机械力响应性高分子膜的构建与表面增强拉曼光谱研究

Mechanochemistry has been an important way of material synthesis, modification and functionalization. Now with the increasing knowledge of underlying molecular mechanism, a serial of mechanosensitive materials named mechanophore-linked polymer have been developed to demonstrate the new reactivity of the mechanical activation of chemical bonds. However, their active responses are mediated through force of different orientation, strength and time, at the molecular scale. To learn the kinetics of mechanochemical processes. It is necessary to further optimize the uniformity and distribution of mechanophore. Here we propose a mechanophore-linked polymer membrane strategy: the mechanophore incorporated polymer brushes are first anchored on surface. The responsive polymer brushes swelling-induced mechanical force activate the mechanical reaction of mechanophore. While the progress could be directly and locally determined by surface enhanced Raman spectroscopy. We anticipate a convenient force generator device stimulate by surface anchored polymer swelling, which can induce simultaneous and uniform force to the molecule monolayer. We also expect a distinctive Raman spectrum shift along with a serials of force modulation. This study will provide a foundation for a new strategy by which to in-situ measure the local stress on interface and understand the fundamental mechanism of mechanical activation.

机械力活化是材料制备、改性及功能化的重要方法之一。该领域的研究热点之一是在高分子链段或网络中引入机械力响应性基团，利用灵敏的光学手段对机械力化学过程进行监控。然而，在分子尺度上，处于无规高分子网络中的基团所感受到的机械力的方向、大小、时间均不一致，无法精确得到机械力活化下分子的动态信息。针对该问题，我们拟将机械力响应性基团一端接枝环境响应性的高分子刷，一端自组装到基底表面，形成基团取向一致的机械力响应性高分子膜。高分子膜在环境条件刺激下发生可控的受限溶胀，在基底界面产生应力并均匀作用于固定于表面的机械力响应性基团。同时利用表面增强拉曼光谱原位监测整个响应过程。通过考察受力时机械力响应性基团的拉曼光谱的变化，研究机械力诱导的化学反应及断键过程。该研究期望发展成一种新的机械力化学研究工具。

机械力活化是材料制备、改性及功能化的重要方法之一。该领域的研究热点之一是在高分子链段或网络中引入机械力响应性基团，利用灵敏的光学手段对机械力化学过程进行监控。然而，在分子尺度上，处于无规高分子网络中的基团所感受到的机械力的方向、大小、时间均不一致，无法精确得到机械力活化下分子的动态信息。针对该问题，我们拟将机械力响应性基团一端接枝环境响应性的高分子刷，一端自组装到基底表面，形成基团取向一致的机械力响应性高分子膜。高分子膜在环境条件刺激下发生可控的受限溶胀，在基底界面产生应力并均匀作用于固定于表面的机械力响应性基团。同时利用表面增强拉曼光谱原位监测整个响应过程。通过考察受力时机械力响应性基团的拉曼光谱的变化，研究机械力诱导的化学反应及断键过程。.在本课题中，我们利用石英晶体微天平与表面增强拉曼光谱研究聚电解质在受限溶胀是在表面产生的应力对相应作用分子的影响，尝试研究了分子受力的拉曼光谱与结构变化的关系。我们设计了原位的可检测高分子溶胀拉伸导致的分子受力行为及响应的方案，并进行了验证。本项目的实施进一步加深了对力参与的相应的化学反应及生化反应的过程的认识与了解。