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Relations between biochemical thermodynamics and biochemical kinetics.

机译:生化热力学与生化动力学之间的关系。

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摘要

The parameters in steady-state or rapid-equilibrium rate equations for enzyme-catalyzed reactions depend on the temperature, pH, and ionic strength, and may depend on the concentrations of specific species in the buffer. When the complete rate equation (i.e. the equation with parameters for the reverse reaction as well as the forward reaction) is determined, there are one or more Haldane relations between some of the kinetic parameters and the apparent equilibrium constant for the reaction that is catalyzed. When the apparent equilibrium constant can be calculated from the kinetic parameters, the equilibrium composition can be calculated. This is remarkable because the kinetic parameters all depend on the properties of the enzymatic site, but the apparent equilibrium constant and the equilibrium composition do not. The effects of ionic strength and pH on the unoccupied enzymatic site and the occupied enzymatic site have to cancel in the Haldane relation or in the calculation of the apparent equilibriumconstant using the rate constants for the steps in the mechanism. Several simple enzymatic mechanisms and their complete rate equations are discussed.
机译:用于酶催化反应的稳态或快速平衡速率方程式中的参数取决于温度,pH和离子强度,并且可能取决于缓冲液中特定物质的浓度。当确定了完全速率方程(即具有用于逆反应和正反应的参数的方程)时,在某些动力学参数与所催化反应的表观平衡常数之间存在一个或多个Haldane关系。当可以从动力学参数计算表观平衡常数时,可以计算出平衡组成。这是惊人的,因为动力学参数都取决于酶位点的性质,但表观平衡常数和平衡组成并不如此。离子强度和pH对未占用酶位和占用酶位的影响必须在Haldane关系中或使用机理步骤中的速率常数计算表观平衡常数时消除。讨论了几种简单的酶机制及其完整的速率方程。

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