This project is in the general area of analytical and surface chemistry and in the subfield of electrochemical reaction dynamics. The electrochemical properties of several widely different modified electrode systems will be investigated, including electrodes modified with polymer and clay films, organized molecular assemblies, and deoxyribonucleic acid (DNA) systems. Electrochemical methods will be used to investigate how the structure, charge and polarity of small molecules affect their interactions with DNA and to attempt selective cleavage of the DNA strand. Electrolytes based on novel inert solvents capable of operation at very low temperatures, e.g., liquid sulfur dioxide, will be used to generate superoxidizing agents that have not previously been prepared. The kinetics and energetics of reactions of organometallic species that exhibit large conformational changes on electron transfer and those that contain multiple electroactive groups will also be studied in order to gain information about the effects of structural changes and intramolecular interactions on oxidation-reduction potential. This research project is concerned with the continued development of electrochemical methods as analytical tools and their application to chemical problems. Electrochemical methods of analysis play a complementary role to the spectroscopic methods more generally used and provide special insight into the kinetics of electron transfer processes and the oxidation-reduction potentials of electrochemical reactions.
