Characterization of semiquinone free radicals formed from stilbene catechol estrogens. An ESR spin stabilization and spin trapping study.
Electron spin resonance spectroscopy has been used to detect, characterize, and to infer structures of o-semiquinones derived from stilbene catechol estrogens. Radicals were generated enzymatically using tyrosinase and were detected as their Mg2+ complexes. It is suggested that initial hydroxylation of stilbene estrogen gives a catechol estrogen in situ; subsequent two-electron oxidation of the catechol to the quinone, followed by reverse disproportionation, leads to the formation of radicals. Consistent with this mechanism, o-phenylenediamine, a quinone trapping agent, inhibits formation of o-semiquinones. A competing mechanism of radical production involves autoxidation of the catechol. Hydroxyl radicals are shown to be produced in this system via a mechanism involving reduction of iron and copper complexes by stilbene catechols. Possible differences in the reactivity of stilbene ortho- and para-semiquinones are discussed.
Kalyanaraman
B
B
Department of Radiology, Medical College of Wisconsin, Milwaukee 53226.
Sealy
R C
RC
Liehr
J G
JG
D016227:Benzoquinones; D003497:Cyclic N-Oxides; D004028:Dienestrol / Q000031:analogs & derivatives / Q000378:metabolism; D004054:Diethylstilbestrol / Q000031:analogs & derivatives / Q000378:metabolism; D004578:Electron Spin Resonance Spectroscopy; D002393:Estrogens, Catechol / Q000378:metabolism*; D005609:Free Radicals; D006589:Hexestrol / Q000031:analogs & derivatives / Q000378:metabolism; D008274:Magnesium / Q000378:metabolism; D015394:Molecular Structure; D014442:Monophenol Monooxygenase / Q000378:metabolism; D010084:Oxidation-Reduction; D011809:Quinones; D013113:Spin Labels; D013267:Stilbenes / Q000378:metabolism*
D016227:Benzoquinones; D003497:Cyclic N-Oxides; D002393:Estrogens, Catechol; D005609:Free Radicals; D011809:Quinones; D013113:Spin Labels; D013267:Stilbenes; D006589:Hexestrol; C025232:semiquinone radicals; C017245:5,5-dimethyl-1-pyrroline-1-oxide; D004054:Diethylstilbestrol; D014442:Monophenol Monooxygenase; D008274:Magnesium; D004028:Dienestrol