The objectives of this research project is to characterize the reactions of superoxide anions with organo-sulfur and halocarbon compounds of biomedical and/or environmental significance as substrates. Specifically the substrates selected for study are the thioamides, which find use as drugs, pesticides, nucleic acid thiobase analogs, and polygalogenated aromatics such as PCB's and PBB's. These halocarbons have been used extensively for 60 years as transformer oils or heat-exchangers fluids and represent a major environmental problem. The substrates will be reacted with electrochemically generated superoxide in aprotic solvents. The method will utilize electrochemical techniques in addition to standard laboratory analytical procedures. The research goal is to characterize the reactions of these substrates with superoxide in aprotic solvents. Specific objectives are as follows: 1. Reaction rates for thiabenzamide derivatives will be measured for Hammet type plot comparison with published toxicity in animals. 2. The reaction of nucleic acid thiobase analogs with superoxide will be studied to obtain the stoichiometry and mechanism of the reaction. 3. Reactions of polyhalogenated benzenes and biphenyls will be studied to obtain the stoichiometry, products, and kinetics of the reactions. The goal of the experimental design is to maximize student involvement in all aspects of the research project. The specific research areas have been selected based on preliminary results obtained from student research projects performed under previous MBRS funding.
