Abstract
A new approach is suggested for an explanation of sterospecific haem degradation to biliverdin and bilirubin. A model is proposed in which an oxygen molecule, bound to the haem iron atom, attacks a methene-bridge carbon atom in an intramolecular reaction. Specificity of macrocyclic ring cleavage is explained on the basis of the different accessibilities of the bound oxygen molecule to the four methene bridges. The consequences of these ideas are assessed in relation to coupled oxidation in model systems and to haem catabolism.
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Selected References
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- '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]
- Beaven G. H., Chen S. H., d' Albis A., Gratzer W. B. A spectroscopic study of the haemin--human-serum-albumin system. Eur J Biochem. 1974 Feb 1;41(3):539–546. doi: 10.1111/j.1432-1033.1974.tb03295.x. [DOI] [PubMed] [Google Scholar]
- 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]
- Brown N. A., King R. F., Shillcock M. E., Brown S. B. Haemoglobin catabolism: the role of ferrihaems in studies of the degradation pathway. Biochem J. 1974 Jan;137(1):135–137. doi: 10.1042/bj1370135. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Brown S. B., King R. F. The structure of haem in pyridine/water mixtures and its implication in studies of haem catabolism. Biochem J. 1976 Feb 1;153(2):479–483. doi: 10.1042/bj1530479. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Collman J. P., Gagne R. R., Reed C. A., Robinson W. T., Rodley G. A. Structure of an iron(II) dioxygen complex; a model for oxygen carrying hemeproteins. Proc Natl Acad Sci U S A. 1974 Apr;71(4):1326–1329. doi: 10.1073/pnas.71.4.1326. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Jones P., Middlemiss D. N. Formation of catalase compound I by reaction with peroxoacetic acid: pH changes in unbuffered systems. Biochem J. 1974 Nov;143(2):473–474. doi: 10.1042/bj1430473. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Jones P., Prudhoe K., Robson T. Oxidation of deuteroferrihaem by hydrogen peroxide. Biochem J. 1973 Oct;135(2):361–365. doi: 10.1042/bj1350361. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Lathe G. H. The degradation of haem by mammals and its excretion as conjugated bilirubin. Essays Biochem. 1972;8:107–148. [PubMed] [Google Scholar]
- Maines M. D., Kappas A. Cobalt induction of hepatic heme oxygenase; with evidence that cytochrome P-450 is not essential for this enzyme activity. Proc Natl Acad Sci U S A. 1974 Nov;71(11):4293–4297. doi: 10.1073/pnas.71.11.4293. [DOI] [PMC free article] [PubMed] [Google Scholar]
- O'Carra P., Colleran E. Methine bridge selectivity in haem-cleavage reactions: relevance to the mechanism of haem catabolism. Biochem Soc Trans. 1976;4(2):209–214. doi: 10.1042/bst0040209. [DOI] [PubMed] [Google Scholar]
- PETRYKA Z., NICHOLSON D. C., GRAY C. H. Isomeric bile pigments as products of the in vitro fission of haemin. Nature. 1962 Jun 16;194:1047–1048. doi: 10.1038/1941047a0. [DOI] [PubMed] [Google Scholar]
- Rüdiger W. Bile pigments: a new degradation technique and its application. Biochem Soc Symp. 1968;28:121–130. [PubMed] [Google Scholar]
- Schmid R. Introduction to haem catabolism and studies on haem oxygenase. Biochem Soc Trans. 1976;4(2):195–197. doi: 10.1042/bst0040195. [DOI] [PubMed] [Google Scholar]
- Schmid R., McDonagh A. F. The enzymatic formation of bilirubin. Ann N Y Acad Sci. 1975 Apr 15;244:533–552. doi: 10.1111/j.1749-6632.1975.tb41553.x. [DOI] [PubMed] [Google Scholar]
- Schonbaum G. R., Lo S. Interaction of peroxidases with aromatic peracids and alkyl peroxides. Product analysis. J Biol Chem. 1972 May 25;247(10):3353–3360. [PubMed] [Google Scholar]
- Yoshida T., Takahashi S., Kikuchi G. Partial purification and reconstitution of the heme oxygenase system from pig spleen microsomes. J Biochem. 1974 May;75(5):1187–1191. doi: 10.1093/oxfordjournals.jbchem.a130494. [DOI] [PubMed] [Google Scholar]
