Theoretical Studies of Environmental and Biochemical Relevance

本研究计划涉及与化学系统的热力学和动力学研究有关的计算物理有机化学的两个流。******(1)热力学研究对于正确理解各种具有环境和生物化学重要性的系统至关重要，分为两个主题领域：氘同位素对酸解离和金属水解的影响，以响应CANDU运营商确定的需要，帮助延长加拿大老化但必不可少的核反应堆的寿命，并帮助设计下一代CANDU反应堆；计算持久性有机污染物的平衡常数，以便适当模拟其在不同介质之间的环境分布和迁移，特别关注对人类健康构成重大风险的多氟和全氟烷基物质（PFASs）。为了响应开发准确方法来估计pfsa的物理化学性质的明确需求，我们的工作将有助于创建更可靠的长期环境命运预测。******(2)动力学研究，利用我们以前在这一领域的工作，将在环境和生物化学相关的系统上进行，也分为两个主题领域：第一个涉及降解持久性有机污染物的氧化和还原过程，使人们更好地了解能够攻击和降解溶液中的有机化合物的高级氧化过程的机制，以便更好地控制反应顺序的速度、最终产物的形成及其产量，并将有助于确定可能的生物补救办法；生物化学动力学的研究，重点关注潜在的各种抗氧化物质对修复蛋白质氧化损伤的重要作用，这是生物氧化剂的主要目标。******我们的理论研究是由这样一个事实，即强大的计算机的可用性和新的理论方法和算法的发展使计算化学成为化学研究实验的补充工具。*****

This research proposal involves two streams in computational physical organic chemistry related to the thermodynamic and kinetic study of chemical systems. ******(1) Thermodynamic studies, essential to properly understand a variety of systems of environmental and biochemical importance, are divided into two thematic areas: Deuterium isotope effects on acid dissociation and metal hydrolysis, in response to a need identified by CANDU operators to help extend the lifetimes of Canada's aging but essential nuclear reactors, and to help design the next generation of CANDU reactors, and; calculating equilibrium constants of persistent organic pollutants (POPs) in order to properly model their environmental distribution and transport between different media, with special attention to poly- and perfluorinated alkyl substances (PFASs) which represent a significant human health risk. In response to a clear need to develop accurate methods to estimate the physico-chemical properties of PFSAs for which little experimental data are available, our work will help create more reliable long-term environmental-fate predictions.******(2) Kinetic studies, which take advantage of our previous work in this area, will be performed on systems of environmental and biochemical relevance, also divided into two thematic areas: The first involves oxidation and reduction processes to degrade POPs, leading to a better understanding of the mechanisms of advanced oxidation processes able to attack and degrade organic compounds in solution, in order to better control the rate of the sequence of reactions, the final products formation, and their yield, and which will help to identify possible bio-remediation solutions, and; biochemical kinetic studies, focusing on the potential of various antioxidant species important for the repair of oxidative damage to proteins, a major target of biological oxidants.******Our theoretical research is facilitated by the fact that the availability of powerful computers and the development of new theoretical methods and algorithms have made computational chemistry a complementary tool to experiment in chemical research.*****