Free Radical Chemistry of Natural Products

  • P. Neta
  • M. G. Simic
Part of the Basic Symposium Series book series (IFTBSS)

Abstract

Free radicals in plant and animal products are far from being thoroughly investigated. Their direct measurements are often lacking and their existence has been usually inferred from either observed products or oxygen depletion studies (Simic and Karel 1980). In both approaches, the deductions are based on comparison with model systems, where free radicals can be observed directly (see, e.g., Hoffman 1981) by electron spin resonance (ESR), spectrophotometry, or some other physicochemical techniques, under strictly controlled conditions. It should be pointed out, however, that only the ESR technique (Sevilla 1981) gives an unequivocal detection of free radicals because it is based on the measurements of unpaired electrons.

Keywords

Tyrosine Superoxide Pyrolysis Nitrite Prostaglandin 

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References

  1. Asmus, K.D 1983. Sulfur-centered free radicals. In Radioprotectors and Anticarcinogens. O.F. Nygarrd and M.G. Simic (Editors), pp. 23–42. Academic Press, NY.Google Scholar
  2. Baignee, A., Howard, J.A., Scaino, J.C., and Stewart, L.C. 1983. Absolute rate constants for reactions of cumyloxy in solution. J. Am. Chem. Soc. 105, 6120–6123.CrossRefGoogle Scholar
  3. Bensasson, R.V., Land. E.J., and Trouscott, T.G. 1983. Flash Photolysis and Pulse Radiolysis. Contributions to the Chemistry of Biology and Medicine. Pergamon Press, Oxford.Google Scholar
  4. Benson, S.W., and Shaw, R. 1968. Thermochemistry of oxidation reactions. Adv. Chem. Ser. 75, 288–294.CrossRefGoogle Scholar
  5. Bielski, B.H.J. 1983A. The chemistry of free and enzyme-bound NAD/NADP radicals. In Radioprotectors and Anticarcinogens. O.F. Nygaard and M.G. Simic (Editors), pp. 43–52. Academic Press, NY.Google Scholar
  6. Bielski, B.H.J. 1983B. Evaluation of the reactivities of HO2/O2 with compounds of biological interest. In Oxy Radicals and Their Scavenger Systems. G. Cohen and R.A. Greenwald (Editors), Vol. 1, pp. 1–7. American Elsevier, NY.Google Scholar
  7. Bothe, E., Schuchmann, M.N., Schulte-Frohlinde, D., and von Sonntag, C. 1978. HO2 elimination from x-hydroxyalkyl-peroxyl radicals in aqueous solution. Photochem. Photobiol. 28, 639–644.CrossRefGoogle Scholar
  8. Butler, J., Land, E.J., Prutz, W.A., and Swallow, A.J. 1982. Charge transfer between tryptophan and tyrosine in proteins. Biochim. Biophys. Acta 705, 150–162.CrossRefGoogle Scholar
  9. Cohen, G., and Greenwald, R.A. (Editors) 1983. Oxy Radicals and Their Scavenger Systems. American Elsevier, NY.Google Scholar
  10. Dinur-Abramovitch, S., and Rabani, J. 1976. Pulse radiolytic investigations of peroxy radicals in aqueous solutions of acetate and glycine. J. Phys. Chem. 80, 1562–1565.CrossRefGoogle Scholar
  11. Farhataziz, and Ross, A.B. 1977. Selected rates of reactions of transients from water in aqueous solutions. III. Hydroxyl radical and perhydroxyl radical and their radical ions. Natl. Stand. Ref. Data Ser. (U.S., Natl. Bur. Stand.) NSRDS- NBS 59.Google Scholar
  12. Fridovich, I. 1972. Superoxide radical and superoxide dismutase. Acc. Chem. Res. 5, 321–326.CrossRefGoogle Scholar
  13. Frimer, A.A. 1982. The organic chemistry of superoxide anion radical. In Super-oxide Dismutase. L.W. Oberley (Editor), Vol. 2, pp. 83–125. CRC Press, Boca Raton, FL.Google Scholar
  14. Gilbert, B.C., Holmes, R.G.G., Laue, H.A.H., and Norman, R.O.C. 1976. Electron spin resonance studies. Part L. Reactions of alkoxyl radicals generated from alkyl hydroperoxides and titanium (III) ion in aqueous solution. J. Chem. Soc., Perkin Trans. 2 pp. 1047–1052.Google Scholar
