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Oxidation of nitric oxide in aqueous solution to nitrite but not nitrate: comparison with enzymatically formed nitric oxide from L-arginine
Open accessAbstract
Nitric oxide (NO) in oxygen-containing aqueous solution has a short half-life that is often attributed to a rapid oxidation to both NO2- and NO3-. The chemical fate of NO in aqueous solution is often assumed to be the same as that in air, where NO is oxidized to NO2 followed by dimerization to N2O4. Water then reacts with N2O4 to form both NO2- and NO3-. We report here that NO in aqueous solution containing oxygen is oxidized primarily to NO2- with little or no formation of NO3-. In the presence of oxyhemoglobin or oxymyoglobin, however, NO and NO2- were oxidized completely to NO3-. Methemoglobin was inactive in this regard. The unpurified cytosolic fraction from rat cerebellum, which contains constitutive NO synthase activity, catalyzed the conversion of L-arginine primarily to NO3- (NO2-/NO3- ratio = 0.25). After chromatography on DEAE-Sephacel or affinity chromatography using 2',5'-ADP-Sepharose 4B, active fractions containing NO synthase activity catalyzed the conversion of L-arginine primarily to NO2- (NO2-/NO3- ratio = 5.6) or only to NO2-, respectively. Unpurified cytosol from activated rat alveolar macrophages catalyzed the conversion of L-arginine to NO2- without formation of NO3-. Addition of 30 microM oxyhemoglobin to all enzyme reaction mixtures resulted in the formation primarily of NO3- (NO2-/NO3- ratio = 0.09 to 0.20). Cyanide ion, which displaces NO2- from its binding sites on oxyhemoglobin, inhibited the formation of NO3-, thereby allowing NO2- to accumulate. These observations indicate clearly that the primary decomposition product of NO in aerobic aqueous solution is NO2- and that further oxidation to NO3- requires the presence of additional oxidizing species such as oxyhemoproteins.
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“This report clearly demonstrated that the dominant oxidation product of NO in aqueous solution is nitrite and that nitrate formation requires additional oxidation by heme proteins.”
From Inorganic nitrite therapy: historical perspective and future directions (2011) · cites this paper as [76]
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MethodModulations of Glypican-1 Heparan Sulfate Structure by Inhibition of Endogenous Polyamine Synthesis
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In Vitro Regulation of an Inducible-Type NO Synthase in the Rat Seminiferous Tubule Cells1
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“Although nitrites (NO2 ) have been described for a long time, with nitrates, as the inert end products of the NO oxidative metabolism (3), recent evidence indicates that under specific conditions, nitrite can be reconverted into”
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“Nitrite is the stable endproduct of the autoxidation of NO• in aqueous solution (Ignarro et al., 1993).”
BackgroundDifferential effects of osteopontin on the cytotoxic activity of macrophages from young and old mice
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Polymeric piezoelectric actuator substrate for osteoblast mechanical stimulation
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“In aqueous buffers and culture conditions nitrite is the principal oxidation product of NO (Ignarro et al., 1993).”
BackgroundCytochrome bd from Escherichia coli catalyzes peroxynitrite decomposition
Borisov, V. B., Forte, E., Siletsky, S. A., Sarti, P., & Giuffrè, A. (2014) · Biochimica et Biophysica Acta (BBA) - Bioenergetics · doi:10.1016/j.bbabio.2014.10.006 · Cited by 48
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Metabolism ofS-nitrosoglutathione by endothelial cells
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“If nitric oxide were the primary decomposition product of GSNO decay, it would be expected that the GSNO would be stoichiometrically converted to nitrite because nitrite is by far the major oxidation product of nitric oxide (19).”
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“It is also worth noting that although we used a validated chemiluminescence method of detecting NO, and its metabolic products nitrite and nitrate, which together are termed NOX [59,60], the in vivo measurement of NO is difficult, as NO has a short half-life and reacts rapidly with ROS, oxygen, metals, sulphydryls, di…”
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Brain nitrite production during global ischemia and reperfusion: an in vivo microdialysis study
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“The levels of nitrite in culture supernatants of lavage cells were determined at the end of an incubation period and used as an indicator of nitric oxide production by lavage cells (Hibbs et al. 1988, Ignarro et al. 1993).”
MethodExogenous nitric oxide elicits chemotaxis of neutrophils in vitro
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Oxygen Regulates Tissue Nitrite Metabolism
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“Although it is accepted that myoglobin oxidizes nitrite (18, 30), this role for Ccox and CYP450 is not characterized.”
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The decomposition of peroxynitrite to nitroxyl anion (NO-) and singlet oxygen in aqueous solution
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The decomposition of peroxynitrite to nitroxyl anion (NO − ) and singlet oxygen in aqueous solution
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Light‐Activated Transfer of Nitric Oxide from a Porous Material
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Hemin activation of an inducible isoform of nitric oxide synthase in vascular smooth-muscle cells
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Markers of lung disease in exhaled breath: nitric oxide
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“The protein quickly binds to calmodulin, independent of intracellular Ca2+ (Belvisi, Mitchell, & Yacoub, 2003), and its resulting bioactivity is longer than its constitutive counterparts (Bateman et al., 2003; Ignarro et al., 1993; Murad, 1996).”
Background
Metadata
- Authors
- Ignarro, L. J., Fukuto, J. M., Griscavage, J. M., Rogers, N. E., & Byrns, R. E.
- Affiliations
- University of California, Los Angeles (US)
- ORCID
- Fukuto, J M
- Venue
- Proceedings of the National Academy of Sciences
- Publisher
- National Academy of Sciences
- Published
- 1993-09
- Volume
- 90
- Issue
- 17
- Pages
- 8103-8107
- ISSN
- 0027-8424 (ISSN-L)
- 1091-6490
- PMC
- PMC47296
- OpenAlex
- W2033379487
- Cited by
- 856
- References
- 28
- Citations by year
- 2026: 14 · 2025: 14 · 2024: 19 · 2023: 21 · 2022: 14 · 2021: 15 · 2020: 21 · 2019: 19 · 2018: 20 · 2017: 21 · 2016: 18 · 2015: 23 · 2014: 28 · 2013: 27 · 2012: 24
- FWCI
- 17.78
- Type
- journal article
- Language
- en
- Open access
- green
- www.ncbi.nlm.nih.gov
- Locations
- Proceedings of the National Academy of Sciences (publishedVersion)
- PubMed Central (publishedVersion)
- PubMed (publishedVersion)
- Funders
- National Institutes of Health (5r01hl040922-11, 5r01hl046388-03, 5r01hl035014-12)
- National Heart, Lung, and Blood Institute (HL 46388, HL-35014, HL 40922)
- Topics
- Health Sciences › Medicine › Physiology (medical) › Nitric Oxide and Endothelin Effects
- Life Sciences › Biochemistry, Genetics and Molecular Biology › Biochemistry › Hemoglobin structure and function
- Life Sciences › Biochemistry, Genetics and Molecular Biology › Molecular Biology › Redox biology and oxidative stress
- Keywords
- NO oxidation, nitrite, nitrate, aqueous solutions, oxyhemoglobin, oxymyoglobin, methemoglobin, nitric oxide synthase, L-arginine, alveolar macrophages, cyanide, heme proteins
- MeSH terms
- Amino Acid Oxidoreductases, Animals, Arginine, Hemeproteins, Humans, Kinetics, Methemoglobin, Myoglobin, Nitrates, Nitric Oxide, Nitrites, Oxidation-Reduction, Oxyhemoglobins, Solutions, Nitric Oxide Synthase
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