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

Authors

  • Dr. Jean-Marie Mouesca,

    1. Laboratoire de Chimie Inorganique et Biologique UMR-E 3 CEA-UJF, Institut de Nanosciences et Cryogénie, CEA-Grenoble, 17 avenue des Martyrs, 38054 Grenoble (France)
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  • Dr. Juan C. Fontecilla-Camps,

    Corresponding author
    1. Metalloproteins Unit, Institut de Biologie Structurale J.P. Ebel Commissariat à l'Énergie Atomique, Centre National de la Recherche Scientifique, Université Joseph Fourier, 41 rue Jules Horowitz, 38027 Grenoble (France)
    • Metalloproteins Unit, Institut de Biologie Structurale J.P. Ebel Commissariat à l'Énergie Atomique, Centre National de la Recherche Scientifique, Université Joseph Fourier, 41 rue Jules Horowitz, 38027 Grenoble (France)
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  • Dr. Patricia Amara

    Corresponding author
    1. Metalloproteins Unit, Institut de Biologie Structurale J.P. Ebel Commissariat à l'Énergie Atomique, Centre National de la Recherche Scientifique, Université Joseph Fourier, 41 rue Jules Horowitz, 38027 Grenoble (France)
    • Metalloproteins Unit, Institut de Biologie Structurale J.P. Ebel Commissariat à l'Énergie Atomique, Centre National de la Recherche Scientifique, Université Joseph Fourier, 41 rue Jules Horowitz, 38027 Grenoble (France)
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  • We thank Drs David Rinaldo and Anne Volbeda for helpful discussions. We appreciate the help from the staff of the computing facility provided by the Commissariat à l’Energie Atomique (CEA/DSV/GIPSI), Saclay, and CCRT, Bruyères-le-Châtel, and thank the CEA and CNRS for institutional funding.

Abstract

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The main difference between O2-sensitive and O2-tolerant [NiFe] hydrogenases is the plasticity of the proximal [4Fe3S] cluster in the latter hydrogenase (see scheme). 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.

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