An electron spin resonance study of free radicals from catechol estrogens.
Electron spin resonance spectroscopy has been used to demonstrate production of semiquinone free radicals from the oxidation of the catechol estrogens 2- and 4-hydroxyestradiol and 2,6- and 4,6-dihydroxyestradiol. Radicals were generated by horseradish peroxidase/H2O2 or tyrosinase/O2, or by autoxidation, and were detected as their complexes with spin-stabilizing metal ions (Zn2+ and/or Mg2+). Radical production occurs via one- or two-electron oxidation of catechol estrogens, depending on the type of activating system. Autoxidation of catechol estrogens produces superoxide and H2O2 at physiological pH values. The present results also indicate a difference in the reactivity of quinones derived from 2- and 4-hydroxyestradiol. The toxicological significance of these reactions is discussed.
D000818:Animals; D016227:Benzoquinones; D055598:Chemical Phenomena; D002621:Chemistry; D003577:Cytochrome P-450 Enzyme System / Q000378:metabolism; D004578:Electron Spin Resonance Spectroscopy; D004958:Estradiol / Q000031:analogs & derivatives / Q000378:metabolism; D002393:Estrogens, Catechol / Q000378:metabolism*; D005260:Female; D005609:Free Radicals; D006735:Horseradish Peroxidase / Q000378:metabolism; D006861:Hydrogen Peroxide / Q000494:pharmacology; D007527:Isoenzymes / Q000378:metabolism; D008274:Magnesium / Q000494:pharmacology; D008954:Models, Biological; D014442:Monophenol Monooxygenase / Q000378:metabolism; D010084:Oxidation-Reduction; D010100:Oxygen / Q000494:pharmacology; D009195:Peroxidase; D010544:Peroxidases / Q000378:metabolism; D011809:Quinones / Q000378:metabolism / Q000633:toxicity; D014599:Uterus / Q000201:enzymology; D015032:Zinc / Q000494:pharmacology
D016227:Benzoquinones; D002393:Estrogens, Catechol; D005609:Free Radicals; D007527:Isoenzymes; D011809:Quinones; C025232:semiquinone radicals; D004958:Estradiol; D003577:Cytochrome P-450 Enzyme System; C001390:2-hydroxyestradiol; D006861:Hydrogen Peroxide; D006735:Horseradish Peroxidase; D010544:Peroxidases; D009195:Peroxidase; D014442:Monophenol Monooxygenase; D008274:Magnesium; D015032:Zinc; D010100:Oxygen