The critical role of a conserved lysine residue in periplasmic nitrate reductase catalyzed reactions.

Campylobacter jejuni 4Fe–4S cluster Molybdenum Nitrate reductase

Journal

Journal of biological inorganic chemistry : JBIC : a publication of the Society of Biological Inorganic Chemistry
ISSN: 1432-1327
Titre abrégé: J Biol Inorg Chem
Pays: Germany
ID NLM: 9616326

Informations de publication

Date de publication:
23 May 2024
Historique:
received: 06 11 2023
accepted: 10 04 2024
medline: 24 5 2024
pubmed: 24 5 2024
entrez: 23 5 2024
Statut: aheadofprint

Résumé

Periplasmic nitrate reductase NapA from Campylobacter jejuni (C. jejuni) contains a molybdenum cofactor (Moco) and a 4Fe-4S cluster and catalyzes the reduction of nitrate to nitrite. The reducing equivalent required for the catalysis is transferred from NapC → NapB → NapA. The electron transfer from NapB to NapA occurs through the 4Fe-4S cluster in NapA. C. jejuni NapA has a conserved lysine (K79) between the Mo-cofactor and the 4Fe-4S cluster. K79 forms H-bonding interactions with the 4Fe-4S cluster and connects the latter with the Moco via an H-bonding network. Thus, it is conceivable that K79 could play an important role in the intramolecular electron transfer and the catalytic activity of NapA. In the present study, we show that the mutation of K79 to Ala leads to an almost complete loss of activity, suggesting its role in catalytic activity. The inhibition of C. jejuni NapA by cyanide, thiocyanate, and azide has also been investigated. The inhibition studies indicate that cyanide inhibits NapA in a non-competitive manner, while thiocyanate and azide inhibit NapA in an uncompetitive manner. Neither inhibition mechanism involves direct binding of the inhibitor to the Mo-center. These results have been discussed in the context of the loss of catalytic activity of NapA K79A variant and a possible anion binding site in NapA has been proposed.

Identifiants

pubmed: 38782786
doi: 10.1007/s00775-024-02057-x
pii: 10.1007/s00775-024-02057-x
doi:

Types de publication

Journal Article

Langues

eng

Sous-ensembles de citation

IM

Subventions

Organisme : National Science Foundation
ID : CHE 2003752
Organisme : NIGMS NIH HHS
ID : GM 139064
Pays : United States

Informations de copyright

© 2024. The Author(s), under exclusive licence to Society for Biological Inorganic Chemistry (SBIC).

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Auteurs

Nitai C Giri (NC)

Department of Chemistry and Chemical Biology, Indiana University Indianapolis, Indianapolis, IN, USA.

Breeanna Mintmier (B)

Department of Chemistry and Chemical Biology, Indiana University Indianapolis, Indianapolis, IN, USA.

Manohar Radhakrishnan (M)

Department of Chemistry and Chemical Biology, Indiana University Indianapolis, Indianapolis, IN, USA.

Jonathan W Mielke (JW)

Department of Chemistry and Biochemistry, University of Wisconsin-Milwaukee, Milwaukee, WI, USA.

Jarett Wilcoxen (J)

Department of Chemistry and Biochemistry, University of Wisconsin-Milwaukee, Milwaukee, WI, USA. jarettw@uwm.edu.

Partha Basu (P)

Department of Chemistry and Chemical Biology, Indiana University Indianapolis, Indianapolis, IN, USA. basup@iu.edu.

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