超分子囊泡介观体系的组装及调控

Compared with the rapid development of macroscopic supramolecular assembly and microscopic supramolecular assembly at the molecular scale, nanoscale, there are relatively few studies on the mesoscopic supramolecular assembly. Therefore, the development of strategy to construct mesoscopic system is one of the opportunities and challenges in supramolecular assembly area. Cells with intracellular nuclei are typical mesoscopic systems, and the cells transmit energy, information, and matter through biomembranes and nano tunnels between membranes. This project will simulate the biomembrane of cells and nuclei and the nano-tunneling between them. It is intended to construct a mesoscopic assembly model of biomimetic dynamic connections between supramolecular vesicles. The main contents are as follows: 1) Prepare water-soluble pillararene macrocycles and cyclodextrin macrocycles based amphiphiles, which could be further assembled into supramolecular vesicles; 2) Assemble nested supramolecular vesicles; 3) Build vesicular mesoscopic systems based on molecular shuttle and molecular tube as bridges, and oligomers with macrocycles at the side chain was used as the molecular tube. Try to study the mass exchange and information communication between membranes. 4) Construction of vesicular mesoscopic systems with three bridges and four bridges. Study construction strategies and dynamic behaviors of supramolecular vesicular mesoscopic systems, as well as the exchange of material and information between them, to not only promote people's understanding to biomembranes and get innovative achievements, but also open a new way for biomimetic research.

与分子尺度、纳米尺度的微观分子组装和宏观尺度超分子组装取得的发展相比，超分子介观组装的研究相对较少，发展构筑介观体系的策略是超分子组装的机遇和挑战之一。细胞是一种典型介观体系，其细胞膜和内部细胞核均通过生物膜构筑而成。该申请项目将模拟细胞和细胞核的生物膜嵌套以及细胞之间的连接，拟构筑超分子囊泡和囊泡间的仿生动态连接的介观组装模型，主要研究内容如下：1）利用水溶性柱芳烃大环和环糊精大环等双亲体组装成基于不同大环主体的超分子囊泡；2）构筑嵌套结构的超分子囊泡；3）进一步构筑基于分子梭和分子管道桥联的囊泡介观体系，分子管道使用大环为侧基的齐聚物，尝试研究两个膜状结构的物质交换和信息通讯；4）初步构筑三桥联和四桥联的囊泡介观体系。研究超分子囊泡介观体系的构筑策略和动态行为，以及它们之间的物质和信息的交换，借此促进人们对生物膜的认识，获得创新性研究成果，仿生研究提供一条新的途径。

与分子尺度、纳米尺度的微观分子组装和宏观尺度超分子组装取得的发展相比,超分子介观组装的研究相对较少，发展构筑介观体系的策略是超分子组装的机遇和挑战之一。本项目针对超分子化学领域中超分子组装协同效应及可控构筑超分子囊泡等介观体系等科学问题主要展开以下工作：1）超分子光捕获纳米介观系统的构筑和超分子光催化。构筑具有多步能量转移特征并能实现光能到化学能转化的人工光捕获体系，所构筑的人工光捕获系统可作为纳米反应器和高效催化剂用于催化α-溴苯乙酮的脱卤反应，显示了超分子人工光催化系统在模拟天然光合作用中的潜在应用。这为更好地模拟和理解自然界中以多通道信息通讯为特征的光捕获天线系统，奠定良好的基础；2）智能超分子药物转运纳米介观体系构筑。双重酸响应释放、前药修饰与诊治结合的策略构筑了基于水溶性柱[5]芳烃等的超分子纳米药物递送系统，实现了抗癌药物的有效递送与可控释放；3）基于超分子自组装策略构筑聚集诱导发光性能的有机功能材料。由多个构建模块自组装而成的拓扑纳米介观结构进行调控和精确控制是研究材料-性能关系的重要研究方向。基于超分子自组装策略构筑长寿命有机发光材料，其在时间分辨荧光成像及光催化领域有着潜在的应用价值。研究了在化学计量比介导下组装体拓扑结构演变及层级诱导手性行为。研究超分子囊泡等介观体系的构筑策略和动态行为，以及它们之间的物质和信息的交换，为人们对生物材料等的认识和仿生研究提供良好的基础。截至目前，依托该项目，项目组成员在国内外有机化学领域发表学术论文29篇，正式接收1篇，其中包括：Angew. Chem. Int. Ed. (1), J. Mater. Chem. A (1)，ACS Appl. Bio Mater. (2), Chem. Commun.（4）, Chem. Eur. J.（3）, Org. Lett.（2）, ACS Mater. Lett. (1), Nature Communn.(1)，Chin. Chem. Lett. (3)，Org. Chem. Front. (1)；并受邀合作编著出版英文版《Supramolecular Catalysts: Design, Fabrication, and Applications》一书。