The Mechanism of Nitrite Reductase.

Per E M Siegbahn
Author Information
  1. Per E M Siegbahn: Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, Stockholm, Sweden. ORCID

Abstract

Cytochrome c nitrite reductase (CcNiR) activates nitrite and produces ammonia. It is one of several enzymes that use a redox-active cofactor to perform its reaction. In this case, the cofactor has a heme with a lysine as the proximal ligand and a charged nearby arginine. The role of a tyrosine, which is also close, has been less clear. There are also four bis-histidine-ligated hemes involved in the electron transfers. CcNiR has been studied before, using essentially the same methods as here. However, the mechanism is very complicated, involving six reductions, and quite different results for the mechanism have been obtained here. For example, the tyrosine has here been found to be redox active in the final step when ammonia is produced. Also, the arginine has here been found to stay protonated throughout the mechanism, which is different from what was found in the previous study. The present results are in very good agreement with experimental findings and are, therefore, another case where the methodology has been shown to work very well. Previous examples include Photosystem II and Nitrogenase, normally considered to be the most important enzymes in nature for the development of life.

Keywords

References

  1. Chem Rev. 2014 Apr 9;114(7):3601-58 [PMID: 24410477]
  2. J Comput Chem. 2006 Nov 30;27(15):1787-99 [PMID: 16955487]
  3. Acc Chem Res. 2009 Dec 21;42(12):1871-80 [PMID: 19856959]
  4. J Phys Chem B. 2024 Oct 10;128(40):9699-9705 [PMID: 39344806]
  5. Inorg Chem. 2015 Jul 6;54(13):6439-61 [PMID: 26098647]
  6. Nature. 1999 Jul 29;400(6743):476-80 [PMID: 10440380]
  7. J Phys Chem A. 2005 Dec 1;109(47):10795-7 [PMID: 16863129]
  8. J Biol Inorg Chem. 2011 Mar;16(3):417-30 [PMID: 21125303]
  9. J Phys Chem B. 2024 Jun 20;128(24):5840-5845 [PMID: 38850249]
  10. Inorg Chem. 2015 Oct 5;54(19):9303-16 [PMID: 26237518]
  11. Biochim Biophys Acta. 2013 Aug-Sep;1827(8-9):1003-19 [PMID: 23103385]
  12. J Phys Chem B. 2025 Jan 9;129(1):111-116 [PMID: 39693510]
  13. Environ Microbiol. 2008 Nov;10(11):3164-73 [PMID: 18721142]
  14. J Comput Chem. 2007 Jan 30;28(2):528-39 [PMID: 17186474]
  15. J Biol Inorg Chem. 2014 Jan;19(1):97-112 [PMID: 24271207]
  16. J Biol Inorg Chem. 2012 Jun;17(5):741-60 [PMID: 22454108]
  17. Phys Chem Chem Phys. 2023 Sep 13;25(35):23602-23613 [PMID: 37622205]
  18. Curr Opin Microbiol. 2001 Jun;4(3):307-12 [PMID: 11378484]
  19. Front Chem. 2018 Dec 21;6:644 [PMID: 30627530]
  20. RSC Adv. 2021 Jan 15;11(6):3495-3508 [PMID: 35424322]

Grants

  1. 2022-22-955/Swedish Research Council
  2. 2018-05973/Swedish Research Council

MeSH Term

Oxidation-Reduction
Nitrite Reductases
Heme
Nitrites
Cytochromes c1
Nitrate Reductases
Cytochromes a1

Chemicals

nitrate reductase (cytochrome)
Nitrite Reductases
Heme
Nitrites
Cytochromes c1
Nitrate Reductases
Cytochromes a1

Word Cloud

Created with Highcharts 10.0.0nitriteenzymesmechanismfoundcreductaseCcNiRammoniacofactorcaseargininetyrosinealsodifferentresultsredoxCytochromeactivatesproducesoneseveraluseredox-activeperformreactionhemelysineproximalligandchargednearbyrolecloselessclearfourbis-histidine-ligatedhemesinvolvedelectrontransfersstudiedusingessentiallymethodsHowevercomplicatedinvolvingsixreductionsquiteobtainedexampleactivefinalstepproducedAlsostayprotonatedthroughoutpreviousstudypresentgoodagreementexperimentalfindingsthereforeanothermethodologyshownworkwellPreviousexamplesincludePhotosystemIINitrogenasenormallyconsideredimportantnaturedevelopmentlifeMechanismNitriteReductaseDFTcytochromemechanismsquantumchemistry

Similar Articles

Cited By

No available data.