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This study shows how the NiFeSe site of an anaerobically purified O2-resistant hydrogenase reacts with air to give a seleninate as the first product. Less oxidized states of the active site are readily reduced in the presence of X-rays. Reductive enzyme activation requires an efficient pathway for water escape.

Graphical abstract: Structural foundations for the O2 resistance of Desulfomicrobium baculatum [NiFeSe]-hydrogenase

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