PMID- 36937601
OWN - NLM
STAT- PubMed-not-MEDLINE
LR  - 20230321
IS  - 2041-6520 (Print)
IS  - 2041-6539 (Electronic)
IS  - 2041-6520 (Linking)
VI  - 14
IP  - 11
DP  - 2023 Mar 15
TI  - Acid-induced nitrite reduction of nonheme iron(ii)-nitrite: mimicking biological 
      Fe-NiR reactions.
PG  - 2935-2942
LID - 10.1039/d2sc06704h [doi]
AB  - Nitrite reductase (NiR) catalyzes nitrite (NO(2) (-)) to nitric oxide (NO) 
      transformation in the presence of an acid (H(+) ions/pH) and serves as a critical 
      step in NO biosynthesis. In addition to the NiR enzyme, NO synthases (NOSs) 
      participate in NO production. The chemistry involved in the catalytic reduction 
      of NO(2) (-), in the presence of H(+), generates NO with a H(2)O molecule 
      utilizing two H(+) + one electron from cytochromes and is believed to be affected 
      by the pH. Here, to understand the effect of H(+) ions on NO(2) (-) reduction, we 
      report the acid-induced NO(2) (-) reduction chemistry of a nonheme Fe(II)-nitrito 
      complex, [(12TMC)Fe(II)(NO(2) (-))](+) (Fe(II)-NO(2) (-), 2), with variable 
      amounts of H(+). Fe(II)-NO(2) (-) upon reaction with one-equiv. of acid (H(+)) 
      generates [(12TMC)Fe(NO)](2+), FeNO(7) (3) with H(2)O(2) rather than H(2)O. 
      However, the amount of H(2)O(2) decreases with increasing equivalents of H(+) and 
      entirely disappears when H(+) reaches  congruent with two-equiv. and shows H(2)O formation. 
      Furthermore, we have spectroscopically characterized and followed the formation 
      of H(2)O(2) (H(+) = one-equiv.) and H(2)O (H(+)  congruent with two-equiv.) and explained why 
      bio-driven NiR reactions end with NO and H(2)O. Mechanistic investigations, using 
      (15)N-labeled-(15)NO(2) (-) and (2)H-labeled-CF(3)SO(3)D (D(+) source), revealed 
      that the N atom in the Fe(14/15)NO(7) is derived from the NO(2) (-) ligand and 
      the H atom in H(2)O or H(2)O(2) is derived from the H(+) source, respectively.
CI  - This journal is (c) The Royal Society of Chemistry.
FAU - Kulbir
AU  - Kulbir
AUID- ORCID: 0000-0001-8583-6920
AD  - Department of Chemistry, Indian Institute of Science Education and Research 
      (IISER) Tirupati 517507 India pankajatiisert@gmail.com 
      pankaj@iisertirupati.ac.in.
FAU - Das, Sandip
AU  - Das S
AUID- ORCID: 0000-0002-4930-9071
AD  - Department of Chemistry, Indian Institute of Science Education and Research 
      (IISER) Tirupati 517507 India pankajatiisert@gmail.com 
      pankaj@iisertirupati.ac.in.
FAU - Devi, Tarali
AU  - Devi T
AD  - Humboldt-Universitat zu Berlin, Institut fur Chemie Brook-Taylor-Strasse 2 D-12489 
      Berlin Germany.
FAU - Ghosh, Somnath
AU  - Ghosh S
AUID- ORCID: 0000-0003-2447-0501
AD  - Department of Chemistry, Indian Institute of Science Education and Research 
      (IISER) Tirupati 517507 India pankajatiisert@gmail.com 
      pankaj@iisertirupati.ac.in.
FAU - Chandra Sahoo, Subash
AU  - Chandra Sahoo S
AUID- ORCID: 0000-0003-2557-1937
AD  - Department of Chemistry, Punjab University Chandigarh Punjab India.
FAU - Kumar, Pankaj
AU  - Kumar P
AUID- ORCID: 0000-0003-2530-7386
AD  - Department of Chemistry, Indian Institute of Science Education and Research 
      (IISER) Tirupati 517507 India pankajatiisert@gmail.com 
      pankaj@iisertirupati.ac.in.
LA  - eng
PT  - Journal Article
DEP - 20230223
PL  - England
TA  - Chem Sci
JT  - Chemical science
JID - 101545951
PMC - PMC10016336
COIS- There are no conflicts to declare.
EDAT- 2023/03/21 06:00
MHDA- 2023/03/21 06:01
PMCR- 2023/02/23
CRDT- 2023/03/20 04:07
PHST- 2022/12/06 00:00 [received]
PHST- 2023/02/14 00:00 [accepted]
PHST- 2023/03/20 04:07 [entrez]
PHST- 2023/03/21 06:00 [pubmed]
PHST- 2023/03/21 06:01 [medline]
PHST- 2023/02/23 00:00 [pmc-release]
AID - d2sc06704h [pii]
AID - 10.1039/d2sc06704h [doi]
PST - epublish
SO  - Chem Sci. 2023 Feb 23;14(11):2935-2942. doi: 10.1039/d2sc06704h. eCollection 2023 
      Mar 15.