空腔内具有氢键供体位点的水溶性大环的合成、识别及应用研究

分子识别是超分子化学和生物物理学的主要研究主题，也是构成人工超分子体系和众多生物功能体系的基础。经过半个世纪的发展，人工分子受体已经取得了令人瞩目的成就，但是仍然很难在水中实现对极性分子的选择性识别。而这对生物分子识别却很常见。这主要是因为在水中利用氢键进行分子识别非常困难。受生物受体结构的启发，我们首次提出了“内修饰分子管”的概念，将氢键键合位点植入到疏水的深穴空腔中，利用疏水效应与氢键之间的协同作用，实现了对部分极性溶剂分子的选择性识别。在此基础上，本项目拟系统地探索多种酰胺内修饰分子管的骨架合成与侧链修饰方法，利用ITC、NMR、X-Ray单晶衍射、荧光光谱、停流光谱等手段揭示其结构变化与识别性能之间的构效关系，理解疏水效应以及氢键的物理有机化学本质，并探索这类新型大环主体分子在环境污染物检测、手性分析、以及超分子自组装材料等方面的应用。

Molecular recognition is one of the central research topics for both supramolecular chemistry and biophysics, and is also the basis of artificial supramolecular systems and numerous biological functional systems. During the last half a century, artificial molecular recognition has made remarkable achievements. Nevertheless, it is still difficult for artificial molecular receptors to selectively recognize polar molecules in water, which is, however, commonplace for biomolecular receptors. This is because molecular recognition with hydrogen bonding in water is challenging. Inspired by the structures of biomolecular receptors, we proposed the concept of “endo-functionalized molecular tubes”, in which hydrogen bonding sites are incorporated inside the deep hydrophobic cavity of molecular tubes. Thus, with the cooperative action between hydrogen bond and hydrophobic effect, selective recognition of several polar solvent molecules in water has been achieved. In this project, we would like to perform a systematic and thorough research on the synthesis, modification and molecular recognition of several amide-based endo-functionalized molecular tubes; By using ITC, NMR, X-ray crystallography, fluorescence spectroscopy, and stopped-flow spectroscopy, we would like to reveal the relationship between molecular recognition and cavity structure, and understand the physical organic origins of hydrophobic effects and hydrogen bonding in water; In addition, we will also explore the applications of these macrocyclic receptors in the detection of environmental pollutants, chiral analysis, and self-assembly materials.