysis with high efficiency and high resolution due to a use of high electric field and a variety of selective modes. CE also has some remarkable advantages, such as quick analysis with low cost, flexibility of choose of chiral selectors, environmental friendliness and so on. The use of CE for the separation of chiral compounds can be dated by the work of Gassmann et al. in 1985 with the separation of dansyl amino acid enantiomers. Since then, many researchers move their focus on this field. CE techniques have been separated a large number of chiral compounds of interest in pharmaceutical, clinical, environmental fields.As a novel inorganic functional material, the mesoporous materials have stimulated exceedingly interests in the field of heterogeneous catalysis, inorganic chemistry, and material science and so on since they were first discovered in 1992. These mesoporous materials with uniformly sized nanochannels, tunable pore size and high surface area has been a focus of recent applications for catalysts, catalytic supports, absorbents, ion exchanges and separations, removal of heavy metals. These materials are potential candidates for a variety of applications in the fields of catalysis, optical devices, photonics, sensors, separation techniques, molecularengineering, drug delivery, sorption, acoustic or electrical insulation, ultra light structure material, etc.The dissertation consist of six parts,Chapter 1, it has been reviewed systematically the importance and methods of enantioseparation by capillary zone electrophoresis (CZE) using macrocyclic antibiotics as chiral selectors.Chapter 2, the chiral selectivity of erythromycin was first examined in CZE using a fused silica capillary column. Excellent chiral separations have been achieved for four derivatives of biphenyldimethylester to the acidic antihepatitis drugs (A1-A4), respectively. The effects of various experimental factors such as chiral selector concentration and pH value, voltage and temperature, organic modifiers on enantiomeric resolution were investigated. Enantioreso-lution was improved significantly with increasing chiral selector concentration while the migration time of the analytes showed slight increase. Enantioselectivities of the chiral solutes were considerable influenced by the content of organic modifiers in running buffer.Enantiomers of two acidic chiral drugs were resolved in the first time by capillary electrophoresis (CE) using the aceteylspiramycin as a chiral selector. The influence of pH value of background electrolyte, the concentration of background electr更多还原