A conformational role for NifW in the maturation of molybdenum nitrogenase P-cluster

Van Stappen, Casey; Jiménez-Vicente, Emilio; Pérez-González, Ana; Yang, Zhi-Yong; Seefeldt, Lance C.; DeBeer, Serena; Dean, Dennis R.; Decamps, Laure

doi:10.1039/D1SC06418E

Title: A conformational role for NifW in the maturation of molybdenum nitrogenase P-cluster

Journal Article · Thu Mar 24 00:00:00 EDT 2022 · Chemical Science

DOI:https://doi.org/10.1039/D1SC06418E· OSTI ID:1847963

^[1]; Jiménez-Vicente, Emilio ^[2];

^[2]; Yang, Zhi-Yong ^[3];

^[3];

^[1]; Dean, Dennis R. ^[2];

^[1]

Max Planck Institute for Chemical Energy Conversion, Stiftstrasse 34-36, 45470 Mülheim an der Ruhr, Germany
Department of Biochemistry, Virginia Polytechnic Institute and State University, Blacksburg, VA 24061, USA
Department of Chemistry and Biochemistry, Utah State University, Logan, UT 84322, USA

Reduction of dinitrogen by molybdenum nitrogenase relies on complex metalloclusters: the [8Fe:7S] P-cluster and the [7Fe:9S:Mo:C:homocitrate] FeMo-cofactor. Although both clusters bear topological similarities and require the reductive fusion of [4Fe:4S] sub-clusters to achieve their respective assemblies, P-clusters are assembled directly on the NifD₂K₂ polypeptide prior to the insertion of FeMo-co, which is fully assembled separately from NifD₂K₂. P-cluster maturation involves the iron protein NifH₂ as well as several accessory proteins, whose role has not been elucidated. In the present work, two NifD₂K₂ species bearing immature P-clusters were isolated from an Azotobacter vinelandii strain in which the genes encoding NifH and the accessory protein NifZ were deleted, and characterized by X-ray absorption spectroscopy and EPR. These analyses showed that both NifD₂K₂ complexes harbor clusters that are electronically and structurally similar, with each NifDK unit containing two [4Fe:4S]^2+/+ clusters. Binding of the accessory protein NifW parallels a decrease in the distance between these clusters, as well as a subtle change in their coordination. These results support a conformational role for NifW in P-cluster biosynthesis, bringing the two [4Fe:4S] precursors closer prior to their fusion, which may be crucial in challenging cellular contexts.

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Research Organization:: Virginia Polytechnic Institute and State University (Virginia Tech), Blacksburg, VA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Max-Planck Society; Peter und Traudl Engelhorn Stiftung; Bill and Melinda Gates Foundation

Grant/Contract Number:: SC0010834; SC0010867; AC02-76SF00515; OPP1143172; INV-005889

OSTI ID:: 1847963

Alternate ID(s):: OSTI ID: 1904224

Journal Information:: Chemical Science, Journal Name: Chemical Science Vol. 13 Journal Issue: 12; ISSN 2041-6520

Publisher:: Royal Society of Chemistry (RSC)Copyright Statement

Country of Publication:: United Kingdom

Language:: English

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