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CO synthesized from the central one-carbon pool as source for the iron carbonyl in O2-tolerant [NiFe]-hydrogenase

Identifieur interne : 000762 ( Ncbi/Checkpoint ); précédent : 000761; suivant : 000763

CO synthesized from the central one-carbon pool as source for the iron carbonyl in O2-tolerant [NiFe]-hydrogenase

Auteurs : Ingmar Bürstel [Allemagne] ; Elisabeth Siebert [Allemagne] ; Stefan Frielingsdorf [Allemagne] ; Ingo Zebger [Allemagne] ; B Rbel Friedrich [Allemagne] ; Oliver Lenz [Allemagne]

Source :

RBID : PMC:5187695

Abstract

Significance

Activation of dihydrogen is by far not a trivial catalytic reaction. Microbes have evolved sophisticated hydrogenases with complex transition metal centers to get access to H2. A recurring feature of these centers is the presence of iron atoms equipped with carbon monoxide ligands. In case of [NiFe]-hydrogenases, which contain a NiFe(CN)2CO catalytic center, biosynthesis of the toxic CO ligand remained elusive. We show that [NiFe]-hydrogenases that are catalytically active in the presence of dioxygen use a dedicated maturase for CO ligand synthesis under aerobic conditions. CO is derived from the most oxidized intermediate of the central one-carbon metabolism, formyl-tetrahydrofolate. This discovery contributes a so far unknown reaction to the one-carbon metabolism and opens perspectives for chemical and of bioinspired catalysis.


Url:
DOI: 10.1073/pnas.1614656113
PubMed: 27930319
PubMed Central: 5187695


Affiliations:


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<sub>2</sub>
. A recurring feature of these centers is the presence of iron atoms equipped with carbon monoxide ligands. In case of [NiFe]-hydrogenases, which contain a NiFe(CN)
<sub>2</sub>
CO catalytic center, biosynthesis of the toxic CO ligand remained elusive. We show that [NiFe]-hydrogenases that are catalytically active in the presence of dioxygen use a dedicated maturase for CO ligand synthesis under aerobic conditions. CO is derived from the most oxidized intermediate of the central one-carbon metabolism, formyl-tetrahydrofolate. This discovery contributes a so far unknown reaction to the one-carbon metabolism and opens perspectives for chemical and of bioinspired catalysis.</p>
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