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动力学定律、相-相展开、重整化群和国际标准化比值校准。

Kinetic laws, phase-phase expansions, renormalization group, and INR calibration.

作者信息

Vlad Marcel O, Corlan Alexandru D, Morán Federico, Spang Rainer, Oefner Peter, Ross John

机构信息

Department of Chemistry, Stanford University, Stanford, CA 94305-5080, USA.

出版信息

Proc Natl Acad Sci U S A. 2009 Apr 21;106(16):6465-70. doi: 10.1073/pnas.0809855106. Epub 2009 Apr 6.

Abstract

We introduce systematic approaches to chemical kinetics based on the use of phase-phase (log-log) representations of the rate equations. For slow processes, we obtain a corrected form of the mass-action law, where the concentrations are replaced by kinetic activities. For fast reactions, delay expressions are derived. The phase-phase expansion is, in general, applicable to kinetic and transport processes. A mechanism is introduced for the occurrence of a generalized mass-action law as a result of self-similar recycling. We show that our self-similar recycling model applied to prothrombin assays reproduces the empirical equations for the International Normalized Ratio calibration (INR), as well as the Watala, Golanski, and Kardas relation (WGK) for the dependence of the INR on the concentrations of coagulation factors. Conversely, the experimental calibration equation for the INR, combined with the experimental WGK relation, without the use of theoretical models, leads to a generalized mass-action type kinetic law.

摘要

我们基于速率方程的相-相(对数-对数)表示法,介绍化学动力学的系统方法。对于慢速过程,我们得到质量作用定律的修正形式,其中浓度被动力学活度所取代。对于快速反应,推导了延迟表达式。一般来说,相-相展开适用于动力学和传输过程。引入了一种机制,用于解释由于自相似循环而出现广义质量作用定律的情况。我们表明,应用于凝血酶原测定的自相似循环模型再现了国际标准化比值校准(INR)的经验方程,以及INR对凝血因子浓度依赖性的瓦塔拉、戈兰斯基和卡尔达斯关系(WGK)。相反,INR的实验校准方程与实验WGK关系相结合,在不使用理论模型的情况下,会导致广义质量作用类型的动力学定律。

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