The Entropic and Enthalpic Contributions to Force-Dependent Dissociation Kinetics of the Pyrophosphate Bond

被引：38
作者：
Hermes, Matthew [1 ]
Boulatov, Roman [1 ]
机构：
[1] Univ Illinois, Dept Chem, Urbana, IL 61801 USA
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2011年 / 133卷 / 50期
关键词：
FREE-ENERGY; STRESS; MODELS;
D O I：
10.1021/ja207421v
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
We report quantum-chemical calculations of the activation free energy of solvolysis of the pyrophosphate bond in a conformationally flexible reactant coupled to a constraining potential. The results reveal a significant contribution of conformational entropy to the force-dependent kinetics of even a fairly small reactant, suggesting that accurate predictions or molecular interpretation of localized reaction kinetics in stretched polymers may require explicit consideration of their force-dependent conformational heterogeneity. We further show that modeling the conformational space of the reactant and the transition state as collections of overlapping harmonic wells accurately predicts the force-dependent activation free energy up to 2 nN without detailed quantum-chemical computations. An estimate of the activation energies is obtained from the minimal (Eyring Bell Evans) model using the local coordinate common to all nucleophilic displacement reactions.
引用
收藏
页码：20044 / 20047
页数：4
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