This Presidential Young Investigator Award from the Inorganic, Bioinorganic and Organometallic Chemistry Program is in the area of bioinorganic chemistry. Metal ions will be used in a variety of ways to probe the structure and function of biomolecules. Noninvasive transition-metal probes will be used to map the binding surfaces of metalloproteins by selective tagging, and the effects of ancillary ligands on the selective recognition between metal complexes and biological macromolecules will be investigated. Intraprotein electron transfer in metalloproteins will be explored through a systematic study of the kinetics and mechanism of electron transfer reactions between active sites of metalloproteins and excited states of inorganic chromophores attached selectively to the protein backbone. Mononuclear and polynuclear transition metal complexes will be used to cross-link metalloproteins to produce potential multielectron redox catalysts. The cleavage of proteins and peptides by metal aquo complexes will be explored, with special focus on the selective delivery of hydrolytic agents to peptide bonds which are not cleavable by common enzymes. Finally, Pt-195 NMR spectroscopy will be developed as a new technique for the study of stereodynamics. This project is expected to provide versatile new tools for the investigation of the function of metalloproteins.
