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The Structural Plasticity of the Proximal [4Fe3S] Cluster is Responsible for the O2 Tolerance of Membrane-Bound [NiFe] Hydrogenases

by: Jean-Marie Mouesca, Juan C. Fontecilla-Camps, Patricia Amara
Angew. Chem. Int. Ed., Vol. 52, No. 7. (11 February 2013), pp. 2002-2006, doi:10.1002/anie.201209063  Key: citeulike:12185329

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Abstract

The main difference between O(2) -sensitive and O(2) -tolerant [NiFe] hydrogenases is the plasticity of the proximal [4Fe3S] cluster in the latter hydrogenase. Deprotonation of a conserved glutamate residue initiates the movement of the iron atom, resulting in its binding to the amide nitrogen atom of one of the two supernumerary cysteine ligands and superoxidation of the proximal cluster. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.


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