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通常的扩散控制反应理论是以球形对称反应体系为背景的,故用在计算酶与带电底物结合反应速率的最大限度时,不可能较合理地考虑各种影响反应速率的效应。而且,在现有的实验中,已出现了这样的佯谬:一些酶与带电底物结合反应的速率比按通常理论所算得的结合速率的最大限度还要大!因此,重新探讨酶-带电底物反应体系中的各种效应,就显得十分必要。为此,本文在以前工作的基础上,探讨了这种非球形对称快速反应体系的动力学特性。通过计算,给出了方向因子、力程因子与离子强度、反应物所带电荷间的定量关系,从而为酶与带电底物的结合反应提供了新的最大限度。并应用到延胡索酸酶及D-甘油醛-3-磷酸脱氢酶的反应中,解释了通常的扩散控制反应理论所不能解释的现象。此外,还探讨了非平衡定态反应体系中Brφnsted方程成立的条件。
The usual theory of diffusion-controlled reaction is based on a spherical symmetric reaction system. Therefore, it is impossible to reasonably consider various effects that affect the reaction rate when calculating the maximum reaction rate of enzyme and charged substrate. Moreover, in the existing experiments, there has been a paradox that some enzymes bind to charged substrates more rapidly than the maximal rate of binding, as calculated by common theory! Therefore, Substrate reaction system in a variety of effects, it is very necessary. Therefore, based on the previous work, this paper discusses the kinetics of this non-spherical symmetric rapid reaction system. Through the calculation, the quantitative relationship between the direction factor, the kinetic factor, the ionic strength and the charge of the reactant is given, which provides a new maximum for the binding reaction between the enzyme and the charged substrate. And applied to fumarase and D-glyceraldehyde-3-phosphate dehydrogenase reaction, explain the usual diffusion control reaction theory can not explain the phenomenon. In addition, the conditions for the Brφnsted equation to be established in an unbalanced stationary reaction system are also discussed.