Peroxynitrite

Peroxynitrite
Chemical structure of the peroxynitrite anion
Names
IUPAC name
Oxido nitrite
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
674445
KEGG
UNII
  • InChI=1S/HNO3/c2-1-4-3/h3H/p-1
    Key: CMFNMSMUKZHDEY-UHFFFAOYSA-M
  • N(=O)O[O-]
Properties
NO3−
Molar mass 62.005 g·mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Reactions of peroxynitrite leading to either apoptotic or necrotic cell death

Peroxynitrite (sometimes called peroxonitrite) is an ion with the formula ONOO−. It is a structural isomer of nitrate, NO−
3. Peroxynitrite is a potent reactive nitrogen species and is highly cytotoxic.

Preparation

Peroxynitrite can be prepared by the reaction of superoxide with nitric oxide:

NO + O−2 → NO(O2)−

It is prepared by the reaction of hydrogen peroxide with nitrite:

H2O2 + NO−
2 → ONOO− + H2O

Its presence is indicated by the absorbance at 302 nm (pH 12, ε302 = 1670 M−1 cm−1).

Reactions

Peroxynitrite is weakly basic with a pKa of ~6.8.

It is reactive toward DNA and proteins.

ONOO− reacts nucleophilically with carbon dioxide. In vivo, the concentration of carbon dioxide is about 1 mM, and its reaction with ONOO− occurs quickly. Thus, under physiological conditions, the reaction of ONOO− with carbon dioxide to form nitrosoperoxycarbonate (ONOOCO−
2) is by far the predominant pathway for ONOO−. ONOOCO−
2 homolyzes to form carbonate radical and nitrogen dioxide, again as a pair of caged radicals. Approximately 66% of the time, these two radicals recombine to form carbon dioxide and nitrate. The other 33% of the time, these two radicals escape the solvent cage and become free radicals. It is these radicals (carbonate radical and nitrogen dioxide) that are believed to cause peroxynitrite-related cellular damage.

Peroxynitrous acid

Its conjugate acid is peroxynitrous acid, which is highly reactive; by contrast, peroxynitrite is stable in basic solutions.[page needed]

See also

References

  1. 1 2 Szabó, Csaba; Ischiropoulos, Harry; Radi, Rafael (August 2007). "Peroxynitrite: biochemistry, pathophysiology and development of therapeutics". Nature Reviews Drug Discovery. 6 (8): 662–680. doi:10.1038/nrd2222. ISSN 1474-1784.
  2. ↑ Bohle, D. Scott; Sagan, Elisabeth S. (2004). "Main Group Compounds". Tetramethylammonium Salts of Superoxide and Peroxynitrite. Inorganic Syntheses. Vol. 34. p. 36. doi:10.1002/0471653683.ch1. ISBN 978-0-471-64750-8.
  3. ↑ Pacher, P; Beckman, J. S; Liaudet, L (2007). "Nitric oxide and peroxynitrite in health and disease". Physiological Reviews. 87 (1): 315–424. doi:10.1152/physrev.00029.2006. PMC 2248324. PMID 17237348.
  4. ↑ Beckman, J. S; Koppenol, W. H (1996). "Nitric oxide, superoxide, and peroxynitrite: The good, the bad, and ugly". American Journal of Physiology. Cell Physiology. 271 (5): C1424–1437. doi:10.1152/ajpcell.1996.271.5.C1424. PMID 8944624.
  5. ↑ Denicola, Ana; Freeman, Bruce A.; Trujillo, Madia; Radi, Rafael (1996-09-01). "Peroxynitrite Reaction with Carbon Dioxide/Bicarbonate: Kinetics and Influence on Peroxynitrite-Mediated Oxidations". Archives of Biochemistry and Biophysics. 333 (1): 49–58. doi:10.1006/abbi.1996.0363. ISSN 0003-9861.
  6. ↑ Holleman, A. F.; Wiberg, E. (2001). Inorganic Chemistry. San Diego: Academic Press. ISBN 0-12-352651-5.
  7. ↑ Koppenol, W. H (1998). "The chemistry of peroxynitrite, a biological toxin". Química Nova. 21 (3): 326–331. doi:10.1590/S0100-40421998000300014.