This grant from the Organic Dynamics Program supports the continuing work of Dr. Patrick S. Mariano at the University of Maryland. Knowledge gained from this research will lead to a more sound understanding of chemical reactions that occur through the intermediacy of charged species generated by the interaction of organic molecules with light. In addition, the investigator will develop new photochemical reactions of potential use in the synthesis of organic chemicals. The experiments that will be carried out by Dr. Mariano are designed to provide information about the mechanistic course of excited-state single-electron-transfer processes and about the influence of structural and environmental factors on the efficiencies of these reactions. Fast kinetic measurements will be used to determine rates of important solution-phase ion radical processes, which serve as the driving force for a number of important ground-state and excited-state single-electron-transfer processes. Exploratory work will be aimed at discovery of new, synthetically useful single-electron-transfer reactions and related electrochemical reactions of donor-acceptor systems. Biochemically relevant photochemical single-electron-transfer reactions will be used to model those involved in the redox chemistry of flavoproteins.
