Grant: Discovery Grants Program - Individual

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.