Structure and electron transfer pathways of an electron-bifurcating NiFe-hydrogenase

Feng, Xiang; Schut, Gerrit J.; Haja, Dominik K.; Adams, Michael W.; Li, Huilin

doi:10.1126/sciadv.abm7546

Title: Structure and electron transfer pathways of an electron-bifurcating NiFe-hydrogenase

Journal Article · Fri Feb 25 00:00:00 EST 2022 · Science Advances

DOI:https://doi.org/10.1126/sciadv.abm7546· OSTI ID:1904582

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Van Andel Institute, Grand Rapids, MI (United States)
University of Georgia, Athens, GA (United States)

Electron bifurcation enables thermodynamically unfavorable biochemical reactions. Four groups of bifurcating flavoenzyme are known and three use FAD to bifurcate. FeFe-HydABC hydrogenase represents the fourth group, but its bifurcation site is unknown. We report cryo-EM structures of the related NiFe-HydABCSL hydrogenase that reversibly oxidizes H₂ and couples endergonic reduction of ferredoxin with exergonic reduction of NAD. FMN surrounded by a unique arrangement of iron sulfur clusters forms the bifurcating center. NAD binds to FMN in HydB, and electrons from H₂ via HydA to a HydB [4Fe-4S] cluster enable the FMN to reduce NAD. Low-potential electron transfer from FMN to the HydC [2Fe-2S] cluster and subsequent reduction of a uniquely penta-coordinated HydB [2Fe-2S] cluster require conformational changes, leading to ferredoxin binding and reduction by a [4Fe-4S] cluster in HydB. This work clarifies the electron transfer pathways for a large group of hydrogenases underlying many essential functions in anaerobic microorganisms.

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Research Organization:: Univ. of Georgia, Athens, GA (United States); Van Andel Institute, Grand Rapids, MI (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: FG02-95ER20175; SC0020085

OSTI ID:: 1904582

Journal Information:: Science Advances, Vol. 8, Issue 8; ISSN 2375-2548

Publisher:: AAASCopyright Statement

Country of Publication:: United States

Language:: English

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