Design & Synthesis of Biomimetic Metallocavities for Nickel Hydrogenases & Copper Oxidases: Modular Assembly w/ tris-pyridylmethanol. The goal of my research is the synthetic analog approach within the field of bioinorganic chemistry whereby small synthetic analogs of biological metal sites are synthesized and studied at the small molecule level of detail. Molecular design of novel inorganic coordination complexes which mimic certain biological sites is the unifying theme. An attention to the structural environment and overall shape of transition metal complexes is as important as the actual ligating atoms when considering reactivity and physical properties. Yet, to date, most attention has been directed towards the immediate coordination environment of the metals. Significant advancements in bioinorganic chemistry will come through a rationale approach of ligand design in which attention is directed bothto the coordination environment and the periphery of the complex. Specifically, my group is interested in the metal sites in nickel hydrogenases and oxidative copper enzymes. The former are responsible for the reversible interconversion of hydrogen to protons and have monomeric nickel active site. The latter represent a much wider class of enzymes which are generically responsible for the activation/binding of oxygen; the copper atoms are found to exist in monomeric to trimeric units. While the coordination environments of these enzymes are diverse, as inferred through spectroscopic means, a recurring theme of facial coordination of metal(s) with 2-3 imidazole groups from histidine is found. We have chosen to develop an entirely new family of ligand which to mimic these sites. While other ligand systems havebeen developed, this new family of ligands will allow a synthetic diversity not possible in any other system. Thus, the initial investigation will require much organic synthesis and identification. Mass spectral data will be critical when developing such systems not only for proof of target ligands but also the identification of side products which oftentimes suggest better synthetic routes. FAB spectral data will be invaluable in identifying the metal complexes of these novel ligand systems when standard techniques, such as NMR, are not applicable.
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