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Fluctuation theory of molecular association and conformational equilibria

机译:分子缔合与构象平衡的涨落理论

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摘要

General expressions relating the effects of pressure, temperature, and composition on solute association and conformational equilibria using the fluctuation theory of solutions are provided. The expressions are exact and can be used to interpret experimental or computer simulation data for any multicomponent mixture involving molecules of any size and character at any composition. The relationships involve particle-particle, particle-energy, and energy-energy correlations within local regions in the vicinity of each species involved in the equilibrium. In particular, it is demonstrated that the results can be used to study peptide and protein association or aggregation, protein denaturation, and protein-ligand binding. Exactly how the relevant fluctuating properties may be obtained from experimental or computer simulation data are also outlined. It is shown that the enthalpy, heat capacity, and compressibility differences associated with the equilibrium process can, in principle, be obtained from a single simulation. Fluctuation based expressions for partial molar heat capacities, thermal expansions, and isothermal compressibilities are also provided.
机译:使用溶液的波动理论,提供了有关压力,温度和组成对溶质缔合和构象平衡的影响的一般表达式。这些表述是准确的,可用于解释任何多组分混合物的实验或计算机模拟数据,这些混合物涉及任何大小和特征的分子,任何组成。该关系涉及平衡中涉及的每个物种附近的局部区域内的粒子-粒子,粒子-能量和能量-能量相关性。特别地,证明了该结果可用于研究肽和蛋白质的缔合或聚集,蛋白质变性和蛋白质-配体结合。还概述了如何从实验或计算机模拟数据中获得相关的波动特性。结果表明,与平衡过程相关的焓,热容量和可压缩性差异原则上可以从单个模拟中获得。还提供了基于摩尔的部分摩尔热容,热膨胀和等温压缩率的表达式。

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