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Reaction of thiyl radicals with alcohols, ethers and polyunsaturated fatty acids: A possible role of thiyl free radicals in thiol mutagenesis?

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Summary

Possible reactions of thiyl free radicals in biological environment are reviewed. In particular hydrogen transfer processes from model C–H compounds like alcohols and ethers as well as from polyunsaturated fatty acids to thiyl radicals are described to proceed with reasonably high rate constants (103 – 104 and 106 – 107 M−1 s−1, respectively). Thiyl radicals have thus to be considered as potentially hazardous species especially with respect to DNA damage and lipid peroxidation.

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References

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

    Google Scholar 

  • Asmus K-D (1990) Sulfur-centered free radicals. In: Packer L, Glazer AN (eds) Methods enzymol. Academic Press, San Diego, pp 168–180

    Google Scholar 

  • Asmus K-D, Bonifacic M (1984) In: Fischer H (ed). Landolt-Börnstein. Zahlenwerte und Funktionen, vol 13b, New Series. Springer, Berlin Heidelberg New York

    Google Scholar 

  • Baker MZ, Badiello R, Tamba M, Quintiliani M, Gorin G (1982) Pulse radiolytic study of hydrogen transfer from glutathione to organic radicals. Int J Radiat Biol 41:596–602

    Google Scholar 

  • Bielski BH, Arudi RL, Sutherland MW (1983) A study of the reactivity of HO2/O ⋅2 − with unsaturated fatty acids. J Biol Chem 258:4759–4761

    Google Scholar 

  • Bonincontro A, Cametti C, Rosi A, Sportelli L (1987) Alteration of membrane conductivity and fluidity in human erythrocyte membranes and erythrocyte ghosts following gammairradiation. Int J Radiat Biol 52:447–457

    Google Scholar 

  • Brault D, Neta P, Patterson LK (1985) The lipid peroxidation model for halogenated hydrocarbon toxicity. Kinetics of peroxyl radical processes involving fatty acids and Fe(III) porphyries. Chem-Biol Interact 54:289–297

    Google Scholar 

  • Carter MH, Josephy PD (1986) Mutagenicity of thionitrites in the Ames test. The biological activity of thiyl free radicals. Biochem Pharmacol 35:3847–3851

    Google Scholar 

  • Elliot AJ, Simsons AS, Sopchyshyn FC (1984) Radiolysis of solutions containing organodisulfides. Radiat Phys Chem 23:377–384

    Google Scholar 

  • Erben-Russ M, Bors W, Winter R, Saran M (1986) The reaction of sulfite anion radical (SO −3 ) with polyunsaturated fatty acids. Radiat Phys Chem 27:419–424

    Google Scholar 

  • Erben-Russ M, Michel Ch, Bors W, Saran M (1987) Absolute rate constants of alkoxyl radical reactions in aqueous solution. J Phys Chem 91:2362–2365

    Google Scholar 

  • Forni LG, Willson RL (1986) Thiyl and phenoxyl free radicals and NADH. Direct observation of one-electron oxidation. Biochem J 240:897–903

    Google Scholar 

  • Forni LG, Mönig J, Mora-Arellano VO, Willson RL (1983) Thiyl free radicals: Direct observation of electron transfer reactions with phenothiazines and ascorbate. J Chem Soc Perkin Trans 2:961–965

    Google Scholar 

  • Glatt H, Protic-Sabljic M, Oesch F (1983) Mutagenicity of glutathione in the Ames test. Science 220:961–962

    Google Scholar 

  • Hasegawa K, Patterson LK (1978) Pulse radiolysis studies in model lipid systems: formation and behavior of peroxy radicals in fatty acids. Photochem Photobiol 28:817–823

    Google Scholar 

  • Hoffman MZ, Hayon E (1973) Pulse radiolysis study of sulfhydryl compounds in aqueous solution. J Phys Chem 77:990–996

    Google Scholar 

  • Horton AA, Fairhurst S (1987) Lipid peroxidation and mechanisms of toxicity. CRC Crit Rev Toxicol 18:27–79

    Google Scholar 

  • Huxtable AJ (1986) Biochemistry of sulfur. Plenum Press, New York London

    Google Scholar 

  • Jagannadham V, Steenken S (1984) One-electron reduction of nitrobenzenes by α-hydroxy alkyl radicals via addition/elimination. An example of an organic inner-sphere electron-transfer reaction. J Am Chem Soc 106:6542–6551

    Google Scholar 

  • John DCA, Douglas KT (1989) Apparent sequence preference in cleavage of linear B-DNA by the Cu(II): thiol system. Biochem Biophys Res Commun 165:1235–1242

