Skip to main content
NCBI home page
Environmental Health Perspectives logoLink to Environmental Health Perspectives
. 1987 Aug;73:147–151. doi: 10.1289/ehp.8773147

Mechanism of autocatalytic oxidation of oxyhemoglobin by nitrite.

H Kosaka 1, I Tyuma 1
PMCID: PMC1474547  PMID: 2822381

Abstract

Oxidation of oxyhemoglobin by nitrite is characterized by the presence of a lag phase followed by autocatalysis. The stoichiometry of the overall reaction is described by the following equation: 4HbO2 + 4NO2- + 4H+ = 4Hb+ + 4NO3- + O2 + 2H2O (Hb denotes hemoglobin monomer). During the oxidation, we detected a free radical at g = 2.005, which is very similar to the methemoglobin free radical generated by the reaction with hydrogen peroxide. Nitrosylhemoglobin was not detected. The oxidation was delayed by the addition of KCN or catalase, but was not modified by superoxide dismutase in phosphate buffer. In bistris buffer, however, superoxide dimutase markedly prolonged the lag phase. The results suggest that during the oxidation, the methemoglobin peroxide compound is generated and converts nitrite into nitrogen dioxide by its peroxidatic activity. Nitrogen dioxide oxidizes oxyhemoglobin to methemoglobin and nitrite, yielding the autocatalytic phase.

Full text

PDF
147

Selected References

These references are in PubMed. This may not be the complete list of references from this article.

