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一条穿越蛋白质溶液热力学与统计力学的崎岖之路。

A Hilly path through the thermodynamics and statistical mechanics of protein solutions.

作者信息

Wills Peter R

机构信息

Department of Physics, University of Auckland, PB 92109, Auckland, 1142, Aotearoa, New Zealand.

出版信息

Biophys Rev. 2016 Dec;8(4):291-298. doi: 10.1007/s12551-016-0226-6. Epub 2016 Oct 25.

DOI:10.1007/s12551-016-0226-6
PMID:28510018
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5425806/
Abstract

The opus of Don Winzor in the fields of physical and analytical biochemistry is a major component of that certain antipodean approach to this broad area of research that blossomed in the second half of the twentieth century. The need to formulate problems in terms of thermodynamic nonideality posed the challenge of describing a clear route from molecular interactions to the parameters that biochemists routinely measure. Mapping out this route required delving into the statistical mechanics of solutions of macromolecules, and at every turn mathematically complex, rigorous, general results that had previously been derived previously, often by Terrell Hill, came to the fore. Central to this work were the definition of the "thermodynamic activity", the pivotal position of the polynomial expansion of the osmotic pressure in terms of molar concentration and the relationship of virial coefficients to details of the forces between limited-size groups of interacting molecules. All of this was richly exploited in the task of taking account of excluded volume and electrostatic interactions, especially in the use of sedimentation equilibrium to determine values of constants for molecular association reactions. Such an approach has proved relevant to the study of molecular interactions generally, even those between the main macromolecular solute and components of the solvent, by using techniques such as exclusion and affinity chromatography as well as light scattering.

摘要

唐·温佐尔在物理生物化学和分析生物化学领域的著作,是二十世纪下半叶在这一广泛研究领域蓬勃发展的某种澳大利亚式研究方法的重要组成部分。根据热力学非理想性来阐述问题的必要性,带来了描述一条从分子相互作用到生物化学家常规测量参数的清晰路径的挑战。规划这条路径需要深入研究大分子溶液的统计力学,而且在每一步,之前常常由特雷尔·希尔推导出来的数学上复杂、严谨且通用的结果都凸显出来。这项工作的核心是“热力学活度”的定义、渗透压关于摩尔浓度的多项式展开的关键地位,以及维里系数与有限大小相互作用分子基团间作用力细节的关系。在考虑排除体积和静电相互作用的任务中,尤其是在利用沉降平衡来确定分子缔合反应常数的值时,所有这些都得到了充分利用。事实证明,这种方法对于一般分子相互作用的研究是相关的,甚至对于主要大分子溶质与溶剂成分之间的相互作用也是如此,通过使用诸如排阻色谱、亲和色谱以及光散射等技术来实现。

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