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| Content Provider | Springer Nature Link |
|---|---|
| Author | Martic, Maja Jakab Simon, Ida émi Haahr, Lærke Tvedebrink Hagen, Wilfred Raymond Christensen, Hans Erik Mølager |
| Copyright Year | 2013 |
| Abstract | Heterometallic [AgFe3S4] iron–sulfur clusters assembled in wild-type Pyrococcus furiosus ferredoxin and two variants, D14C and D14H, are characterized. The crystal structure of the [AgFe3S4] D14C variant shows that the silver(I) ion is indeed part of the cluster and is coordinated to the thiolate group of residue 14. Cyclic voltammetry shows one redox pair with a reduction potential of +220 mV versus the standard hydrogen electrode which is assigned to the [AgFe3S4]2+/+ couple. The oxidized form of the [AgFe3S4] D14C variant is stable in the presence of dioxygen, whereas the oxidized forms of the [AgFe3S4] wild type and D14H variants convert to the [Fe3S4] ferredoxin form. The monovalent d 10 silver(I) ion stabilizes the [Fe3S4]+/0 cluster fragment, as opposed to divalent d 10 metal ions, resulting in more than 0.4 V difference in reduction potentials between the silver(I) and, e.g., zinc(II) heterometallic [MFe3S4] ferredoxins. The trend in reduction potentials for the variants containing the [AgFe3S4] cluster is wild type ≤ D14C < D14H and shows the same trend as reported for the variants containing the [Fe3S4] cluster, but is different from the D14C < D14H < wild type trend reported for the [Fe4S4] ferredoxin. The similarity in the reduction potential trend for the variants containing the heterometallic [AgFe3S4] cluster and the [Fe3S4] cluster can be rationalized in terms of the electrostatic influence of the residue 14 side chains, rather than the dissociation constant of this residue, as is the case for [Fe4S4] ferredoxins. The trends in reduction potentials are in line with there being no electronic coupling between the silver(I) ion and the Fe3S4 fragment. |
| Starting Page | 261 |
| Ending Page | 276 |
| Page Count | 16 |
| File Format | |
| ISSN | 09498257 |
| Journal | JBIC Journal of Biological Inorganic Chemistry |
| Volume Number | 18 |
| Issue Number | 2 |
| e-ISSN | 14321327 |
| Language | English |
| Publisher | Springer-Verlag |
| Publisher Date | 2013-01-08 |
| Publisher Place | Berlin, Heidelberg |
| Access Restriction | One Nation One Subscription (ONOS) |
| Subject Keyword | Ferredoxin Pyrococcus furiosus Heterometallic Silver Mass spectrometry Biochemistry Microbiology |
| Content Type | Text |
| Resource Type | Article |
| Subject | Biochemistry Inorganic Chemistry |
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