Oxene transfer, electron abstraction, and cooxidation in the epoxidation of stilbene and 7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene by hemoglobin.
Hemoglobin plus H2O2 oxidizes trans-stilbene to trans-stilbene oxide, cis-stilbene to cis- and trans-stilbene oxide, and trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene to anti-trans-7,8,9,10-tetrahydroxy-7,8,9,10-tetrahydrobenzo[a]pyrene. Oxidation of cis- and trans-stilbene to the corresponding cis- and trans-epoxides proceeds exclusively with incorporation of oxygen from the peroxide. Oxidation of cis-stilbene to the trans-epoxide, however, proceeds without detectable incorporation of oxygen from the peroxide and partial incorporation of oxygen from O2. The epoxidations in which stereochemistry is conserved thus appear to involve ferryl oxygen transfer, whereas the epoxidations in which stereochemistry is inverted are proposed to involve protein-mediated cooxidation [Ortiz de Montellano, P.R., & Catalano, C.E. (1985) J. Biol. Chem. 260, 9265-9271] and possibly electron abstraction-water addition. The epoxidation of trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene incorporates oxygen from H2O2 and H2O but not O2. The oxidation of this substrate is thus consistent with ferryl oxygen transfer and electron abstraction but not protein-mediated cooxidation.
Department of Pharmaceutical Chemistry, School of Pharmacy, University of California, San Francisco 94143.
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Catalano
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Ortiz de Montellano
D000818:Animals; D002273:Carcinogens / Q000378:metabolism*; D002417:Cattle; D004101:Dihydroxydihydrobenzopyrenes / Q000378:metabolism*; D004579:Electron Transport; D004852:Epoxy Compounds; D006420:Hemeproteins / Q000378:metabolism*; D006736:Horses; D006861:Hydrogen Peroxide / Q000378:metabolism; D008706:Methemoglobin / Q000378:metabolism*; D008786:Metmyoglobin / Q000378:metabolism*; D010084:Oxidation-Reduction; D010103:Oxygen Isotopes; D013237:Stereoisomerism; D013267:Stilbenes / Q000378:metabolism*
D002273:Carcinogens; D004101:Dihydroxydihydrobenzopyrenes; D004852:Epoxy Compounds; D006420:Hemeproteins; D010103:Oxygen Isotopes; D013267:Stilbenes; D008786:Metmyoglobin; C017228:benzo(a)pyrene 7,8-dihydrodiol; D008706:Methemoglobin; D006861:Hydrogen Peroxide