多重手性COFs色谱填料的设计合成及其手性分离性能研究

The efficient separation of different kinds of chiral drugs with diverse structures is still the frontier and hot spot in the field of separation and analysis. Chiral covalent organic frameworks (COFs) have important potential applications in the adsorption and separation of chiral drugs due to their controllable chirality, regular pore structure, large specific surface area and governable pore size. Since the synthesis of chiral COFs with good crystallinity, diverse structures and various pore sizes are still faced with challenges, the multiple chiral COFs have never been reported. The main contents of the project include: Firstly, design and synthesize different building blocks with multiple chirality through the "bottom-up" strategy by controlling the types of chiral groups, the position of chiral groups, the size of chiral groups monomer, chiral axle and chiral plane. Secondly, combined with reticular chemistry, oxidation and reduction reactions, construct a series of new imine-linked chiral COFs, amide-linked chiral COFs and chiral COFs linked by carbon-nitrogen bonds. Thirdly, combine multiple chiral COFs with chromatography. Explore the separation performance of multiple structure chiral drugs by utilizing multiple chiral COFs as a new type of chiral stationary phase. This project extends the application of chiral COFs in the field of chiral chromatographic separation and provides new materials and new methods for the high efficiency separation of chiral drugs.

结构多样、种类多样的手性药物的高效分离仍然是分离分析研究领域的前沿与热点。手性共价有机骨架材料（COFs）因其手性可调控的特征、规则的孔道结构、较大的比表面积和孔道尺寸可调控等特点，在手性药物的吸附和分离方面有重要潜在应用。由于构筑同时具有较高的结晶性、多孔性和手性等因素的手性COFs仍面临困难，含有多重手性的COFs目前更是尚未作报道。本项目拟利用“自下而上”的构筑策略，通过调控手性基团的种类、手性基团的位置、手性基团的尺寸、手性轴和手性面等手性单元，合成具有多重手性的反应单体；再结合框架化学、氧化还原反应和色谱技术，制备系列拓扑结构和孔径可调的含有多重手性的COFs色谱固定相；探究多重手性COFs色谱填料对多结构类型、多种类的手性药物的分离性能。本项目拓展了手性COFs材料在手性色谱分离领域的应用，也为手性药物的高效分离提供了新材料与新方法。

结构多样、种类多样的手性药物的高效分离仍然是分离分析研究领域的前沿与热点。手性共价有机骨架材料（COFs）因其手性可调控的特征、规则的孔道结构、较大的比表面积和孔道尺寸可调控等特点，在手性药物的吸附和分离方面有重要潜在应用。由于构筑同时具有较高的结晶性、多孔性和手性等因素的手性COFs仍面临困难。本项目的研究工作围绕手性COFs材料的构筑和功能导向的COFs材料的设计合成及其应用性能开展研究，面向手性分离问题，能源问题和环境问题，致力于发展基于有机多孔材料的手性色谱填料，催化剂和传感器，取得了一系列研究成果。通过后修饰的策略和单体调控策略，构筑了三种手性COFs材料，分别对对苯乙醇，α-苯乙胺，和位置异构体2-氯苯胺和3-氯苯胺有一定的拆分效果。我们还构筑了面向绿色合成的异相催化剂（Phen-PAF）、电催化剂（M-TP-COFs）、复合酶催化剂（COFHD-GOX）和荧光传感器（PY-SE-COF），去除对环境有害的有机污染物和重金属离子。以第一作者在国际学术刊物上面发表相关论文6篇。已申请国家专利2项。本项目的研究工作对手性COFs色谱填料的合成以及功能导向的COFs材料的构筑有一定的指导意义。