An NMR structural study of nickel-substituted rubredoxin
authors Goodfellow, BJ; Duarte, ICN; Macedo, AL; Volkman, BF; Nunes, SG; Moura, I; Markley, JL; Moura, JJG
nationality International
journal JOURNAL OF BIOLOGICAL INORGANIC CHEMISTRY
author keywords NMR; Rubredoxin; [Fe-4S] centre; Paramagnetic protein; Nickel
keywords CLOSTRIDIUM-PASTEURIANUM RUBREDOXIN; DENSITY-FUNCTIONAL CALCULATIONS; RHUS VERNICIFERA STELLACYANIN; TORSION ANGLE DYNAMICS; ACTIVE-SITE STRUCTURE; PSEUDOCONTACT SHIFTS; DESULFOVIBRIO-GIGAS; PARAMAGNETIC METALLOPROTEINS; DIPOLAR COUPLINGS; REDUCTION POTENTIALS
abstract The Ni(II) and Zn(II) derivatives of Desulfovibrio vulgaris rubredoxin (DvRd) have been studied by NMR spectroscopy to probe the structure at the metal centre. The beta CH(2) proton pairs from the cysteines that bind the Ni(II) atom have been identified using 1D nuclear Overhauser enhancement (NOE) difference spectra and sequence specifically assigned via NOE correlations to neighbouring protons and by comparison with the published X-ray crystal structure of a Ni(II) derivative of Clostridium pasteurianum rubredoxin. The solution structures of DvRd(Zn) and DvRd(Ni) have been determined and the paramagnetic form refined using pseudocontact shifts. The determination of the magnetic susceptibility anisotropy tensor allowed the contact and pseudocontact contributions to the observed chemical shifts to be obtained. Analysis of the pseudocontact and contact chemical shifts of the cysteine H beta protons and backbone protons close to the metal centre allowed conclusions to be drawn as to the geometry and hydrogen-bonding pattern at the metal binding site. The importance of NH-S hydrogen bonds at the metal centre for the delocalization of electron spin density is confirmed for rubredoxins and can be extrapolated to metal centres in Cu proteins: amicyanin, plastocyanin, stellacyanin, azurin and pseudoazurin.
publisher SPRINGER
issn 0949-8257
year published 2010
volume 15
issue 3
beginning page 409
ending page 420
digital object identifier (doi) 10.1007/s00775-009-0613-6
web of science category Biochemistry & Molecular Biology; Chemistry, Inorganic & Nuclear
subject category Biochemistry & Molecular Biology; Chemistry
unique article identifier WOS:000275104400011
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