Research Institute for Electronic Science, Hokkaido University , N20, W10, Kita-Ku, Sapporo 001-0020, Japan.
Adolphe Merkle Institute, University of Fribourg , Chemin des Verdiers 4, CH-1700 Fribourg, Switzerland.
J Am Chem Soc. 2018 Feb 7;140(5):1584-1587. doi: 10.1021/jacs.7b12405. Epub 2018 Jan 24.
The integration of mechanophores, motifs that transduce mechanical forces into chemical reactions, allows creating materials with stress-dependent properties. Typical mechanophores are activated by cleaving weak covalent bonds, but these reactions can also be triggered by other stimuli, and this renders the behavior unspecific. Here we show that this problem can be overcome by extending the molecular-shuttle function of rotaxanes to mechanical activation. A mechanically interlocked mechanophore composed of a fluorophore-carrying macrocycle and a dumbbell-shaped molecule containing a matching quencher was integrated into a polyurethane elastomer. Deformation of this polymer causes a fluorescence turn-on, due to the spatial separation of fluorophore and quencher. This process is specific, efficient, instantly reversible, and elicits an easily detectable optical signal that correlates with the applied force.
力敏基团(能够将机械力转化为化学反应的结构单元)的整合使得具有应力依赖性性质的材料的构建成为可能。典型的力敏基团通过切断弱共价键来激活,但这些反应也可以被其他刺激触发,这使得行为变得不具有特异性。在这里,我们通过将轮烷的分子梭功能扩展到机械激活来克服这个问题。一个由荧光团负载大环和一个哑铃形分子组成的机械互锁力敏基团,其中哑铃形分子包含一个匹配的猝灭剂,被整合到聚氨酯弹性体中。这种聚合物的变形会导致荧光开启,这是由于荧光团和猝灭剂的空间分离。这个过程是特异性的、高效的、瞬间可逆的,并产生一个容易检测的光学信号,该信号与所施加的力相关联。