Abstract
Ni‐free hydrogenases commonly exhibit a gav > 2 EPR spectrum in their most oxidised level. This spectrum has been linked with the active site and generally attributed to an oxidised HIPIP‐type, [4Fe‐4S]3+ cluster. We report the low temperature magnetic circular dichroism (MCD) spectrum of 2,6‐dichlorophenolindo‐phenol (DCPIP)‐oxidised Desulfovibrio vulgaris hydrogenase (DvH2ase), which exhibits an axial gav > 2 EPR spectrum. Paramagnetic MCD is observed, which however is shown to arise from an EPR‐silent, para‐magnetic species with S > . No evidence of paramagnetic MCD arising from the gav > 2 EPR‐detectable species is obtained. We conclude that: (1) DCPIP‐oxidised DvH2ase does not contain either a [4Fe‐4S]3+ or an oxidised 3Fe cluster; (ii) an EPR‐silent species with MCD characteristics somewhat similar to those of the oxidised ‘P’ clusters of the dye‐oxidized iron‐molybdenum protein of nitrogenase is present in DCPIP‐oxidised DvH2ase; (iii) the MCD and EPR of the gav > 2 species exhibit characteristics in common with those of the gav > 2 species produced by Fe(CN)6 3− oxidation of the [4Fe‐4S]2+ cluster of the 7Fe ferredoxin I of Azotobacter vinelandii [(7Fe)FdI). We suggest that the gav > 2 EPR signal of this and other hydrogenases arises from a species chemically analogous to that observed in (7Fe)FdI.
References
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Dates
Type | When |
---|---|
Created | 23 years, 1 month ago (July 25, 2002, 3:58 a.m.) |
Deposited | 1 year, 11 months ago (Sept. 16, 2023, 2:09 a.m.) |
Indexed | 1 year, 9 months ago (Nov. 23, 2023, 7:20 a.m.) |
Issued | 40 years, 7 months ago (Jan. 21, 1985) |
Published | 40 years, 7 months ago (Jan. 21, 1985) |
Published Online | 23 years, 9 months ago (Nov. 2, 2001) |
Published Print | 40 years, 7 months ago (Jan. 21, 1985) |
@article{Stephens_1985, title={Magnetic circular dichroism of DCPIP‐oxidised Desulfovibrio vulgaris hydrogenase}, volume={180}, ISSN={1873-3468}, url={http://dx.doi.org/10.1016/0014-5793(85)80223-4}, DOI={10.1016/0014-5793(85)80223-4}, number={1}, journal={FEBS Letters}, publisher={Wiley}, author={Stephens, P.J. and Devlin, F. and McKenna, M.C. and Morgan, T.V. and Czechowski, M. and DerVartanian, D.V. and Peck, H.D. and LeGall, J.}, year={1985}, month=jan, pages={24–28} }