This subproject is one of many research subprojects utilizing the resources provided by a Center grant funded by NIH/NCRR. The subproject and investigator (PI) may have received primary funding from another NIH source, and thus could be represented in other CRISP entries. The institution listed is for the Center, which is not necessarily the institution for the investigator. A variety of enzymes use copper to activate O2 and to mediate a range of O2 reactivities. Small synthetic molecules offer a means of probing fundamental issues of Cu/O2 chemistry, in a detailed and systematic way. XAS at the Cu K-edge has proven to be an increasingly powerful technique in Cu/O2 chemistry, for its ability to probe such important variables as Cu oxidation state, Cu-Cu distance, as well as Cu coordination geometry, in the solid or solution state. We propose a series of experiments directed at understanding such basic issues as the nuclearity of Cu : O2 reactivity under different conditions, ligand effects on the structure of the Cu/O2 species which form, and structure-reactivity correlations in these species. Because these small molecules serve as enzyme active site models, work proposed in this study addresses bioinorganic activation of O2 by copper as well as several more fundamental issues in metal/O2 chemistry.
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