Mechanochemical Transduction of Externally Applied Forces to Mechanophores
Mechanochemical Transduction of Externally Applied Forces to Mechanophores
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DOI：
10.1021/ja104958e
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发表时间：
2010-08-04
影响因子：
15
通讯作者：
Marx, Dominik
中科院分区：
文献类型：
--
作者：
Ribas-Arino, Jordi;Shiga, Motoyuki;Marx, Dominik
我们提出了一项关于脂肪族聚合物链在将外力传递到机械团中所起的作用的理论研究，这是力谱和声学实验的核心。在引入突变理论的严格方法后，我们证明了顺式1，2-二取代苯并环丁烯的断裂力与连接的高分子链的长度有显著的依赖关系，包括奇偶效应。这一意想不到的发现通过建立断裂力和机械基团与传导链交界处的局部变形之间的关联，进一步得到了合理的解释。力变换的黑森揭示了与这些链的相关结构参数相关的调和力常数与力的惊人的相关性。我们的发现不仅强调了在考虑机械力化学操纵时明确考虑聚合物链的必要性，而且还揭示了通过剪裁力传感链分子来调节力学响应性聚合物性能的可能性。
We present a theoretical study on the role played by aliphatic polymer chains in the transduction of external forces to mechanophores being at the heart of force spectroscopy and sonication experiments. Upon introducing a rigorous approach rooted in catastrophe theory, we demonstrate that the rupture force of a cis 1,2-disubstituted benzocyclobutene features a remarkable dependence, including odd-even effects, on the length of attached polymer chains. This unexpected finding is furthermore rationalized by establishing a correlation between the rupture force and local distortions of the mechanophore at its junctions with the transducing chains. The force-transformed Hessians unveil a surprising force-dependence of harmonic force constants associated with relevant structural parameters of these chains. Not only do our findings highlight the necessity of taking into account the polymer chains explicitly when thinking about mechanochemical manipulation, but they also announce the possibility of tuning the properties of mechanoresponsive polymers by tailoring the force-transducing chain molecules.