Interconversion between [4Fe-4S] cubane and [3Fe-4S] cuboidal states represents one of the simplest structural changes an iron–sulphur cluster can undertake. This reaction is implicated in oxidative damage and in modulation of the activity and regulation of certain enzymes, and it is therefore important to understand the factors governing cluster stability and the processes that activate cluster conversion. In the present study, protein film voltammetry has been used to induce and monitor the oxidative conversion of [4Fe-4S] into [3Fe-4S] clusters in different variants of Azotobacter vinelandii ferredoxin I (AvFdI; the 8Fe form of the native protein), and ΔThr14/ΔAsp15, Thr14 → Cys (T14C) and C42D mutants. The electrochemical results have been correlated with the differing oxygen sensitivities of [4Fe-4S] clusters, and comparisons have been drawn with other ferredoxins (Desulfovibrio africanus FdIII, Clostridium pasteurianum Fd, Thauera aromatica Fd and Pyrococcus furiosus Fd). In contrast with high-potential iron–sulphur proteins (HiPIPs) for which the oxidized species [4Fe-4S]3+ is inert to degradation and can be isolated, the hypervalent state in these ferredoxins (most obviously the 3+ level) is very labile, and the reduction potential at which this is formed is a key factor in determining the cluster's resistance to oxidative damage.
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December 2001
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Research Article|
December 10 2001
Influence of electrochemical properties in determining the sensitivity of [4Fe-4S] clusters in proteins to oxidative damage
Gareth J. TILLEY;
Gareth J. TILLEY
∗Department of Chemistry, Oxford University, OX1 3QR, England, U.K.
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Raul CAMBA;
Raul CAMBA
∗Department of Chemistry, Oxford University, OX1 3QR, England, U.K.
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Barbara K. BURGESS;
Barbara K. BURGESS
†Department of Molecular Biology and Biochemistry, University of California Irvine, Irvine, CA 92717, U.S.A.
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Fraser A. ARMSTRONG
Fraser A. ARMSTRONG
1
∗Department of Chemistry, Oxford University, OX1 3QR, England, U.K.
1To whom correspondence should be addressed (e-mail Fraser.Armstrong@chem.ox.ac.uk).
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Publisher: Portland Press Ltd
Received:
July 25 2001
Revision Received:
October 03 2001
Accepted:
October 08 2001
Online ISSN: 1470-8728
Print ISSN: 0264-6021
The Biochemical Society, London ©2001
2001
Biochem J (2001) 360 (3): 717–726.
Article history
Received:
July 25 2001
Revision Received:
October 03 2001
Accepted:
October 08 2001
Citation
Gareth J. TILLEY, Raul CAMBA, Barbara K. BURGESS, Fraser A. ARMSTRONG; Influence of electrochemical properties in determining the sensitivity of [4Fe-4S] clusters in proteins to oxidative damage. Biochem J 15 December 2001; 360 (3): 717–726. doi: https://doi.org/10.1042/bj3600717
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