新型杯[6]芳烃衍生物的设计合成及其功能超分子组装体的构筑

This project will study the design, synthesis and construction of functional supramolecular assemblies based on amphiphilic calix[6]arene derivatives. At first a series of novel assembly primitives, including sulfonic ions, carboxylate ions, quaternary ammonium cations and anthracene alkynyl units, derived from calix[6]arenes were rationally designed and efficiently synthesized. Then the assembly behaviors of these prepared amphiphilic calixarenes in solution and in solid state will be studied in details. A series of nano-metre scale suprestructures such as supramolecular-capsules, micelles and vesicles would be obtained by using the hydrophobic and pi-pi stacking interactions. Through the metal-ligand coordination and inclusion complexation driven self-assembly methods, the versatile organic supramolecular arthitectures with well defined shapes and sizes such as nano-tubes, nano-sheets and nano-fibers will be obtained and studied. The conditions of assembly of amphiphilic calixarenes are explored by structure characterization and property measurement. The relationship of the structure and configuration of the amphiphilic calixarenes with formation of nano-assembly, and the strategy of assembly methods will be greatly developed and highlighted. Furthermore, the mechanisms of assembly are clarifed. Finally, the inclusion and release effect of the assemblies with the drug molecules will be explored. It will provide a new thought and a new method in the development of targeted drug delivery and controlled release applications.

本项目拟开展以杯[6]芳烃为骨架的新型组装基元设计、合成以及有机功能超分子组装体构筑的研究。设计合成一系列含有磺酸根离子、羧酸根离子、季铵盐正离子和蒽炔单元的新型杯[6]芳烃组装基元，研究这些功能分子在固态和液态下的组装行为，通过疏水作用和pi-pi堆积作用，构筑成分子胶囊、胶束、囊泡等纳米超分子组装体；通过杯芳烃功能分子络合客体分子或配位金属离子对其自组装行为进行调控，从而构筑成大尺寸、多功能化杯芳烃有机超分子组装体，如纳米管、纳米片、纳米纤维等；通过系统的结构表征和性能测试，探索两亲型杯[6]芳烃功能分子的组装条件，并深入研究其机理，尤其是两亲型杯[6]芳烃功能分子的结构、构型与有序组装体形成的内在联系，从而揭示分子有序自组装聚集体的构筑规律。在此基础上，进一步探索杯芳烃功能超分子自组装体与药物分子的包结、释放作用，为开发具有靶向释放功能的药物载体研究提供理论指导和崭新的思路。

本项目我们主要开展了新型杯芳烃衍生物的设计合成、超分子组装体及多孔聚合物的构筑研究。首先我们设计合成一系列含有氨基单元的新型杯芳烃组装基元，首先开展了间甲氧基苯酚杯[4]芳烃衍生物的组装机理和性能研究，接下来，我们将课题进行了延伸，将新型的杯[4]芳烃的组装基元在一定条件下聚合构筑得到含有杯芳烃的多孔聚合物，探讨了取代基的改变，会引起其形貌和性能的不同；同时，我们还详细研究了该类聚合物对水中碘的吸附性能，这为开发新型超分子功能材料提供新的方法和途径；另外，我们还以过渡金属催化合成有机小分子的前期研究为基础，利用杯芳烃多孔聚合物高比表面积的优点，进而将此类聚合物与金属进行配位，进行了聚合物负载金属后催化性能的探索，为实现有机小分子的高效、绿色合成提供新的思路。