刺激响应型超分子聚合物的竞争调控机制研究及其在智能材料中的应用

Stimuli-responsive supramolecular polymers (SRSPs) showed promising applications in the field of smart materials. However, the potential uses of the SRSPs are largely dependent on the stimuli-responsive properties of the SRSPs. Therefore, the developments of new stimuli-responsive mechanisms are very important. In view of these, to enrich stimulus-responsiveness properties of SRSPs, this project introduced a novel “competitively control mode” into the design of SRSPs. As the main point of the “competitively control mode”, the stimuli-responsiveness of the SRSPs could be selectively controlled by the competitive among two or more different self-assemble driving forces. And more importantly, by introduce difference competitive self-assemble driving forces; we can obtain different stimuli-responsiveness. By these means, the stimuli-responsiveness of the SRSPs could be easily controlled by the rationally introduction of suitable competitive self-assemble driving forces. Therefore, the SRSPs possess expected properties could be rationally developed according to this approach. This project will design and synthesis a series of multi-self-assemble driving forces based supramolecular polymer monomer, study the approach of the introduction of different competitive self-assemble driving forces and their competitively control mechanism. Finally, we could develop a series of SRSPs with various stimuli-responsive properties based on the “competitively control mode”. Therefore, this project has the promising application perspective and important academic value.

刺激响应型超分子聚合物在智能材料领域有着诱人的应用前景。超分子聚合物特定的刺激响应性能是决定其功能和用途的核心要素。因此研究和建立新的刺激响应机制对开发新型智能材料具有重要的意义。本项目在申请者前期工作的基础上提出了通过竞争自组装控制超分子聚合物刺激响应性能的模式。这种模式的核心思路是在超分子聚合物的自组装体系中引入竞争机制，当一种或几种自组装驱动力之间存在竞争时，可利用这种竞争作用实现对刺激响应的选择性控制。更为重要的是，通过引入不同的竞争作用可实现对不同刺激的选择性响应。这样可以通过引入适当的竞争机制实现对刺激响应有目的地控制，从而制备出具有预期功能的刺激响应型超分子聚合物。本项目将设计合成具有多重自组装位点的单体分子和超分子聚合物、重点研究不同竞争机制的引入方法、竞争原理及模式以及在这些竞争机制控制下超分子聚合物的刺激响应性能。这项研究具有一定的应用前景和较好的学术意义。

刺激响应型超分子聚合物由于其丰富的刺激响应性能在众多领域有着诱人的应用前景。超分子材料的刺激响应机理决定其性能和用途，因此研究和发展刺激响应新机制对开发新型智能材料具有重要的意义。本项目提出了“通过竞争自组装控制超分子聚合物刺激响应性能”的新思路，围绕该核心思路，本项目成功的设计提出或总结发现了几种新颖的调控超分子聚合物刺激响应性能的新机理或新模式，如“多重竞争调控模式”、“竞争氧化还原”机理、“外墙-π”作用和“阳离子-π”作用的竞争机理和“阴离子诱导的超分子聚合”等机理。本项目成功地将这些调控超分子聚合物刺激响应的新机理和新途径应用到了刺激响应型超分子聚合物材料的设计中，制备了多个系列的新型超分子聚合物。在这些新机理的调控下，所得的超分子聚合物实现了对氰根、氟离子等多种重要阴离子；汞离子、铅离子、铬离子、铜离子、铁离子、稀土金属离子等阳离子；氨基酸、染料分子、苦味酸、甲醛分子等多种重要客体分子的高选择性高灵敏响应。这些材料不仅可以用于方便快捷和低成本地高灵敏检测和分离这些离子、分子，还可用于离子响应型荧光显示材料，保密书写材料等。本项目所提出和发现的调控超分子聚合物刺激响应的新机理和新模式为今后刺激响应型超分子聚合物和超分子智能材料的研究提供了一定的理论基础和设计思路，另外，本项目研制的系列刺激响应型超分子聚合物材料也具有很好的应用前景。