溶剂粘度对酶促反应的影响模型
Model for solvent viscosity effect on enzymatic reactions
摘要:
为什么酶促反应的反应速率常数通常与溶剂粘度的分数幂指数成反比仍然是一个三十年前的难题。现有的解释的现象调用的修改1。传统的Kramers理论或2.斯托克斯定律我们表明,有一个替代的解释的现象,在这些修改实际上都不是必不可少的。我们和解1。和2.与实验观察到的相关性。我们假设,在溶剂中的酶溶液有或没有助溶剂分子是一个合奏的样品具有不同的粘度值的系统沿反应坐标的运动。我们假设该粘度由共溶剂分子的重量$q$和蛋白质基质和溶剂分子的重量$1-q$的贡献组成。我们在我们的系统中引入异质性的帮助下,分布的重量$q$。我们验证了直接替代的分布的未知函数的积分方程的解。模型的所有参数都与实验观测值有关。一般形式主义的例证分析的文献实验数据从hemerythin的氧逃逸。
英文摘要:
Why reaction rate constants for enzymatic reactions are typically inversely proportional to fractional power exponents of solvent viscosity remains to be already a thirty years old puzzle. Available interpretations of the phenomenon invoke to either a modification of 1. the conventional Kramers' theory or that of 2. the Stokes law. We show that there is an alternative interpretation of the phenomenon at which neither of these modifications is in fact indispensable. We reconcile 1. and 2. with the experimentally observable dependence. We assume that an enzyme solution in solvent with or without cosolvent molecules is an ensemble of samples with different values of the viscosity for the movement of the system along the reaction coordinate. We assume that this viscosity consists of the contribution with the weight $q$ from cosolvent molecules and that with the weight $1-q$ from protein matrix and solvent molecules. We introduce heterogeneity in our system with the help of a distribution over the weight $q$. We verify the obtained solution of the integral equation for the unknown function of the distribution by direct substitution. All parameters of the model are related to experimentally observable values. General formalism is exemplified by the analysis of literature experimental data for oxygen escape from hemerythin.
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