Department of Chemistry, University of Illinois, Urbana, Illinois 61801, USA.
J Am Chem Soc. 2012 May 9;134(18):7620-3. doi: 10.1021/ja301928d. Epub 2012 May 1.
We demonstrate an accurate prediction of the micromechanical behavior of a single chain of cyclopropanated polybutadiene, which is governed by rapid isomerization of the cyclopropane moieties at ~1.2 nN, from the force-rate correlation of this reaction measured in a small series of increasingly strained macrocycles. The data demonstrate that a single physical quantity, force, uniquely defines the dynamics across length scales from >100 to <1 nm and that strain imposed through molecular design and that imposed by micromanipulation techniques have equivalent effects on the kinetics of a chemical reaction. This represents a new method of screening potential monomers for applications in stress-responsive materials that could also facilitate atomistic interpretations of single-molecule force experiments.
我们展示了对单链环丙基聚丁二烯的微观力学行为的精确预测，该行为受环丙烷部分在~1.2 nN 下的快速异构化控制，这是从小系列逐渐应变大环中测量的这种反应的力-速率相关性得出的。该数据表明，单一物理量，即力，独特地定义了从>100 到<1nm 的长度尺度上的动力学，并且通过分子设计施加的应变和通过微操作技术施加的应变对化学反应动力学具有等效的影响。这代表了一种筛选潜在单体以应用于响应应力材料的新方法，也可以促进对单分子力实验的原子解释。
