Skip to main content
PMC home page
Proceedings of the National Academy of Sciences of the United States of America logoLink to Proceedings of the National Academy of Sciences of the United States of America
. 1981 Sep;78(9):5508–5512. doi: 10.1073/pnas.78.9.5508

beta-meso-Phenylbiliverdin IX alpha and N-phenylprotoporphyrin IX, products of the reaction of phenylhydrazine with oxyhemoproteins.

S Saito, H A Itano
PMCID: PMC348775  PMID: 6946488

Abstract

Oxyhemoglobin and oxymyoglobin were allowed to react aerobically with phenylhydrazine and p-tolylhydrazine. The chloroform extract of each reaction mixture, after treatment with H2SO4/methanol, yielded a blue pigment and a green pigment, which were identified by electronic absorption, mass, and proton NMR spectroscopy as the dimethyl esters of beta-meso-arylbiliverdin IX alpha and N-arylprotoporphyrin IX, respectively. N-Phenylprotoporphyrin IX dimethyl ester formed complexes with Zn2+, Cd2+, and Hg2+ but not with other cations. The proton NMR spectrum of the zinc complex suggested binding of the phenyl group to one of the two pyrrole rings of protoporphyrin IX with a propionic acid substituent. The effectiveness of phenylhydrazine as an inducer of Heinz body formation may be due to destabilization of the hemoglobin molecule by the replacement of heme with phenyl adducts of biliverdin and protoporphyrin.

Full text

PDF
5511

Selected References

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

  1. 'Carra P. O., Colleran E. HAEM catabolism and coupled oxidation of haemproteins. FEBS Lett. 1969 Nov 29;5(4):295–298. doi: 10.1016/0014-5793(69)80372-8. [DOI] [PubMed] [Google Scholar]
  2. BEAVEN G. H., WHITE J. C. Oxidation of phenylhydrazines in the presence of oxyhaemoglobin and the origin of Heinz bodies in erythrocytes. Nature. 1954 Feb 27;173(4400):389–391. doi: 10.1038/173389b0. [DOI] [PubMed] [Google Scholar]
  3. Bonnett R., Dimsdale M. J. The meso-reactivity of porphyrins and related compounds. V. The meso-oxidation of metalloporphyrins. J Chem Soc Perkin 1. 1972;20:2540–2548. doi: 10.1039/p19720002540. [DOI] [PubMed] [Google Scholar]
  4. Bonnett R., McDonagh A. F. The meso-reactivity of porphyrins and related compounds. VI. Oxidative cleavage of the haem system. The four isomeric biliverdins of the IX series. J Chem Soc Perkin 1. 1973;9:881–888. doi: 10.1039/p19730000881. [DOI] [PubMed] [Google Scholar]
  5. Carrell R. W., Lehmann H. The unstable haemoglobin haemolytic anaemias. Semin Hematol. 1969 Apr;6(2):116–132. [PubMed] [Google Scholar]
  6. Goldberg B., Stern A., Peisach J. The mechanism of superoxide anion generation by the interaction of phenylhydrazine with hemoglobin. J Biol Chem. 1976 May 25;251(10):3045–3051. [PubMed] [Google Scholar]
  7. Hirota K., Itano H. A., Vedvick T. S. Oxidative degradation of haemoglobin by nitrosobenzene in the erythrocyte. Biochem J. 1978 Sep 15;174(3):693–697. doi: 10.1042/bj1740693. [DOI] [PMC free article] [PubMed] [Google Scholar]
  8. Itano H. A., Hirota K., Vedvick T. S. Ligands and oxidants in ferrihemochrome formation and oxidative hemolysis. Proc Natl Acad Sci U S A. 1977 Jun;74(6):2556–2560. doi: 10.1073/pnas.74.6.2556. [DOI] [PMC free article] [PubMed] [Google Scholar]
  9. Jackson A. H., Dearden G. R. N-methylporphyrins. Ann N Y Acad Sci. 1973;206:151–176. doi: 10.1111/j.1749-6632.1973.tb43210.x. [DOI] [PubMed] [Google Scholar]
  10. Lemberg R., Cortis-Jones B., Norrie M. Chemical mechanism of the oxidation of protohaematin to verdohaematin. Biochem J. 1938 Jan;32(1):171–186. doi: 10.1042/bj0320171. [DOI] [PMC free article] [PubMed] [Google Scholar]
  11. O'Carra P., Colleran E. Separation and identification of biliverdin isomers and isomer analysis of phycobilins and bilirubin. J Chromatogr. 1970 Aug 12;50(3):458–468. doi: 10.1016/s0021-9673(00)97973-1. [DOI] [PubMed] [Google Scholar]
  12. Ortiz de Montellano P. R., Beilan H. S., Kunze K. L., Mico B. A. Destruction of cytochrome P-450 by ethylene. Structure of the resulting prosthetic heme adduct. J Biol Chem. 1981 May 10;256(9):4395–4399. [PubMed] [Google Scholar]
  13. Ortiz de Montellano P. R., Beilan H. S., Kunze K. L. N-Methylprotoporphyrin IX: chemical synthesis and identification as the green pigment produced by 3,5-diethoxycarbonyl-1,4-dihydrocollidine treatment. Proc Natl Acad Sci U S A. 1981 Mar;78(3):1490–1494. doi: 10.1073/pnas.78.3.1490. [DOI] [PMC free article] [PubMed] [Google Scholar]
  14. Perutz M. F. The Croonian Lecture, 1968. The haemoglobin molecule. Proc R Soc Lond B Biol Sci. 1969 May 20;173(1031):113–140. doi: 10.1098/rspb.1969.0043. [DOI] [PubMed] [Google Scholar]
  15. Rasmussen R. D., Yokoyama W. H., Blumenthal S. G., Bergstrom D. E., Ruebner B. H. High-performance liquid chromatographic separation and quantification of the four biliverdin dimethyl ester isomers of the IX series. Anal Biochem. 1980 Jan 1;101(1):66–74. doi: 10.1016/0003-2697(80)90041-x. [DOI] [PubMed] [Google Scholar]
  16. Stoll M. S., Gray C. H. The preparation and characterization of bile pigments. Biochem J. 1977 Apr 1;163(1):59–101. doi: 10.1042/bj1630059. [DOI] [PMC free article] [PubMed] [Google Scholar]
  17. Vedvick T. S., Itano H. A. The reaction of halophenylhydrazines with oxygen in the presence of oxyhemoglobin and metal ions. Biochim Biophys Acta. 1981 Jan 21;672(2):214–218. doi: 10.1016/0304-4165(81)90395-0. [DOI] [PubMed] [Google Scholar]
  18. de Matteis F., Gibbs A. H., Jackson A. H., Weerasinghe S. Conversion of liver haem into N-substituted porphyrins or green pigments. Nature of the substituent at the pyrrole nitrogen atom. FEBS Lett. 1980 Sep 22;119(1):109–112. doi: 10.1016/0014-5793(80)81009-x. [DOI] [PubMed] [Google Scholar]

Articles from Proceedings of the National Academy of Sciences of the United States of America are provided here courtesy of National Academy of Sciences

RESOURCES