两亲性高分子在化学振荡反应中自组装行为的研究

Controlled self-assembly of polymers is an important bridge that connects polymer science and life science. In recent years, plenty of methods to regulate the self-assembly of polymers have been established. However, living bodies are complex dissipative structure. Therefore, for further studying the self-assembly of polymers in living bodies and creating new biomimic materials, it is still necessary to develop new method to regulate the self-assembly of polymers on the basis of the previous methods to get an insight into the self-assembly of polymers in dissipative systems and promote the research of controlled self-assembly of polymers to dissipative systems far from thermodynamic equilibrium. In this project, the self-assembly of polymers will be coupled with chemical oscillations, which are typical dissipative systems. The self-assembly behaviors of polymers under the chemical oscillations’ control will be investigated. Furthermore, the relationship between their self-assembly under the chemical oscillations’ control and their self-assembly under thermodynamic control, and the difference between the molecular structures of the polymers and their self-assembly behaviors in chemical oscillations will be also investigated. At last, the project will also build the mechanisms of the formation, dissociation and deformation of the aggregates formed by the amphiphilic polymers in chemical oscillations, by referring the method of studying the mechanisms of chemical oscillations.

高分子的可控自组装是连接高分子科学与生命科学的重要桥梁。近年来，人们已经建立了多种调控高分子自组装的方法。然而，生命体是复杂的耗散结构。因此，为了进一步认识生命体中高分子的组装规律和创造新型仿生功能材料，仍然有必要在传统调控方法的基础上，拓展调控高分子自组装的新方法，来认识高分子在耗散体系中自组装行为的特点和规律，将高分子可控自组装的研究推向远离平衡态的耗散体系。本项研究拟将高分子自组装与化学振荡这种经典的耗散体系耦合，研究两亲性高分子在化学振荡调控下的自组装行为，以及这种自组装行为与两亲性高分子在热力学平衡态下的自组装行为的联系和区别，还有不同分子结构的两亲性高分子在化学振荡中自组装行为的差异。最后，本项目还将结合化学振荡机理研究中的思路和方法，研究两亲性高分子组装体在化学振荡反应中形成、解离以及变化等过程的机理。

分子自组装是联系化学科学与生命科学以及材料科学的重要桥梁。目前为止，人们对热力学平衡态下的分子自组装（静态自组装）有非常深入的研究，但对热力学非平衡态下分子的组装行为了解上不充分。本项目的主要研究内容是具有刺激—响应性的两亲性嵌段高分子在化学振荡这种非平衡体系中的自组装行为。本项目选取了几种pH或碘响应的两亲性嵌段高分子，研究了他们在单峰（单次）振荡，semi-batch振荡，以及全振荡反应中的自组装行为。研究发现，这些响应性嵌段高分子的自组装行为会随着相应化学振荡反应的进行而发生变化。一种响应性嵌段高分子在化学振荡中的自组装行为与其在相同条件下的静态自组装行为有时会表现出差异。把响应性的高分子加入到化学振荡反应中后，化学振荡反应的周期和振幅都会发生缩小，缩小的程度与响应性高分子的加入量正相关。本项目还成功建立了加入响应性高分子后化学振荡反应的机理模型，通过机理模型推导出了理论的振荡曲线与实际振荡曲线比较符合，而且由机理模型推导出的振荡周期与高分子浓度间的正相关性也与实验结果基本相符。最后，我们将上述刺激—响应性嵌段高分子修饰到碳纳米管上，再与单峰振荡反应耦合，实现了水中有机污染物的可控、快速去除以及吸附剂的循环利用。