酶促反应活化能分布与反应前指数的关系
Relationship between preexponent and distribution over activation barrier energies for enzymatic reactions
摘要:
揭示了酶/蛋白质反应的速率常数和活化能分布的前指数之间的关系。我们认为一个酶的解决方案作为一个整体的个别分子与不同的值所描述的分布的活化势垒能。从溶剂粘度对前指数的影响出发,导出了该分布的积分方程,并求出了近似解。我们的方法使我们能够达到双重目的。一方面,它产生了一个简单的解释的溶剂粘度依赖于酶/蛋白质反应,既不需要修改的Kramers'理论,也不需要的斯托克斯定律。另一方面,我们的方法使我们能够推导出的激活势垒能量的分布形式。得到的函数有一个熟悉的钟形的形式,是在定性与单酶动力学测量的结果。一般形式主义的例证文献实验数据的分析。
英文摘要:
A relationship between the preexponent of the rate constant and the distribution over activation barrier energies for enzymatic/protein reactions is revealed. We consider an enzyme solution as an ensemble of individual molecules with different values of the activation barrier energy described by the distribution. From the solvent viscosity effect on the preexponent we derive the integral equation for the distribution and find its approximate solution. Our approach enables us to attain a twofold purpose. On the one hand it yields a simple interpretation of the solvent viscosity dependence for enzymatic/protein reactions that requires neither a modification of the Kramers' theory nor that of the Stokes law. On the other hand our approach enables us to deduce the form of the distribution over activation barrier energies. The obtained function has a familiar bell-shaped form and is in qualitative agreement with the results of single enzyme kinetics measurements. General formalism is exemplified by the analysis of literature experimental data.
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