ExplorEnz: EC 1.12.1.4

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1.12.1.4

Accepted name:

hydrogenase (NAD⁺, ferredoxin)

Reaction:

2 H₂ + NAD⁺ + 2 oxidized ferredoxin = 5 H⁺ + NADH + 2 reduced ferredoxin

Other name(s):

bifurcating [FeFe] hydrogenase; [FeFe]-HydABC hydrogenase; [NiFe]-HydABCSL hydrogenase

Systematic name:

hydrogen:NAD⁺, ferredoxin oxidoreductase

Comments:

The enzyme, which contains either an [FeFe] cluster (H-cluster) or [NiFe] cluster, as well as multiple iron-sulfur clusters, uses flavin-based electron bifurcation to transfer electrons between H₂ and both NAD⁺ and ferredoxin. The enzyme from Thermotoga maritima works in the direction of evolving hydrogen as a means of eliminating excess reducing equivalents. The enzyme from the acetogenic bacterium Acetobacterium woodii drives the endergonic reduction of ferredoxin with H₂ as the reductant by coupling it to the exergonic electron transfer from hydrogen to NAD⁺.

Links to other databases:

BRENDA, EXPASY, KEGG, MetaCyc, PDB

References:

1.	Verhagen, M.F., O'Rourke, T. and Adams, M.W. The hyperthermophilic bacterium, Thermotoga maritima, contains an unusually complex iron-hydrogenase: amino acid sequence analyses versus biochemical characterization. Biochim. Biophys. Acta 1412 (1999) 212–229. [DOI] [PMID: 10482784]
2.	Schut, G.J. and Adams, M.W. The iron-hydrogenase of Thermotoga maritima utilizes ferredoxin and NADH synergistically: a new perspective on anaerobic hydrogen production. J. Bacteriol. 191 (2009) 4451–4457. [DOI] [PMID: 19411328]
3.	Chongdar, N., Pawlak, K., Rudiger, O., Reijerse, E.J., Rodriguez-Macia, P., Lubitz, W., Birrell, J.A. and Ogata, H. Spectroscopic and biochemical insight into an electron-bifurcating [FeFe] hydrogenase. J. Biol. Inorg. Chem. 25 (2020) 135–149. [DOI] [PMID: 31823008]
4.	Feng, X., Schut, G.J., Haja, D.K., Adams, M.WW. and Li, H. Structure and electron transfer pathways of an electron-bifurcating NiFe-hydrogenase. Sci Adv 8:eabm7546 (2022). [DOI] [PMID: 35213221]
5.	Furlan, C., Chongdar, N., Gupta, P., Lubitz, W., Ogata, H., Blaza, J.N. and Birrell, J.A. Structural insight on the mechanism of an electron-bifurcating [FeFe] hydrogenase. Elife 11:e79361 (2022). [DOI] [PMID: 36018003]

[EC 1.12.1.4 created 2011]