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H-Atom Abstraction by Thiyl Radicals

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Abstract

It is widely accepted and experimentally confirmed that thiyl radicals are formed as intermediate species in biological systems by several different processes (1-3). Thiyl radicals have long been considered unreactive and harmless. Their fate has commonly been ascribed to the dimerization reaction, i.e. the formation of disulfide molecules. However, generally this reaction is not very likely to occur in biological systems, as pointed out by Wardman (3). This is due to the low steady-state concentration of thiyl radicals. Furthermore, there is accumulating experimental evidence that thiyl radicals are also highly reactive toward molecular species. The redox properties of thiyl radicals, their pronounced tendency to stabilize by forming three-electron bonded complexes and the mechanism of addition to oxygen have recently been reviewed (1,3-6). Only the H-atom abstraction reaction by thiyl radicals, recently recognized to have pronounced biological significance, will be discussed here.

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References

  1. C. von Sonntag, The Chemical Basis of Radiation Biology, 1987. Taylor and Francis, London.

    Google Scholar 

  2. R.P. Mason, E.s.r. investigation of thiyl free radical metabolites of glutathione and drugs. In: Sulfur-Centered Reactive Intermediates in Chemistry and Biology, 1990 (C. Chatgilialoglu and K.-D. Asmus, Eds.). NATO-ASI series A, Plenum Press, New York, in press.

    Google Scholar 

  3. P. Wardman, Conjugation and oxidation of glutathione via thiyl free radicals. In: Glutathione Conjugation, 1988 (H. Sies and B. Ketterer, Eds.), p.p. 44–72. Academic Press, London.

    Google Scholar 

  4. K.-D. Asmus, Three-electron bonded radical species. In: Sulfur-Centered Reactive Intermediates in Chemistry and Biology, 1990 (C. Chatgilialoglu and K.-D. Asmus, Eds.). NATO-ASI series A, Plenum Press, New York, in press.

    Google Scholar 

  5. D.A. Armstrong, Redox systems with S-centered radical species. In: Sulfur- Centered Reactive Intermediates in Chemistry and Biology, 1990 (C. Chatgilialoglu and K.-D. Asmus, Eds.). NATO-ASI series A, Plenum Press, New York, in press.

    Google Scholar 

  6. M. Tamba, G. Simone and M. Quintiliani, Interactions of thiyl free radicals with oxygen: a pulse radiolysis study, Int. J. Radiat. Biol. 50, 595–600 (1986).

    Article  CAS  Google Scholar 

  7. O.F. Nygaard and M.G. Simic (Eds.), Radioprotectors and Anticarcinogens, 1983, Academic Press, New York.

    Google Scholar 

  8. P.C. Jocelyn, Biochemistry of the SH Group, 1972, Academic Press, London.

    Google Scholar 

  9. D.F. McMillen and D.M. Golden, Hydrocarbon bond dissociation energies. Annu. Rev. Phys. Chem. 33,493–532 (1982).

    Article  CAS  Google Scholar 

  10. C. Schöneich, K.-D. Asmus, U. Dillinger and F. v. Bruchhausen, Thiyl radical attack on polyunsaturated fatty acids: a possible route to lipid peroxidation. Biochem. Biophys. Res. Commun.161,113–120 (1989).

    Article  PubMed  Google Scholar 

  11. M. D’Aquino, C. Dunster and R.L. Willson, Vitamin A and glutathionemediated free radical damage: competing reactions with polyunsaturated fatty acids and vitamin C. Biochem. Biophys. Res. Commun. 161, 1199–1203 (1989).

    Article  PubMed  Google Scholar 

  12. A.A. Stark, D.A. Pagano and E. Zeiger, Oxidative mutagenesis by the glutathione-gamma-glutamyl transpeptidase system: mechanism and possible relevance to hepatocarcinogenesis. (These proceedings).

    Google Scholar 

  13. W.A. Pryor, G. Gojon and D.F. Church, Relative rate constants for hydrogen atom abstraction by the cyclohexanethiyl and benzenethiyl radicals. J. Org. Chem. 43, 793–800 (1978).

    CAS  Google Scholar 

  14. R.W. Alder, M. Bonifaae and K.-D. Asmus, Reaction of a stable N..N bonded radical cation with free radicals generated by pulse radiolysis: exceedingly rapid hydrogen abstraction from C-H bonds. J. Chem. Soc. Perkin Trans. II,277–284 (1986).

    Google Scholar 

  15. A.J. Elliot, A.S. Simsons and F.C. Sopchyshyn, Radiolysis of solutions containing organo-disulphides. Radiat. Phys. Chem. 23, 377–384 (1984).

    CAS  Google Scholar 

  16. M.S. Akhlaq, H.-P. Schuchmann and C. v. Sonntag, The reverse of the “repair” reaction of thiols: H-abstraction at carbon by thiyl radicals. Int. J. Radiat. Biol. 51,91–102 (1987).

    Article  CAS  Google Scholar 

  17. C. Schöneich, M. Bonifa6i6 and K.-D. Asmus, Reversible H-atom abstraction from alcohols by thiyl radicals: determination of absolute rate constants by pulse radiolysis. Free Radical Res. Commun. 6, 393–405 (1989).

    Article  Google Scholar 

  18. . K. Schöfer and K.-D. Asmus, Reaction of thiols and disulfides with phosphite radicals. A chain mechanism and RS•/PO32-• equilibrium. J. Phys. Chem. 85, 852–855 (1981).

    Article  Google Scholar 

  19. R.M. Kellogg, Thiyl radicals. In: Methods in Free Radical Chemistry, 1969 (E.S. Huyser, Ed.), Vol. II, pp. 1–120. Marcel Dekker, New York.

    Google Scholar 

  20. D. Brault and P. Neta, One-electron reduction of ferriporphyrins and reactions of ferric and ferrous porphyrins with a halothane-derived radical. J. Phys. Chem. 86,3405–3410 (1982).

    Article  CAS  Google Scholar 

  21. C. Schöneich, M. Bonifa6i6 and K.-D. Asmus, to be published.

    Google Scholar 

  22. P. Neta, R.E. Huie, S. Mosseri, L.V. Shastri, J.P. Mitral, P. Maruthamuthu and S. Steenken, Rate constants for reduction of substituted methylperoxyl radicals by ascorbate ions and TMPD. J. Phys. Chem. 93,4099–4104 (1989).

    Article  CAS  Google Scholar 

  23. H.R. Glatt, M. Protić-Sabljić and F. Oesch Mutagenicity of glutathione and cysteine in the Ames test. Science 220, 961–963 (1983).

    Article  PubMed  CAS  Google Scholar 

  24. A.A. Stark, A. Arad, S. Siskindovich, D.A. Pagano and E. Zeiger, Effect of pH on mutagenesis by thiols in Sallmonella typhimurium TA 102. Mutat. Res. 224,89–94 1989.

    Article  PubMed  CAS  Google Scholar 

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Bonifačić, M. (1991). H-Atom Abstraction by Thiyl Radicals. In: Nygaard, O.F., Upton, A.C. (eds) Anticarcinogenesis and Radiation Protection 2. Springer, Boston, MA. https://doi.org/10.1007/978-1-4615-3850-9_34

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  • DOI: https://doi.org/10.1007/978-1-4615-3850-9_34

  • Publisher Name: Springer, Boston, MA

  • Print ISBN: 978-1-4613-6718-5

  • Online ISBN: 978-1-4615-3850-9

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