Biochemistry (Moscow)

, Volume 67, Issue 8, pp 880–888 | Cite as

Peroxyl Radical Is Produced upon the Interaction of Hypochlorite with tert-Butyl Hydroperoxide

  • O. M. PanasenkoEmail author
  • A. N. Osipov
  • A. V. Chekanov
  • J. Arnhold
  • V. I. Sergienko


As we reported previously, hypochlorite interacting with organic hydroperoxides causes their decomposition ((1995) Biochemistry (Moscow), 60, 1079-1086). This interaction was supposed to be a free-radical process and serve as a source of free radicals initiating lipid peroxidation (LP). The present study is the first attempt to detect and identify free radicals produced in the reaction of hypochlorite with tert-butyl hydroperoxide, (CH3)3COOH, which we have used as an example of organic hydroperoxides. We have used a direct method for free radical detection, EPR of spin trapping, and the following spin traps: N-tert-butyl-α-phenylnitrone (PBN) and α-(4-pyridyl-1-oxyl)-N-tert-butylnitrone (4-POBN). When hypochlorite was added to (CH3)3COOH in the presence of a spin trap, an EPR spectrum appeared representing a superposition of two signals. One of them belonged to a spin adduct formed as a result of direct interaction of hypochlorite with the spin trap (hyperfine splitting constants were: αβH H = 0.148 mT; aN = 1.537 mT; and ΔHPP = 0.042 mT for 4-POBN and αβH = 0.190 mT; aN = 1.558 mT; and ΔHPP = 0.074 mT for PBN). The other signal was produced by hypochlorite interactions with (CH3)3COOH itself (hyperfine splitting constants were: αβH = 0.233 mT; aN = 1.484 mT; ΔHPP = 0.063 mT and αβH = 0.360 mT; aN = 1.547 mT; ΔHPP = 0.063 mT for 4-POBN and PBN, respectively). Comparison of spectral characteristics of this spin adduct with those of tert-butoxyl or tert-butyl peroxyl radicals produced in known reactions of (CH3)3COOH with Fe2+ and Ce4+, respectively, showed that the radical (CH3)3COO. is produced from the interaction of hypochlorite with (CH3)3COOH. Like Ce4+ but not Fe2+, hypochlorite addition to (CH3)3COOH was accompanied by a bright flash of chemiluminescence characteristic of the reactions in which peroxyl radicals are produced. Thus, all these results suggest peroxyl radical production in the reaction of hypochlorite with hydroperoxide. This reaction is one of the most possible ways for the initiation of free-radical LP that occurs in vivo, when hypochlorite interacts with unsaturated lipids comprising natural protein–lipid complexes, such as lipoproteins and biological membranes.

hypochlorite hydroperoxide tert-butyl hydroperoxide free radicals peroxyl radical lipid peroxidation spin traps 


