THEORETICAL STUDIES ON THE DYNAMIC ASPECTS OF MACROMOLECULAR FUNCTION

大分子功能动力学方面的理论研究

• 批准号: 3854790
• 负责人: A SZABO
• 金额: --
• 依托单位: NATIONAL INSTITUTE OF DIABETES AND DIGESTIVE AND KIDNEY DISEASES
• 依托单位国家: 美国
• 资助国家: 美国
• 起止时间: 至
• 项目状态: 未结题
• 来源: https://reporter.nih.gov/project-details/3854790
• 关键词: chemical association; chemical binding; chemical kinetics; chemical reaction; computer simulation; diffusion; fluorescence; fluorimetry; ligands; macromolecule; mathematical model; microelectrodes; molecular dynamics; thermodynamics

The theory of geminate and bimolecular diffusion influenced reactions was used to interpret the rebinding of carbon monoxide to protoheme following photodissociation measured over ten decades of time (1ps to 10ms). It was shown that the highly nonexponential behavior of the initial geminate phase, which cannot be explained using simple kinetic schemes, is a reflection of the diffusive motion of the reactants. Molecular dynamics simulations have been used to obtain the kinetics of a simple model of fluorescence quenching in a hard sphere liquid. These computer generated "experimental" results we then used to test the Smoluchowski theory of irreversible reactions. Considering the many particle nature of the problem, the agreement between theory and simulations was surprisingly good over a wide range of quencher concentrations. The Smoluchowski theory has been generalized to treat second order reversible diffusion-influenced bimolecular reactions. It was shown that a small initial deviation of the concentrations from their equilibrium values decays to zero nonexponentially in contrast to the prediction of ordinary chemical kinetics. A theory was developed to obtain the time dependent rate of binding of ligands to a cell partially covered by receptors. A special case of the result derived in this work was used to find an analytic expression for the current at a random array of microdisk electrodes. Finally, a new brownian dynamics algorithm was developed to simulate the time dependent bimolecular rate coefficient for reactions involving species with complex geometries that interact via an arbitrary potential.

Geminate和双分子扩散的理论影响了反应 被用来解释一氧化碳对原始的重新固定 在光解离时测量了十年的时间（1PS至1PS） 10ms）。 结果表明，高度非义务行为 最初的Geminate阶段，无法使用简单的动力学来解释 方案是反应物扩散运动的反映。 分子动力学模拟已用于获得动力学 在硬球液体中荧光淬灭的简单模型。 这些计算机生成的“实验”结果我们然后用于测试 不可逆反应的Smoluchowski理论。 考虑到 问题的许多粒子性质，理论与 在广泛的淬火器中，仿真非常好 浓度。 Smoluchowski理论已被概括为治疗 二阶可逆扩散影响的双分子反应。 它 结果表明，浓度与其浓度的初始偏差很小 平衡值衰减至零非分数与 普通化学动力学的预测。 一个理论已发展为 获得配体与细胞的结合率部分的时间依赖性率 被受体覆盖。 这项工作得出的结果的特殊情况 被用来以随机的方式找到电流的分析表达 微电极电极阵列。 最后，一种新的布朗动态 开发算法是为了模拟时间依赖的双分子速率 涉及具有复杂几何形状物种的反应系数 通过任意潜力相互作用。