Wu Mengjiao, Guo Zhen, He Weiye, Yuan Wei, Chen Yulan
Department of Chemistry, Key Laboratory of Mechanism Theory and Equipment Design of State Ministry of Education, Tianjin University Tianjin 300354 China
Chem Sci. 2020 Dec 8;12(4):1245-1250. doi: 10.1039/d0sc06140a.
Self-reporting polymers, which can indicate damage with perceptible optical signals in a tailored force range, are useful as stress-sensitive sensors. We demonstrate a simple approach to realize this function by embedding two distinct mechanophores - rhodamine () and bis(adamantyl)-1,2-dioxetane (), in polyurethane/polylactic acid blends. The deformed blends generate red coloration and red chemiluminescence. Such a unique dual-responsive behavior was evaluated by solid-state UV-vis spectroscopy, macroscopic tensile tests with RGB and light intensity analyses, which supported a stress-correlated occurrence of the ring-opening of , the scission of and the fluorescence resonance energy transfer process between the respective mechanochemical species. Complementarity stemming from the difference in properties and manifestations of the two mechanophores is essential. That is, the more labile allows shifting the appreciable optical changes to a much lower force threshold; the transient nature and high dynamic range of mechanochemiluminescence from map in real time where and when many of the covalently incorporated dioxetane bonds break; besides, the disrupted yet non-scissile structure of acts as a fluorescent acceptor to effectively harvest chemiluminescence from ruptured . The current strategy is thus empowering multi-functional mechano-responsive polymers with greatly improved sensitivity and resolution for multimodal stress reporting.
自报告聚合物能够在特定的力范围内以可感知的光学信号指示损伤,可用作应力敏感传感器。我们展示了一种简单的方法来实现这一功能,即将两种不同的机械发色团——罗丹明()和双(金刚烷基)-1,2-二氧杂环丁烷()嵌入聚氨酯/聚乳酸共混物中。变形后的共混物会产生红色着色和红色化学发光。通过固态紫外-可见光谱、带有RGB和光强度分析的宏观拉伸试验对这种独特的双响应行为进行了评估,这些试验支持了与应力相关的、的开环、的断裂以及各机械化学物种之间的荧光共振能量转移过程的发生。两种机械发色团在性质和表现上的差异所产生的互补性至关重要。也就是说,更不稳定的能将明显的光学变化转移到低得多的力阈值;的机械化学发光的瞬态性质和高动态范围能够实时映射许多共价结合的二氧杂环丁烷键断裂的位置和时间;此外,的被破坏但未断裂的结构充当荧光受体,以有效收集来自断裂的的化学发光。因此,当前的策略赋予了多功能机械响应聚合物极大提高的灵敏度和分辨率,用于多模态应力报告。