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Keywords:

  • hydrogenases;
  • iron–sulfur cluster;
  • redox chemistry;
  • superoxidation
Thumbnail image of graphical abstract

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.