发展可控分子组装新方法——催组装 (一)

The concept of cassemblysis was proposed as a new method of controllable molecular assembly, based on the analogy between molecular assembly and chemical synthesis. In order to develop the experimental and theoretical methodologies of cassemblysis and also to explore the potential application to prepare functional materials, two systems were proposed in this program: (1) Investigation of the TPPS chiral cassemblysis system to understand the mechanism of cassemblysis. The main focus will be the association between molecular structure and efficiency of cassemblyst, design and fabrication of highly efficient cassemblyst, and revealing the mode of the interaction between cassemblyst and building blocks at the molecular level. (2) Construction of the photoelectro-catassemblysis system to develop a new method for fabricating functional materials. The main focus will be rational design and fabrication of the building blocks (including molecules and modified nanoparticles), optimizating the experimental parameters of electrochemical and photochemical process, and regulating the property of photoelectro-catassemblyst by nanofabrication. This proposal is intended to open a new avenue in controllable assembly, by developing the novel made-in-China concept of cassemblysis.

通过对分子组装和化学合成中调控手段的类比分析，提出可控组装新方法——催组装。旨在发展催组装的实验和理论方法学并探索催组装在功能材料制备中的潜在应用。具体开展以下两个体系的研究：一、以理解催组装机理为目的，研究TPPS手性催组装体系及其动力学过程。考察该体系中催组剂分子结构与其效率的关联，设计和合成更高效率催组剂，揭示催组剂与组装基元之间在分子层次上的作用方式。二、 以发展催组装为核心的组装体乃至材料制备新方法为目的，构建光电催组联体系，合成适用于该体系的分子以及纳米粒子组装基元。设计和优化光电催组联中光、电实验体系和溶液循环体系，通过纳米加工与化学修饰调控光电催组剂性能，提高制备材料效率。通过发展催组装新方法，在可控组装领域开拓具有我国特色的方向。

本项目发展了催组装的概念和理论，给出其定义：催组剂是一类能够在不改变总吉布斯自由能变化的条件下加速组装的物质，由催组剂促进的过程可称为催组装。我们创造一个新的英文单词“catassembly”来描述这一组装领域的全新概念，通过总结分析大量与催组装相关的实例，进一步加深了对催组装特点及催组装研究方法学的理解，该结果发表于英国皇家化学会的期刊《化学会评论》（Chem. Soc. Rev., 2014, 43, 399–411）。我们研究了卟啉衍生物TPPS、咪唑分子、手性小分子的三元体系和光电催组联体系这两个催组装体系，研究和讨论了手性小分子作为组装体系催组剂时发挥的作用及机理，设计并实现了电场控制下的光电催组联过程。