基于耗散自组装的智能超分子荧光体系的设计、构筑和应用研究

Energy driven assembly processes exist widely in organisms and nature. Recently, chemist use dissipative self-assembly to describe the energy driven assembly processes exist in living organisms on Earth. This project is intended to construct energy (chemical fuel) driven intelligent fluorescent emission system through the combination of dissipative self-assembly and supramolecular assembly. The designed energy driven intelligent fluorescent emission system attempts to simulate the ATP-driven bioluminescence process in nature from the perspective of supramolecular assembly. The main research contents are as follows: Firstly, we intend to study the "chemical fuel" driven esterification/hydrolysis process of pillar[5]arene. Then, we will attempts to construct "chemical fuel" driven supramolecular vesicle based on esterification/hydrolysis process of pillar[5]arene. After that, we will try to construct "chemical fuel" driven intelligent fluorescent emission system based on the "chemical fuel" driven supramolecular vesicle, which can be used to simulate the ATP-driven bioluminescence process in nature. The results of this project could help people study and imitate biological assembly processes from the perspective of supramolecular assembly. Moreover, this project could help people develop new energy-driven intelligent luminescent materials.

生命体和自然界生化活动中普遍存在着外界能量驱动下进行的组装过程，近年来，化学家引入了耗散自组装(Dissipative Self-assembly)的概念，来描述生命活动中存在的这种依赖外界能量驱动的组装行为。本项目拟将耗散自组装与超分子组装结合，构筑外界能量（“化学燃料”）驱动的智能荧光发射体系，该体系从超分子组装的角度模拟了自然界中ATP驱动的生物发光过程，主要研究内容如下：首先，本项目拟对“化学燃料”驱动的水溶性柱芳烃酯化/水解过程进行研究；在此基础上，利用“化学燃料”驱动的酯化/水解过程，进行“化学燃料”驱动的超分子囊泡组装/解组装研究；最后，利用“化学燃料”驱动超分子囊泡组装/解组装过程，进行“化学燃料”驱动的智能荧光发射体系的构筑，用于模拟自然界中ATP驱动的生物发光过程，项目结果有望在从超分子组装角度帮助人们研究和模仿生物组装过程以及研究开发新型能量驱动型智能发光材料。

能量驱动的耗散组装过程对于自然界中生物体各种生化过程都至关重要，也是构建真正的仿生材料的基础。本项目围绕构筑“化学燃料”驱动的耗散自组装功能体系，设计并构筑了耗散自组装型的功能化超分子水凝胶:(1)利用碳二亚胺EDC作为驱动多羧酸型化合物组装的“化学燃料”，构建了碳二亚胺EDC驱动的多羧酸耗散型水凝胶体系，该凝胶可被作为潜在的自擦拭型书写材料和信息保密材料使用。(2)利用硫酸二甲酯作为驱动多羧酸型化合物组装的“化学燃料”，将耗散自组装过程与聚集诱导发光效应(AIE)相结合，我们构筑了可以模仿能量驱动型生物发光过程的水凝胶，为开发和构建仿生物发光材料提供了方法和参考。（3）进一步我们还在基于四苯乙烯衍生物的人工光捕获纳米材料和圆偏振发光材料方面进行了探索，为进一步发展构筑结构和功能复杂的“化学燃料”驱动型耗散自组装体系奠定了研究基础。本项目的研究成果不仅发展了“化学燃料”驱动型耗散自组装水凝胶的构筑思路和方法，同时也为构造和发展具有复杂功能的耗散自组装材料提供了研究思路和参考。