  15. Gilbert, B.C., Holmes, R.G.G., and Norman, R.O.C. 1977. Electron spin resonance studies. Part LII. Reactions of secondary alkoxyl radicals. J. Chem. Res. Miniprint pp. 101–113.Google Scholar
  16. Gilbert, B.C., Marshall, P.D.R., Normal, R.O.C., Pineda, N., and Williams, P.S. 1981. Electron spin resonance studies. Part 61. The generation and reactions of the t-butoxyl radical in aqueous solution. J. Chem. Soc., Perkin Trans. 2 pp. 1392–1400.Google Scholar
  17. Hoffman, M.Z. 1981. State of the Art Symposium: Radiation Chemistry. J. Chem. Educ. 58 (2).CrossRefGoogle Scholar
  18. Howard, J.A. 1982. Absolute rate constants for reactions of oxyl radicals. Adv. Free Radical Chem. 4, 49–173.Google Scholar
  19. Huie, R.E., and Neta, P. 1984. The chemical behavior of SO3 and SO5 radicals in aqueous solutions. J. Phys Chem.Google Scholar
  20. Ingold, K.U. 1969. Peroxy radicals. Acc. Chem. Res. 2 (1), 1–9.CrossRefGoogle Scholar
  21. Josephson, E.S., and Peterson, M.S. (Editors) 1983. Preservation of Food by Ionizing Radiation. CRC Press, Boca Raton, FL.Google Scholar
  22. Marshall, P.J., Kulmacz, R.J., and Lands, W.E.M. 1984. Hydroperoxides, free radicals and prostaglandin synthesis. In Oxygen Radicals in Chemistry and Biology. W. Bors, M. Saran, and D. Tait (Editors), pp. 299–305. Walter de Gruyter, Berlin.CrossRefGoogle Scholar
  23. Nawar, W.W. 1983. Radiolysis of nonaqueous components of foods. In Preservation of Food by Ionizing Radiation. E.S. Josephson and M.S. Peterson (Editors), Vol. 2, pp. 75–124. CRC Press, Boca Raton, FL.Google Scholar
  24. Neta, P., Dizdaroglu, M., and Simic, M.G. 1984. Radiolytic studies of the cumyloxyl radical in aqueous solutions. Isr. J. Chem. 24, 25–28.Google Scholar
  25. Paul, H., Small, R.D., Jr., and Scaiano, J.C. 1978. Hydrogen abstraction by tert-butoxy radicals. A laser photolysis and electron spin resonance study. J. Am. Chem. Soc. 100, 4520–4527.CrossRefGoogle Scholar
  26. Porter, W.L. 1980. Recent trends in food applications of antioxidants. In Autoxidation in Food and Biological Systems. M.G. Simic and M. Karel (Editors), pp. 295–365. Plenum Press, NY.Google Scholar
  27. Sawyer, D.T., and Nanni, E.J., Jr. 1981. Redox chemistry of dioxygen species and their chemical reacivity. In Oxygen and Oxy Radicals in Chemistry and Biology. M. A. J. Rodgers and E. L. Powers (Editors), pp. 15–44. Academic Press, NY.Google Scholar
  28. Sawyer, D.T., and Valentine, J.S. 1981. How super is superoxide? Acc. Chem. Res. 14, 393–399.CrossRefGoogle Scholar
  29. Sevilla, M.D. 1981. Electron spin resonance of radiation produced free radicals. J. Chem. Educ. 58 (2), 106–110.CrossRefGoogle Scholar
  30. Simic, M.G. 1981. Free radical mechanisms in autoxidation processes. J. Chem. Educ. 58 (2), 125–131.CrossRefGoogle Scholar
  31. Simic, M.G. 1983. Radiation chemistry of water-soluble food components. In Preservation of Food by Ionizing Radiation. E.S. Josephson and M.S. Peterson (Editors), Vol. 2, pp. 1–73. CRC Press, Boca Raton, FL.Google Scholar
  32. Simic, M.G., and Karel, M. (Editors) 1980. Autoxidation in Food and Biological Systems. Plenum Press, NY.Google Scholar
  33. Willson, R.L. 1983. Free radical repair mechanisms and the interaction of glutathione and vitamins C and E. In Radioprotectors and Anticarcinogens. O.F. Nygaard and M.G. Simic (Editors), pp. 1–22. Academic Press, NY.Google Scholar
  34. Yukawa, Y. (Editor) 1965. Handbook of Organic Structural Analysis. W.A. Benjamin, NY.Google Scholar

Copyright information

© AVI Publishing Co. 1985

Authors and Affiliations

  • P. Neta
    • 1
  • M. G. Simic
    • 2
  1. 1.Chemical Kinetics DivisionNational Bureau of StandardsGaithersburgUSA
  2. 2.Radiation Physics DivisionNational Bureau of StandardsGaithersburgUSA

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