共价有机框架材料(COFs)涂层毛细管的制备及其在毛细管电泳分离和测定环境内分泌干扰物中的应用研究

The covalent organic frameworks (COFs) possess specific properties of large surface areas, abundant topological structures, highly ordered pore structures, easy modification, and high thermal stability. Owing to the above outstanding properties, in this project, through utilizing layer by layer self assembly, covalent bonding, and physical adsorption methods et al., 5-8 kinds of two/three dimensional COFs will be immobilized on the capillary inner wall to prepare novel COFs coated capillaries with the properties of stable performance, temperate separation conditions and strong separation ability. Then, the separation ability of the prepared COFs coated capillaries will be investigated by separation of trace environmental endocrine disruptors in complex samples and the one/two dimensional capillary electrophoresis systems suitable for environmental endocrine disruptors separation will be established. Furthermore, the corresponding separation mechanism will also be studied and mathematical model represented for the relationship between the structure of the COFs coating in the capillary inner wall and the electrophoretic migration behavior of model analytes of environmental endocrine disruptors will be constructed. Carring out this research not only plays an important role in the exploration of new coating materials, the development of novel coating technique and the establishment of new high performance separation system, but is of great significance for the application of COFs in analytical chemisry especially in capillary electrophoresis and the determination of environmental endocrine disruptors in complex samples.

本项目拟根据有机框架材料(COFs)比表面积高、拓扑结构丰富、孔结构高度有序、孔道表面易修饰、热稳定性高等特点，利用层层自组装、共价键合、物理吸附等方法将5-8种二维和三维COFs固定于毛细管内壁，制备性能稳定、分离条件温和、分离能力强的新型涂层毛细管，并以其为分离通道建立用于分离测定复杂样品中微量环境内分泌干扰物质的一维和二维毛细管电泳新体系，研究相应的分离机理，提出描述COFs涂层结构与环境内分泌干扰物质电泳迁移行为关系的数学模型。开展本项目研究不仅对于毛细管电泳新型涂层材料的开发、新涂层技术的发展、新体系的建立具有重要作用，而且对于COFs在分析化学特别是毛细管电泳中的应用和复杂样品中微量环境内分泌干扰物的测定也具有重要意义。

随着社会的发展，环境内分泌干扰物对人类健康的危害和生态环境的破坏越来越受到人们的关注。迄今为止，用于检测环境内分泌干扰物的主要方法为气相色谱和液相色谱，但是由于样品组成复杂，这些方法难以满足实际样品分析要求。因此，发展分离能力强、灵敏度高、能满足实际样品分析要求的新方法是十分必要的。本项目根据有机框架材料(COFs)比表面积高、拓扑结构丰富、孔结构高度有序、孔道表面易修饰、热稳定性高等特点，合成了5种可用于毛细管涂层材料的COFs材料（其中两种是我们首次设计合成的具有新型拓扑结构的手性COFs材料），并通过XRD、TEM、FT-IR、XPS等手段对它们的结构进行了表征。在此基础上，以它们为涂层材料利用层层自组装、共价键合等方法制备了5种COFs涂层毛细管，并以其为分离通道分别建立了用于分离测定环境内分泌干扰物４-硝基苯酚、２,４-二硝基苯酚和２,４,６-三硝基苯酚，双酚A及其类似物，卡维地洛、维拉帕米等手性药物和功能有机小分子的开管毛细管电色谱新方法。所制备COF-涂层毛细管连续运行120-200次分离效果基本保持不变。还对分离机理进行了研究，证明了分析物与COFs涂层之间的π-π相互作用及COFs的尺寸选择作用、微孔手性环境是影响分离行为的主要因素。本项目的开展及所取得的研究成果不仅显著提高了毛细管电泳分离测定环境内分泌干扰物的能力、拓宽了COFs材料的应用范围，而且对纳米分析化学和生命分析化学的发展具有重要意义。