Systematic Determination of Complex Reaction Mechanisms

复杂反应机理的系统测定

• 批准号: 0107927
• 负责人: John Ross
• 金额: $ 32.4万
• 依托单位: Stanford University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2001
• 资助国家: 美国
• 起止时间: 2001-07-01 至 2005-11-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0107927&HistoricalAwards=false
• 关键词: Systematic; Determination; Complex; Reaction; Mechanisms

John Ross of Stanford University is supported by the Theoretical and Computational Chemistry Program to develop further approaches to the determination of reaction pathways and mechanisms of complex reaction systems. The effort emphasizes the need for methods with small numbers of measurements, possibly of limited accuracy. Four new methods will be explored. In the first, a pulse perturbation approach will be examined using theory, model reaction calculations, and experiments, in order to elucidate the causal connectivities of species in the reaction pathways. A variant of this approach, a delayed response method, will be studied using theory and calculations with the goal of providing information on the number of chemical species in the reaction pathways, on rate coefficients, and on the reaction mechanism. Genetic algorithm methods will be used on a model system to study the possibility that oscillatory chemical reactions may have evolved in biological systems as a result of regular periodic perturbations, focusing on evolutionary changes in a reaction mechanism due to external effects. Finally, the reaction mechanism and stochastic analysis of memory effects and oscillations in single-molecule reactions will be investigated. Establishing how chemical reactions occur is an important goal in all fields of chemistry, including biological chemistry. This task has been approached, for nearly the last hundred years, by determining the chemical species present, studying separately the rates of various elementary chemical reactions in the entire reaction system, and then guessing the reaction mechanism, which is the proper combination of elementary reaction steps that lead from reactions to products that reproduce observations. For complex chemical reaction systems, this is an arduous and often controversial task, since many different proposed reaction mechanisms frequently fit the available data. The research that will be carried out in this project approaches the solution of chemical reaction mechanism problems from an alternative viewpoint, and the outcomes may have substantial impact on the determination of the mechanisms of complex chemical and biochemical systems in vitro, and ultimately in vivo.

斯坦福大学的John Ross得到了理论和计算化学计划的支持，以开发进一步的方法来确定复杂反应系统的反应途径和机制。 这一努力强调了需要少量测量的方法，可能精度有限。 将探索四种新方法。 在第一，脉冲微扰方法将使用理论，模型反应计算和实验，以阐明物种的因果联系的反应途径。 这种方法的一个变体，延迟响应方法，将使用理论和计算进行研究，其目标是提供有关反应途径中的化学物质的数量，速率系数和反应机理的信息。 遗传算法方法将被用于一个模型系统，研究振荡化学反应可能已经在生物系统中作为一个有规律的周期性扰动的结果演变的可能性，重点是由于外部效应的反应机制的演变变化。 最后，将研究单分子反应中记忆效应和振荡的反应机理和随机分析。 确定化学反应是如何发生的，是所有化学领域（包括生物化学）的重要目标。 在过去的近百年里，通过确定存在的化学物种，分别研究整个反应系统中各种基元化学反应的速率，然后猜测反应机理，这是从反应到再现观察结果的产物的基元反应步骤的适当组合。 对于复杂的化学反应体系，这是一项艰巨且经常有争议的任务，因为许多不同的反应机理经常符合现有的数据。本项目的研究将从另一个角度探讨化学反应机理问题的解决方案，其结果可能对体外和最终体内复杂化学和生化系统的机理的确定产生重大影响。