Crystal Structure of a Carbon Monoxide Dehydrogenase Reveals a [Ni-4Fe-5S] Cluster

@article{Dobbek2001CrystalSO,
  title={Crystal Structure of a Carbon Monoxide Dehydrogenase Reveals a [Ni-4Fe-5S] Cluster},
  author={Holger Dobbek and Vitali A. Svetlitchnyi and Lothar Gremer and Robert Huber and Ortwin Meyer},
  journal={Science},
  year={2001},
  volume={293},
  pages={1281 - 1285}
}
The homodimeric nickel-containing CO dehydrogenase from the anaerobic bacterium Carboxydothermus hydrogenoformanscatalyzes the oxidation of CO to CO2. A crystal structure of the reduced enzyme has been solved at 1.6 angstrom resolution. This structure represents the prototype for Ni-containing CO dehydrogenases from anaerobic bacteria and archaea. It contains five metal clusters of which clusters B, B′, and a subunit-bridging, surface-exposed cluster D are cubane-type [4Fe-4S] clusters. The… 
A Ni-Fe-Cu Center in a Bifunctional Carbon Monoxide Dehydrogenase/ Acetyl-CoA Synthase
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A metallocofactor containing iron, sulfur, copper, and nickel has been discovered in the enzyme carbon monoxide dehydrogenase/acetyl-CoA (coenzyme A) synthase from Moorella thermoacetica and suggests a newly discovered role for copper in biology.
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The structures define the mechanism of CO oxidation and CO2 reduction at the Ni-Fe site of cluster C, where CO2 acts as a bridging ligand between Ni and the asymmetrically coordinated Fe, where it completes the square-planar coordination of the Ni ion.
Interaction of Potassium Cyanide with the [Ni-4Fe-5S] Active Site Cluster of CO Dehydrogenase from Carboxydothermus hydrogenoformans*
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A model of the CO oxidation mechanism at the [Ni-4Fe-5S] active site cluster of CODHIICh from C. hydrogenoformans is summarized and the square-planar coordination of nickel by 4S ligands is recovered, which includes the reformation of the Ni-(μ2S)-Fe1 bridge.
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The structural details of a CO2 reducing enzyme reveal long-distance coupling of active sites and tungsten redox centers, and the arrangement of [4Fe-4S] clusters functions as an electron relay but potentially also couples the four tungstopterin active sites over 206 angstroms.
Maturation of the [Ni–4Fe–4S] active site of carbon monoxide dehydrogenases
TLDR
It is questioned the conception that the maturation of all CODH depends on the accessory protein CooC described as essential for nickel insertion into the active site, and the available literature reveals biological variations in C ODH active site biosynthesis.
Mechanism of carbon monoxide oxidation at the active site [Ni-4Fe-5S] cluster of carbon monoxide dehydrogenase from Carboxydothermus hydrogenoformans
  • S. Ha
  • Chemistry, Biology
  • 2009
TLDR
This research work focuses on the interaction of cluster C with CO analogue potassium cyanide and analysis of the resulting type of nickel coordination and on the effect of sodium sulfide on the enzymatic activities of the native CODHIICh.
Structural bases for the catalytic mechanism of Ni-containing carbon monoxide dehydrogenases.
TLDR
This work proposes a catalytic cycle that is consistent with both observations and stereochemistry, and gives alternatives to one of the most difficult aspects of the cycle, namely, the location of the two electrons in the most reduced state of the C-cluster.
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