【作者】 王娟；

【导师】 林子俺；

【作者基本信息】 福州大学 ， 药物分析学， 2014， 硕士

【摘要】 有机聚合物整体柱由于制备简单,易于改性且生物兼容性好等优点在分离分析领域得到广泛应用。尽管如此,由于聚合物固定相中主要含有大孔和中孔结构,因此,小分子化合物难以得到高效的分离。纳米材料具有比表面积大、形态多样及可塑性强等特点,在以色谱和电泳技术为基础的分离科学领域已得到广泛应用。将纳米材料作为致孔剂或功能单体掺杂到整体柱固定相,有望改善聚合整体柱的孔结构,进而提高整体柱柱效和分离选择性。基于此,本文致力于发展两种基于纳米基质掺杂的毛细管整体柱,系统地探讨了其色谱保留行为及分离机理,并将其应用于一系列小分子的分离研究。本论文主要从以下三个方面进行阐述：第一章综述了毛细管电色谱的基本理论,毛细管电色谱柱的分类、制备等技术；介绍纳米材料的特性、制备方法及其在色谱中的应用；着重介绍了有机聚合物整体柱的制备方法及纳米材料在整体柱中的应用,围绕纳米材料掺杂到整体柱中的方法进行了讨论；此外,还简单介绍了本论文的研究意义及研究内容。第二章以甲基丙烯酸缩水甘油酯(GMA)、2-丙烯酰胺-2-甲基-1-丙磺酸(AMPS)为功能单体,乙二醇二甲基丙烯酸酯(EDMA)为交联剂,以环己醇和十二醇为液体致孔剂,将磁性Fe3O4纳米粒子均匀分散在该二元致孔剂中作为纳米致孔,制备了基于磁性纳米粒子致孔的有机聚合物整体柱。实验优化了单体和交联剂的比例、致孔剂的配比及掺杂Fe3O4纳米粒子的最优浓度。与未掺杂Fe3O4纳米粒子的整体柱相比,该整体柱在分离烷基苯、苯酚类和苯胺类时,呈现出较好的分离性能和柱效,并成功地应用于生物碱、麻醉剂等药物的高效分离。第三章以3-丙烯酰胺基苯硼酸(AAPBA)为功能单体,以季戊四醇三丙烯酸酯(PETA)为三元交联剂,以乙二醇和环己醇为二元致孔剂,将氧化石墨烯(GO)掺杂到预聚混合溶液中,制备了基于GO掺杂的苯硼酸型整体柱。实验考察了AAPBA以及GO浓度对整体柱性能及色谱保留机制的影响,在最优条件下,该整体柱表现出疏水、亲水及阳离子交换的色谱行为。与未掺杂GO整体柱相比,该整体柱在分离苯系物、苯酚类物质、多环类物质及多肽等方面获得满意的结果。更多还原

【Abstract】 Polymer monolithic columns have been widely used in the field of separation science because of their simple preparation, convenient modification and good biological compatibility. However,due to its inherent property of a dual-pore structure in polymer-based monoliths, it is difficult to achieve high separation efficiency in the separation of small molecules. Recently, nanomaterials have been widely used in separation science especially in chromatographic solid phase and electrophoresis due to their unique advantages such as large surface area, diverse morphology and flexible structure. Incorporating nanomaterials with monothic solid phase or as nano-template is a desirable solution to improve the pore structure of monolithic columns, and thus to enhance the separation efficiency based on this motivation, we devoted to develop two different kinds of polymer-based monolithic columns by using magnetic nanoparticles as nano-template and graphene oxide(GO) as an incorporated monomer, respectively. Accordingly, their chromatographic retention mechanisms were systematically evaluated in detail. High efficiency separation of a series of small molecules can be achieved. The thesis consists of three chapters as follow:In chapter 1, the theory of capillary electrochromatography, the classification of capillary monolithic columns and their preparation method, as well as namomaterial’s property and their applications in chromatography were introduced in detail. In this part, the connection and applications between monolithic columns and materials were mainly introduced. Besides, the aim and significance of this thesis were also briefly presented.In chapter 2, preparation of Fe3O4 nanopartical-based monolithic column by in situ copolymerization of glycidyl methacrylate (GMA) and ethylene glycol dimethacrylate (EDMA) as monomers in a binary porogenic solvent (cyclohexanol and dodecanol) was described. Different ratios of monomers, porogens and Fe3O4 nanoparticals were used for optimizing the properties of monolithic column. Compared with the bare monolithic column, the nano-template column presented bettter separation and efficiency performance when separating alkylbenzenes, phenols and anilines.The purposed monolithic column was also applied to efficiently separate alkaloids and anaesthetics. The successful applications demonstrated that the glycidyl methacrylate based monoliths prepared by using nano-template are a good alternative for enhanced separation efficiency of small molecules.In chapter 3, GO-based monolithic column by in situ copolymerization of 3-acrylamide benzene boric acid (AAPBA) and pentaerythritol triarylate (PETA) as monomers in a binary porogenic solvent (glycol and cyclohexanol) was prepared. The ratios of AAPBA to PETA, the composition of porogenic solvent and the quantity of GO in the solvent were optimized in detail as to the column properties (e.g. permeability, morphologyand selectivity). A series of amides were used to evaluate the monolithic column performance in terms of hydrophobic, hydrophilic and cation-exchange interactions. Compared with the monolith without the incorporation of GO, the solution and efficiency in the poly (GO-co-AAPBA-co-PETA) monolithic column were much higher and better. Besides, the ratio of ACN in the mobile phase, the concentratin of PBS and the applied voltage were also be evaluated. In addition, the GO-based monolithic column was successfully applied to separate alkylbenzenes, phenols, and peptides, respectively.更多还原