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  1. 1.
    Klebanov, G. I., Vladimirov, Yu. A., Benov, L. C., and Ribarov, S. R. (1988) Byul. Eksp. Biol. Med., 105, 674–677.Google Scholar
  2. 2.
    Hiramatsu, K., Rosen, H., Heinecke, J. W., Wolfbaur, G., and Chait, A. (1987) Arteriosclerosis, 7, 55–60.Google Scholar
  3. 3.
    Panasenko, O. M., Vol'nova, T. V., Osipov, A. N., Azizova, O. A., and Vladimirov, Yu. A. (1991) Biomed. Sci., 1, 581–589.Google Scholar
  4. 4.
    Scaccini, C., and Jialal, I. (1994) Free Rad. Biol. Med., 16, 49–55.Google Scholar
  5. 5.
    Evgina, S. A., Panasenko, O. M., Sergienko, V. I., and Vladimirov, Yu. A. (1992) Biol. Membr. (Moscow), 9, 946–953.Google Scholar
  6. 6.
    Stelmaszynska, T., Kukovetz, E., Egger, G., and Schaur, R. J. (1992) Int. J. Biochem., 24, 121–128.Google Scholar
  7. 7.
    Panasenko, O. M., Evgina, S. A., Aidyraliev, R. K., Sergienko, V. I., and Vladimirov, Yu. A. (1994) Free Rad. Biol. Med., 16, 143–148.Google Scholar
  8. 8.
    Panasenko, O. M., Arnhold, J., Schiller, J., Arnold, K., and Sergienko, V. I. (1994) Biochim. Biophys. Acta, 1215, 259–266.Google Scholar
  9. 9.
    Panasenko, O. M., Evgina, S. A., Driomina, E. S., Sharov, V. S., Sergienko, V. I., and Vladimirov, Yu. A. (1995) Free Rad. Biol. Med., 19, 133–140.Google Scholar
  10. 10.
    Panasenko, O. M., and Arnhold, J. (1996) Biol. Membr. (Moscow), 13, 89–99.Google Scholar
  11. 11.
    Panasenko, O. M. (1997) Biofactors, 6, 181–190.Google Scholar
  12. 12.
    Morris, J. C. (1966) J. Phys. Chem., 70, 3798–3805.Google Scholar
  13. 13.
    Panasenko, O. M., Arnhold, J., Vladimirov, Yu. A., and Sergienko, V. I. (1995) Biochemistry (Moscow), 60, 1079–1086.Google Scholar
  14. 14.
    Arnhold, J., Panasenko, O. M., Schiller, J., Arnold, K., Vladimirov, Yu. A., and Sergienko, V. I. (1996) Z. Naturforsch., 51c, 386–394.Google Scholar
  15. 15.
    Panasenko, O. M., Arnhold, J., Vladimirov, Y. A., Arnold, K., and Sergienko, V. I. (1997) Free Rad. Res., 27, 1–12.Google Scholar
  16. 16.
    Vladimirov, Yu. A., and Archakov, A. I. (1972) Lipid Peroxidation in Biological Membranes [in Russian], Nauka, Moscow.Google Scholar
  17. 17.
    Panasenko, O. M., Arnhold, J., and Schiller, J. (1997) Biochemistry (Moscow), 62, 951–959.Google Scholar
  18. 18.
    Kanofsky, J. R. (1989) Chem.-Biol. Interact., 70, 1–28.Google Scholar
  19. 19.
    Panasenko, O. M., and Arnhold, J. (1999) Free Rad. Res., 30, 479–487.Google Scholar
  20. 20.
    Vasil'ev, Yu. B., Sergienko, V. I., Grinberg, V. A., and Martynov, A. K. (1990) Advances in Science and Technology. Electrochemistry and Medicine [in Russian], Vol. 31, VINI-TI, Moscow, pp. 10–54.Google Scholar
  21. 21.
    Duling, D. R. (1994) J. Magn. Reson., B 104, 105–110.Google Scholar
  22. 22.
    Osipov, A. I. (1983) EPR Studies of Free Radicals Generated on Peroxidation: Candidate's dissertation [in Russian], Moscow State University, Moscow.Google Scholar
  23. 23.
    Sies, H., Stahl, W., and Sundquist, A. R. (1992) Ann. N. Y. Acad. Sci., 669, 7–20.Google Scholar
  24. 24.
    Vladimirov, Yu. A., Olenev, V. I., Suslova, T. B., and Cheremisina, Z. P. (1980) Adv. Lipid Res., 17, 173–249.Google Scholar
  25. 25.
    Candeias, L. P., Patel, K. B., Stratford, M. R., and Wardman, P. (1993) FEBS Lett., 333, 151–153.Google Scholar
  26. 26.
    Candeias, L. P., Stratford, M. R., and Wardman, P. (1994) Free Rad. Res., 20, 241–249.Google Scholar
  27. 27.
    Osipov, A. N., Y akutova, E. Sh., and Vladimirov, Yu. A. (1993) Biofizika, 38, 390–396.Google Scholar
  28. 28.
    Panasenko, O. M., and Sergienko, V. I. (1993) Biol. Membr. (Moscow), 10, 341–382.Google Scholar
  29. 29.
    Panasenko, O. M., Azizova, O. A., and Vladimirov, Yu. A. (1992) in Soviet Medical Reviews. Section B: Physicochemical Aspects of Medicine Reviews (Lopukhin, Yu. M., ed.) Harwood Academic Publishers, New York, Vol. 3, Pt. 3, pp. 1–74.Google Scholar
  30. 30.
    Berliner, J. A., and Heinecke, J. W. (1996) Free Rad. Biol. Med., 20, 707–727.Google Scholar

Copyright information

© MAIK “Nauka/Interperiodica” 2002

Authors and Affiliations

  • O. M. Panasenko
    • 1
    Email author
  • A. N. Osipov
    • 2
  • A. V. Chekanov
    • 1
  • J. Arnhold
    • 3
  • V. I. Sergienko
    • 1
  1. 1.Research Institute of Physico-Chemical MedicineMoscowRussia
  2. 2.Russian State Medical UniversityMoscowRussia
  3. 3.Institute of Medical Physics and BiophysicsUniversity of LeipzigLeipzigGermany

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