  1. Ames B. N., Cathcart R., Schwiers E., Hochstein P. Uric acid provides an antioxidant defense in humans against oxidant- and radical-caused aging and cancer: a hypothesis. Proc Natl Acad Sci U S A. 1981 Nov;78(11):6858–6862. doi: 10.1073/pnas.78.11.6858. [DOI] [PMC free article] [PubMed] [Google Scholar]
  2. BETKE K., GREINACHER I., TIETZE O. Oxydation menschlicher und tierischer Oxyhämoglobine durch Natriumnitrit. Naunyn Schmiedebergs Arch Exp Pathol Pharmakol. 1956;229(3):220–232. [PubMed] [Google Scholar]
  3. Chiodi H., Collier C. R., Mohler J. G. In vitro methemoglobin formation in human blood exposed to NO2. Environ Res. 1983 Feb;30(1):9–15. doi: 10.1016/0013-9351(83)90160-3. [DOI] [PubMed] [Google Scholar]
  4. GEORGE P., IRVINE D. H. The reaction between metmyoglobin and hydrogen peroxide. Biochem J. 1952 Nov;52(3):511–517. doi: 10.1042/bj0520511. [DOI] [PMC free article] [PubMed] [Google Scholar]
  5. HOWELL R. R., WYNGAARDEN J. B. On the mechanism of peroxidation of uric acids by hemoproteins. J Biol Chem. 1960 Dec;235:3544–3550. [PubMed] [Google Scholar]
  6. Hodgson E. K., Fridovich I. The role of O2- in the chemiluminescence of luminol. Photochem Photobiol. 1973 Dec;18(6):451–455. doi: 10.1111/j.1751-1097.1973.tb06449.x. [DOI] [PubMed] [Google Scholar]
  7. Imaizumi K., Tyuma I., Imai K., Kosaka H., Ueda Y. In vivo studies on methemoglobin formation by sodium nitrite. Int Arch Occup Environ Health. 1980 Feb;45(2):97–104. doi: 10.1007/BF01274129. [DOI] [PubMed] [Google Scholar]
  8. KAKIZAKI T., SATO M., TSURUTA H., HASEGAWA H. [OXIDATION OF HORSE OXYHEMOGLOBIN BY SODIUM NITRITE]. Seikagaku. 1965 Jan;37:14–20. [PubMed] [Google Scholar]
  9. KING N. K., WINFIELD M. E. The mechanism of metmyoglobin oxidation. J Biol Chem. 1963 Apr;238:1520–1528. [PubMed] [Google Scholar]
  10. Kosaka H., Imaizumi K., Imai K., Tyuma I. Stoichiometry of the reaction of oxyhemoglobin with nitrite. Biochim Biophys Acta. 1979 Nov 23;581(1):184–188. doi: 10.1016/0005-2795(79)90235-6. [DOI] [PubMed] [Google Scholar]
  11. Kosaka H., Imaizumi K., Tyuma I. Mechanism of autocatalytic oxidation of oxyhemoglobin by nitrite. An intermediate detected by electron spin resonance. Biochim Biophys Acta. 1982 Apr 3;702(2):237–241. doi: 10.1016/0167-4838(82)90508-8. [DOI] [PubMed] [Google Scholar]
  12. Kosaka H., Tyuma I. Production of superoxide anion by N,N-bis(2-hydroxyethyl)-iminotris(hydroxymethyl)methane buffer during oxidation of oxyhemoglobin by nitrite and effect of inositol hexaphosphate on the oxidation. Biochim Biophys Acta. 1982 Dec 20;709(2):187–193. doi: 10.1016/0167-4838(82)90460-5. [DOI] [PubMed] [Google Scholar]
  13. Misra H. P., Squatrito P. M. The role of superoxide anion in peroxidase-catalyzed chemiluminescence of luminol. Arch Biochem Biophys. 1982 Apr 15;215(1):59–65. doi: 10.1016/0003-9861(82)90278-8. [DOI] [PubMed] [Google Scholar]
  14. Oda H., Nogami H., Nakajima T. Reaction of hemoglobin with nitric oxide and nitrogen dioxide in mice. J Toxicol Environ Health. 1980 May;6(3):673–678. doi: 10.1080/15287398009529884. [DOI] [PubMed] [Google Scholar]
  15. Ortiz de Montellano P. R., Catalano C. E. Epoxidation of styrene by hemoglobin and myoglobin. Transfer of oxidizing equivalents to the protein surface. J Biol Chem. 1985 Aug 5;260(16):9265–9271. [PubMed] [Google Scholar]
  16. Roy A. K., Kahl R., Jung F. Uber die Reaktion zwischen Natriumnitrit und Hämoglobin. II. Hemmstoffe der autokatalytischen Reaktion. Acta Biol Med Ger. 1969;22(3):445–459. [PubMed] [Google Scholar]
  17. Smith R. C., Nunn V. Prevention by 3-N-ribosyluric acid of the oxidation of bovine hemoglobin by sodium nitrite. Arch Biochem Biophys. 1984 Jul;232(1):348–353. doi: 10.1016/0003-9861(84)90550-2. [DOI] [PubMed] [Google Scholar]
  18. Tomoda A., Matsukawa S., Takeshita M., Yoneyama Y. Effect of inositol hexaphosphate on hemoglobin oxidation by nitrite and ferricyanide. Biochem Biophys Res Commun. 1977 Feb 21;74(4):1469–1474. doi: 10.1016/0006-291x(77)90607-6. [DOI] [PubMed] [Google Scholar]
  19. Tomoda A., Tsuji A., Yoneyama Y. Involvement of superoxide anion in the reaction mechanism of haemoglobin oxidation by nitrite. Biochem J. 1981 Jan 1;193(1):169–179. doi: 10.1042/bj1930169. [DOI] [PMC free article] [PubMed] [Google Scholar]
  20. WINTERHALTER K. H., HUEHNS E. R. PREPARATIONS, PROPERTIES, AND SPECIFIC RECOMBINATION OF ALPHA-BETA-GLOBIN SUBUNITS. J Biol Chem. 1964 Nov;239:3699–3705. [PubMed] [Google Scholar]
  21. Watanabe S., Ogata M. Generation of superoxide and hydrogen peroxide during interaction of nitrite with human hemoglobin. Acta Med Okayama. 1981 Jun;35(3):173–178. doi: 10.18926/AMO/31285. [DOI] [PubMed] [Google Scholar]
  22. Wegner T. N. Simple and sensitive procedure for determining nitrate and nitrite in mixtures in biological fluids. J Dairy Sci. 1972 May;55(5):642–644. doi: 10.3168/jds.S0022-0302(72)85550-4. [DOI] [PubMed] [Google Scholar]

Articles from Environmental Health Perspectives are provided here courtesy of National Institute of Environmental Health Sciences

RESOURCES