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Structural and spectroscopic characterization of CO inhibition of [NiFe]-hydrogenase from Citrobacter sp. S-77.


ABSTRACT: Hydrogenases catalyze the reversible oxidation of H2. Carbon monoxide (CO) is known to be a competitive inhibitor of O2-sensitive [NiFe]-hydrogenases. Although the activities of some O2-tolerant [NiFe]-hydrogenases are unaffected by CO, the partially O2-tolerant [NiFe]-hydrogenase from Citrobacter sp. S-77 (S77-HYB) is inhibited by CO. In this work, the CO-bound state of S77-HYB was characterized by activity assays, spectroscopic techniques and X-ray crystallography. Electron paramagnetic resonance spectroscopy showed a diamagnetic Ni2+ state, and Fourier-transform infrared spectroscopy revealed the stretching vibration of the exogenous CO ligand. The crystal structure determined at 1.77 Å resolution revealed that CO binds weakly to the nickel ion in the Ni-Fe active site of S77-HYB. These results suggest a positive correlation between O2 and CO tolerance in [NiFe]-hydrogenases.

SUBMITTER: Imanishi T 

PROVIDER: S-EPMC8805213 | biostudies-literature | 2022 Feb

REPOSITORIES: biostudies-literature

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Structural and spectroscopic characterization of CO inhibition of [NiFe]-hydrogenase from Citrobacter sp. S-77.

Imanishi Takahiro T   Nishikawa Koji K   Taketa Midori M   Higuchi Katsuhiro K   Tai Hulin H   Hirota Shun S   Hojo Hironobu H   Kawakami Toru T   Hataguchi Kiriko K   Matsumoto Kayoko K   Ogata Hideaki H   Higuchi Yoshiki Y  

Acta crystallographica. Section F, Structural biology communications 20220127 Pt 2


Hydrogenases catalyze the reversible oxidation of H<sub>2</sub>. Carbon monoxide (CO) is known to be a competitive inhibitor of O<sub>2</sub>-sensitive [NiFe]-hydrogenases. Although the activities of some O<sub>2</sub>-tolerant [NiFe]-hydrogenases are unaffected by CO, the partially O<sub>2</sub>-tolerant [NiFe]-hydrogenase from Citrobacter sp. S-77 (S77-HYB) is inhibited by CO. In this work, the CO-bound state of S77-HYB was characterized by activity assays, spectroscopic techniques and X-ray c  ...[more]

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