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分子间相互作用反应动力学的动力学分析。

Moment analysis for reaction kinetics of intermolecular interactions.

机构信息

Department of Chemistry, Faculty of Science, Rikkyo University, Toshima-ku, Tokyo, Japan.

出版信息

Electrophoresis. 2018 Dec;39(23):3032-3039. doi: 10.1002/elps.201800218. Epub 2018 Sep 12.

Abstract

Moment equations were developed on the basis of the principle of relativity for analyzing elution peak profiles measured by ACE to analytically determine the association (k ) and dissociation (k ) rate constants of intermolecular interactions. Basic equations representing the mass balance, mass transfer rate, and reaction kinetics in ACE system in a Galilean coordinate system S were transformed to those in another coordinate system S', which imaginarily moved with respect to S. Moment equations for ACE peaks in S' in the time domain were derived from the analytical solution of the modified basic equations in the Laplace domain. Moment equations for ACE peaks in S were derived from those in S' by the inverse Galilean transformation. The moment equations were used for analyzing some ACE data previously published to determine k and k values. It was demonstrated that the moment equations were effective for extracting the information about affinity kinetics of intermolecular interactions from the elution peak profiles measured by ACE. The moment equations were also used to discuss the influence of mass transfer and reaction kinetics on ACE peak profiles. Some results of the numerical calculations are also indicated in Supporting Information.

摘要

基于相对论原理,我们推导出了矩方程,用于分析 ACE 测量得到的洗脱峰轮廓,以分析确定分子间相互作用的缔合(k)和离解(k)速率常数。在伽利略坐标系 S 中表示 ACE 系统中质量平衡、传质速率和反应动力学的基本方程被转换为另一个坐标系 S'中的方程,该坐标系想象为相对于 S 移动。从拉普拉斯域中修正基本方程的解析解中推导出了 S'中 ACE 峰的时域矩方程。通过逆伽利略变换,从 S'中的矩方程推导出 S 中的 ACE 峰的矩方程。利用矩方程分析了先前发表的一些 ACE 数据,以确定 k 和 k 值。结果表明,矩方程可有效从 ACE 测量得到的洗脱峰轮廓中提取分子间相互作用的亲和动力学信息。矩方程还用于讨论传质和反应动力学对 ACE 峰轮廓的影响。在支持信息中还给出了一些数值计算的结果。

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