    Google Scholar 

  • Kessler M, Höper J, Harrison DK, Skolasinska K, Klövekorn WP, Sebening F, Volkholz HJ, Beier I, Kernbach C, Rettig V, Richter H (1984) Tissue O2 under normal and pathological conditions. In: Lübbers DW, Acker H, Leniger-Follert E, Goldstick TK (eds) Oxygen transport to tissue V. Plenum Press, New York London

    Google Scholar 

  • McMillen DF, Golden DM (1982) Hydrocarbon bond dissociation energies. Ann Rev Phys Chem 33:493–532

    Google Scholar 

  • Mönig J, Asmus K-D, Forni LG, Willson RL (1987) On the reaction of molecular oxygen with thiyl radicals: a re-examination. Int J Radiat Biol 52:589–602

    Google Scholar 

  • Porter NA, Wujek DG (1988) The autoxidation of polyunsaturated lipids. In: Quintanilha (ed) Reactive oxygen species in chemistry, biology, and medicine: NATO ASI series, series A: Life Sciences, vol 146. Plenum Press, New York, pp 55–79

    Google Scholar 

  • Pryor WA, Gojon G, Church DF (1978) Relative rate constants for hydrogen atom abstraction by the cyclohexanethiyl and benzenethiyl radicals. J Org Chem 43:793–800

    Google Scholar 

  • Schäfer K, Asmus K-D (1981) Reaction of thiols and disulfides with phosphite radicals. A chain mechanism and RS/PO 23 −⋅ equilibrium. J Phys Chem 85:852–855

    Google Scholar 

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

    Google Scholar 

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

    Google Scholar 

  • Schulte-Frohlinde D (1989) The effect of oxygen and thiols on the radiation damage of DNA. Free Radical Res Commun 6:181–183

    Google Scholar 

  • Searle AJF, Willson RL (1983) Stimulation of microsomal lipid peroxidation by iron and cysteine. Characterization and the role of free radicals. Biochem J 212:549–554

    Google Scholar 

  • Small RD, jr, Scaiano JC, Patterson LK (1979) Radical processes in lipids. A laser photolysis study oft-butoxy radical reactivity toward fatty acids. Photochem Photobiol 29:49–51

    Google Scholar 

  • Stark A, Arad A, Siskindovich S, Pagano DA, Zeiger E (1989) Effect of pH on mutagenesis by thiols in Salmonella typhimurium TA 102. Mutat Res 224:89–94

    Google Scholar 

  • Tamba M, Quintiliani M (1984) Kinetic studies of reactions involved in hydrogen transfer from glutathione to carbohydrate radicals. Radiat Phys Chem 23:259–263

    Google Scholar 

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

    Google Scholar 

  • Tien M, Bucher JR, Aust SD (1982) Thiol-dependent lipid peroxidation. Biochem Biophys Res Commun 107:279–285

    Google Scholar 

  • Torchinsky YM (1981) Sulfur in proteins. Pergamon Press, Oxford New York Toronto

    Google Scholar 

  • Von Sonntag C (1987) The chemical basis of radiation biology. Taylor & Francis, London New York Philadelphia

    Google Scholar 

  • Wardman P (1988) Conjugation and oxidation of glutathione via thiyl free radicals. In: Sies H, Ketterer B (eds) Glutathione conjugation. Academic Press, New York, pp 43–72

    Google Scholar 

  • Willson, RL, Slater TF (1975) Carbon tetrachloride and biological damage: pulse radiolysis studies of associated free radical reactions. In: Adams GE, Fielden EM, Michael BD (eds) Fast processes in radiation chemistry and biology. The Institute of Physics. Wiley, New York

    Google Scholar 

  • Wolfenden BS, Willson RL (1982) Radical-cations as reference chromogens in kinetic studies of one-electron transfer reactions: pulse radiolysis studies of 2,2′-azinobis-(3-ethylbenzthiazoline-6-sulphonate). J Chem Soc Perkin Trans 2:805–812

    Google Scholar 

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Authors and Affiliations

  1. Abteilung Strahlenchemie, Hahn-Meitner-Institut Berlin, Bereich S, Glienicker Strasse 100, D-1000, Berlin 39, Germany

    C. Schöneich & K. -D. Asmus

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  1. C. Schöneich
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  2. K. -D. Asmus
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Paper given at the workshop “Molecular Radiation Biology”. German Section of the DNA Repair Network, München-Neuherberg, 21.–23.3.1990

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Schöneich, C., Asmus, K.D. Reaction of thiyl radicals with alcohols, ethers and polyunsaturated fatty acids: A possible role of thiyl free radicals in thiol mutagenesis?. Radiat Environ Biophys 29, 263–271 (1990). https://doi.org/10.1007/BF01210407

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  • DOI: https://doi.org/10.1007/BF01210407

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