手性共价有机框架材料的设计合成及在手性色谱分离中的应用

Crystalline covalent organic frameworks (COFs) constructed from organic building units via strong covalent bonds have received significant attention due to their unusual properties such as low density, high surface area, tunable pore size, facilely-tailored functionality as well as excellent thermostability. The rational design and construction of chiral COFs is one of the hot and difficult subjects in the field of COF materials, however, chiral COFs have not yet been used as chiral stationary phases for chromatography enantioseparations. On the basis of the above considerations, in this project, we are going to design C2 symmetric hydrazides containing chiral sites or potential post-modification sites, and use them as precursors to react with different aldehydes to offer highly stable hydrazone or β-ketoenamine-linked chiral COFs. The as-prepared chiral COFs will be directly coated on the inner walls of capillary column by dynamic coating method, and then used for capillary gas chromatography enantioseparations. Meanwhile, chiral COFs@SiO2 composites, which can be fabricated by the integration of chiral COFs with surface-modified silica gels, will also be utilized as chiral stationary phases for high-performance liquid chromatography enantioseparations. Based on the above research, this project aims to study the thermodynamics, kinetics, and interaction mechanisms between chiral COF materials and chiral molecules and illustrate the relationship between COF structures and properties. Eventually, some new chiral separation materials are expected to be obtained.

由有机构筑基元通过强共价键连接成的晶态共价有机框架（COFs）材料因其具有密度小、比表面积高、骨架大小可调、孔道易修饰及热稳定性好等非凡的性质而引起了人们的广泛关注。手性COFs材料的设计与合成是目前的研究热点和难点，而使用手性COFs材料作为固定相用于手性色谱分离方面的研究还尚未见报道。基于以上考虑，本项目拟通过含手性位点或含潜在后修饰位点的C2对称酰肼类前体的设计，使之与不同醛类前体反应制备高稳定性的腙类或β-酮烯胺类手性COFs材料。然后利用动态涂覆法将手性COFs涂敷在毛细管内壁，研究材料在毛细管气相色谱手性分离中的应用。同时将手性COFs键合到表面修饰的多孔硅胶上制备出手性COFs@SiO2复合材料，研究该材料在高效液相色谱手性分离中的应用。最终结合两者研究手性COFs材料与手性对映体之间相互作用的热、动力学以及作用机理等，总结出构效关系，从而优化得到新型的手性COFs分离材料。

共价有机框架 (COFs) 材料因其具有质量轻、稳定性好、结构规整、比表面积高、骨架大小可调、孔道可修饰等优点而引起了人们的广泛关注。手性和非手性COFs材料在色谱分离和识别上的应用研究还较少，基于此，本项目选取特定的体系作为研究对象，完成了几方面的研究，包括：腙类和β-酮烯胺类手性COFs材料的设计合成、含特殊功能基团的非手性COFs材料的合成与性质、具有新拓扑结构的亚胺连接型非手性COFs材料的合理设计与可控合成以及这些功能COFs材料在高效液相色谱、毛细管气相色谱及在分子和离子识别中的应用研究等。研究成果丰富了手性COFs材料和新拓扑类型COFs材料的种类，进一步证实了COFs材料在色谱分离、分子和离子识别中具有很大的潜在应用价值。研究成果大部分已经发表，共计发表论文24篇，其中SCI收录论文22篇, 而第一或通讯作者共18篇，第一申请人申请发明专利3项。此外，通过项目的研究，申请人成功获得副教授资格并培养了三名硕士研究生、多名本科生以及协助培养一名博士研究生。