Department of Chemistry, University of Illinois, Urbana, IL 61801, USA.
Chem Soc Rev. 2011 May;40(5):2359-84. doi: 10.1039/c0cs00148a. Epub 2011 Jan 31.
The purpose of this critical review is to introduce the reader to an increasingly important class of phenomena: enormous changes in rates of simple chemical reactions within macromolecules as they are stretched by interactions with the environment. In these chemomechanical, or mechanochemical, phenomena the effect of the macromolecular environment can be visualized as a spring (harmonic or anharmonic) bridging and pulling apart a pair of atoms of the macromolecule. Being able to predict how the parameters of this spring affect the kinetics of the reactions occurring between the constrained atoms may create revolutionary opportunities for designing new reactions, molecules and materials that would capture large-scale deformations to drive useful chemistry or, conversely, that would propel autonomous micro- and nanomechanical devices by coupling them to the concerted motion of atoms that convert reactants into products. Although chemists have long studied and exploited coupling between molecular strain and reactivity in small molecules, a quantitative understanding of the relationship between large-scale (>50 nm) strain and localized reactivity presents unique conceptual and experimental challenges. Below we discuss both the phenomenology and the interpretive framework of chemomechanical phenomena (102 references).
在大分子与环境相互作用时，其中简单化学反应速率发生巨大变化。在这些化学机械或机械化学现象中，大分子环境的影响可以被视为连接和拉开大分子中一对原子的弹簧（谐或非谐）。能够预测这种弹簧的参数如何影响约束原子之间反应的动力学，可能为设计新的反应、分子和材料提供革命性的机会，这些反应、分子和材料可以捕获大规模变形以驱动有用的化学，或者相反，通过将它们与原子的协同运动耦合起来，从而推动自主的微纳机械装置，将反应物转化为产物。尽管化学家们长期以来一直在研究和利用小分子中分子应变与反应性之间的耦合，但对大尺度（>50nm）应变与局部反应性之间的关系的定量理解提出了独特的概念和实验挑战。下面我们将讨论化学机械现象的现象学和解释框架（102 篇参考文献）。
