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Ph Dependent Reversible Formation Of A Binuclear Ni2 Metal-Center Within A Peptide Scaffold, Breena C. Keegan, Daniel Ocampo, Jason M. Shearer
Ph Dependent Reversible Formation Of A Binuclear Ni2 Metal-Center Within A Peptide Scaffold, Breena C. Keegan, Daniel Ocampo, Jason M. Shearer
Chemistry Faculty Research
A disulfide-bridged peptide containing two Ni2+ binding sites based on the nickel superoxide dismutase protein, {Ni2(SODmds)} has been prepared. At physiological pH (7.4), it was found that the metal sites are mononuclear with a square planar NOS2 coordination environment with the two sulfur-based ligands derived from cysteinate residues, the nitrogen ligand derived from the amide backbone, and a water ligand. Furthermore, S K-edge X-ray absorption spectroscopy indicated that the two cysteinate sulfur atoms ligated to nickel are each protonated. Elevation of the pH to 9.6 results in the deprotonation of the cysteinate sulfur atoms, …