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Article Dans Une Revue Journal of Biological Inorganic Chemistry Année : 2022

Stability of the H-cluster under whole-cell conditions-formation of an H-trans-like state and its reactivity towards oxygen

Résumé

Hydrogenases are metalloenzymes that catalyze the reversible oxidation of molecular hydrogen into protons and electrons. For this purpose, [FeFe]-hydrogenases utilize a hexanuclear iron cofactor, the H-cluster. This biologically unique cofactor provides the enzyme with outstanding catalytic activities, but it is also highly oxygen sensitive. Under in vitro conditions, oxygen stable forms of the H-cluster denoted H-trans and H-inact can be generated via treatment with sulfide under oxidizing conditions. Herein, we show that an H-trans-like species forms spontaneously under intracellular conditions on a time scale of hours, concurrent with the cells ceasing H-2 production. Addition of cysteine or sulfide during the maturation promotes the formation of this H-cluster state. Moreover, it is found that formation of the observed H-trans-like species is influenced by both steric factors and proton transfer, underscoring the importance of outer coordination sphere effects on H-cluster reactivity.
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Dates et versions

hal-04047930 , version 1 (27-03-2023)

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Citer

Marco Lorenzi, Pierre Ceccaldi, Patricia Rodriguez-Macia, Holly Jayne Redman, Afridi Zamader, et al.. Stability of the H-cluster under whole-cell conditions-formation of an H-trans-like state and its reactivity towards oxygen. Journal of Biological Inorganic Chemistry, 2022, 27 (3), pp.345-355. ⟨10.1007/s00775-022-01928-5⟩. ⟨hal-04047930⟩
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