US-France Cooperative Research: Molecular Dynamics Simulation of Proton Transfer Reactions in Solution

美法合作研究：溶液中质子转移反应的分子动力学模拟

• 批准号: 8914989
• 负责人: James Hynes
• 金额: $ 0.79万
• 依托单位: University of Colorado at Boulder
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 1990
• 资助国家: 美国
• 起止时间: 1990-04-01 至 1992-09-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=8914989&HistoricalAwards=false
• 关键词: US; France; Cooperative; Research; Molecular

This award will support collaborative research between Dr. James Hynes, University of Colorado, and Dr. Daniel Borgis, Laboratoire de Physique Theoretique des Liquides, University of Pierre and Marie Curie, Paris, France. The objective of the project is to develop an improved theory for treating simple proton transfer reactions in solution. Protein transfer reactions in solution play a central role in chemistry, in particular in acid-base chemistry and enzyme catalysis. However, no comprehensive molecular level description of such reactions and their rates yet exist. In part, this is due to their special character, which includes quantum proton tunnelling through a barrier rather than classical thermal activation over it, and an essential involvement of the surrounding polar solvent molecules strongly coupled to the proton. Aided by recent advances in theoretical and computer simulation techniques, the investigators propose to perform molecular dynamics computer simulation of model proton transfer reactions in polar solvents. Reaction rates will be calculated and the role of solvent polarity and dynamics, and of certain molecular vibrations, will be determined. Simple yet realistic models will be initially employed to clarify the essential reaction features and to establish the simulation techniques. The systems studied will then progress to even more realistic systems directly susceptible to experimental investigation. Emphasis will be placed on calculating quantities (e.g. solvent dependence, isotope effects) which can guide the interpretation of experiments. A detailed microscopic description of proton transfer reactions is expected to result from the project. The proposed study should provide theoretical insight into understanding this important reaction class and also should provide an impetus for new experiments to probe the influence on these rates of solvent polarity and dynamics. The project will benefit for the complementary expertise of the two investigators in this rapidly developing area of physical chemistry.

该奖项将支持科罗拉多大学 James Hynes 博士和法国巴黎皮埃尔和玛丽居里大学液体物理理论实验室 Daniel Borgis 博士之间的合作研究。 该项目的目标是开发一种改进的理论来处理溶液中的简单质子转移反应。 溶液中的蛋白质转移反应在化学中发挥着核心作用，特别是在酸碱化学和酶催化中。 然而，尚不存在此类反应及其速率的全面分子水平描述。 在某种程度上，这是由于它们的特殊特性，其中包括量子质子隧道穿过势垒而不是其上的经典热激活，以及周围极性溶剂分子与质子强耦合的重要参与。 借助理论和计算机模拟技术的最新进展，研究人员建议对极性溶剂中的模型质子转移反应进行分子动力学计算机模拟。 将计算反应速率，并确定溶剂极性和动力学以及某些分子振动的作用。 最初将采用简单而现实的模型来阐明基本的反应特征并建立模拟技术。 然后，所研究的系统将发展为直接易于实验研究的更现实的系统。 重点将放在计算可以指导实验解释的数量（例如溶剂依赖性、同位素效应）。 该项目预计将产生质子转移反应的详细微观描述。 拟议的研究应该为理解这一重要的反应类别提供理论见解，并且还应该为新的实验提供动力，以探讨对溶剂极性和动力学速率的影响。 该项目将受益于两位研究人员在这个快速发展的物理化学领域的互补专业知识。