Resonance Raman Studies of Nickel Tetrathiolates and Nickel-Substituted Rubredoxins and Desulforedoxin

Yun Hua Huang, Isabel Moura, José J. G. Moura, Jean LeGall, Jae Bum Park, Michael W. W. Adams, Michael K. Johnson

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21 Citations (Scopus)

Abstract

Low-temperature resonance Raman spectroscopy has been used to investigate the nickel coordination geometry in the [Ni(SPh)4]2− anion in solution, Ni(II)-substituted rubredoxins from Desulfovibrio gigas and Pyrococcus furiosus, and Ni(II)-substituted desulforedoxin from D. gigas. Ni-S vibrational modes have been assigned on the basis of 58Ni/60Ni isotope shifts, polarization studies, and comparison with structurally characterized tetrathiolate Ni(II) complexes. The results indicate tetragonally elongated tetrahedral [NiS4] cores in the [Ni(SPh)4]2− anion in solution and in both Ni(II)-rubredoxins and a distorted square planar [NiS4] core in Ni(II)-desulforedoxin. Cysteine deformation modes that are enhanced via coupling with Ni-S stretching modes are observed near 400 cm−1 in the spectra of both native and Ni(II)-substituted rubredoxins. The potential of resonance Raman for investigating Ni-cysteinate centers in other metalloproteins and for elucidating the conformation of coordinating cysteine residues is discussed in light of these new results.

Original languageEnglish
Pages (from-to)406-412
Number of pages7
JournalInorganic Chemistry
Volume32
Issue number4
DOIs
Publication statusPublished - 1 Jan 1993

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