Skip to main content
SpringerLink
Log in

Antioxidant Chemistry of α-Tocopherol in Biological Systems

Roles of Redox Cycles and Metabolism

  • Chapter
Fat-Soluble Vitamins

Part of the book series: Subcellular Biochemistry ((SCBI,volume 30))

Abstract

Vitamin E is the family name given to a group of tocopherols and tocotrienols that function as the principal lipid-soluble chain-breaking antioxidants in biological membranes and lipoproteins. α-Tocopherol (1) and, to a lesser extent, λ-tocopherol (2) constitute an essential component of cellular defense against endogenous and exogenous oxidants.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Log in via an institution
Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 129.00
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 169.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD 169.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  • Bisby, R. H., and Parker, A. W., 1995, Reaction of ascorbate with the a-tocopheroxyl radical in micellar and bilayer membrane systems, Arch. Biochem. Biophys. 317:170–178.

    Article  PubMed  CAS  Google Scholar 

  • Bowry, V. W., and Stocker, R., 1993, Tocopherol-mediated peroxidation. The prooxidant effect of vitamin E on the radical-initiated oxidation of human low-density lipoprotein, J. Am. Chem. Soc. 115:6029–6044.

    Article  CAS  Google Scholar 

  • Bowry, V. W., Mohr, D., Cleary, J., and Stocker, R., 1995, Prevention of tocopherol-mediated peroxidation in ubiquinol-10-free human low density lipoprotein, J. Biol. Chem. 270:5756–5763.

    Article  PubMed  CAS  Google Scholar 

  • Burton, G. W., and Ingold, K. U., 1981, Autoxidation of biological molecules. 1. The antioxidant activity of vitamin E and related chain-breaking phenolic antioxidants in vitro, J. Am. Chem. Soc. 103:6472–6477.

    Article  CAS  Google Scholar 

  • Burton, G. W., and Ingold, K. U., 1986, Vitamin E: Application of the principles of physical organic chemistry to the exploration of its structure and function, Acc. Chem. Res. 19:194–201.

    Article  CAS  Google Scholar 

  • Burton, G. W., Doba, T., Gabe, E. J., Hughes, L., Lee, F. L., Prasad, L., and Ingold, K. U., 1985, Autoxidation of biological molecules. 4. Maximizing the antioxidant activity of phenols, J. Am. Chem. Soc. 107:7053–7065.

    Article  CAS  Google Scholar 

  • Burton, G. W., Wronska, U., Stone, L., Foster, D. O., and Ingold, K. U., 1990, Biokinetics of dietary RRR-alpha-tocopherol in the male guinea pig at three dietary levels of vitamin C and two levels of vitamin E. Evidence that vitamin C does not “spare” vitamin E in vivo, Lipids 25:199–210.

    Article  PubMed  CAS  Google Scholar 

  • Chan, A. C., Tran, K., Raynor, T., Ganz, P. R., and Chow, C. K., 1991, Regeneration of vitamin E in human platelets, J. Biol Chem. 266:17290–17295.

    PubMed  CAS  Google Scholar 

  • Chow, C. K., Draper, H. H., Csallany, A. S., and Chiu, M., 1967, The metabolsim of C14-alpha-tocopheryl quinone and C14-alpha-tocopheryl hydroquinone, Lipids 2:390–396.

    Article  PubMed  CAS  Google Scholar 

  • Christen, S., Woodall, A. A., Shigenaga, M. K., Southwell-Keely, P. T., Duncan, M. W., and Ames, B. N., 1997, gamma-Tocopherol traps mutagenic electrophiles such as NOX and complements α-tocopherol: Physiological implications, Proc. Natl. Acad. Sci. USA 94:3217–3222.

    Article  PubMed  CAS  Google Scholar 

  • Clough, R. L., Yee, B. G., and Foote, C. S., 1979, Chemistry of singlet oxygen. 30. The unstable primary product of tocopherol photooxidation, J. Am. Chem. Soc. 101:683–686.

    Article  CAS  Google Scholar 

  • Cooney, R. V., Harwood, P. J., Franke, A. A., Narala, K., Sundstrom, A. K., Berggren, P. O., and Mordan, L. J., 1995, Products of gamma-tocopherol reaction with NO2 and their formation in rat insulinoma (RINm5F) cells, Free Radic. Biol. Med. 19:259–269.

    Article  PubMed  CAS  Google Scholar 

  • Csallany, A. S., and Ha, Y. L., 1992, α-Tocopherol oxidation mediated by Superoxide anion. I. Reactions in aprotic and protic conditions, Lipids 27:195–200.

    Article  PubMed  CAS  Google Scholar 

  • d’Ischia, M., and Novellino, L., 1996, Nitric oxide-induced oxidation of α-tocopherol, Bioorg. Med. Chem. 4:1747–1753.

    Article  PubMed  Google Scholar 

  • d’Ischia, M., Costantini, C., and Prota, G., 1991, Dye-sensitized photooxidation of vitamin E revisited. New 7-oxaspiro[4.5]dec-1-ene-3,6-dione products by oxygenation and ring contraction of α-tocopherol, J. Am. Chem. Soc. 113:8353–8356.

    Article  Google Scholar 

  • de Groot, H., Hegi, U., and Sies, H., 1993, Loss of α-tocopherol upon exposure to nitric oxide or the syndonimine SIN-1, FEBS Lett. 315:139–142.

    Article  PubMed  Google Scholar 

  • Dix, T. A., and Marnett, L. J., 1985, Conversion of linoleic acid hydroperoxide to hydroxy, keto, epoxyhydroxy, and trihydroxy fatty acids by hematin, J. Biol. Chem. 260:5351–5357.

    PubMed  CAS  Google Scholar 

  • Durckheimer, W., and Cohen, L. A., 1964, The chemistry of 9-hydroxy-alpha-tocopherone, a quinone hemiacetal, J. Am. Chem. Soc. 86:4388–4393.

    Article  Google Scholar 

  • Fukuzawa, K., Ikebata, W., and Sohmi, K., 1993, Location, antioxidant and recycling dynamics of α-tocopherol in liposome membranes, J. Nutr. Sci. Vitaminol. 39:S9–S22.

    Article  PubMed  CAS  Google Scholar 

  • Giamvala, D. H., Church, D. F., and Pryor, W. A., 1986, Kinetics of ozonation. 4. Reactions of ozone with alpha-tocopherol and oleate and linoleate esters in carbon tetrachloride and in aqueous micellar solvents, J. Am. Chem. Soc. 108:6646–6651.

    Article  Google Scholar 

  • Glascott, P. A., Tsyganskaya, M., Gilfor, E., Zern, M., and Farber, J. L., 1996, The antioxidant function of the physiological content of vitamin C, Mol. Pharmacol. 50:994–999.

    PubMed  CAS  Google Scholar 

  • Gorbunov, N. V., Osipov, A. N., Sweetland, M. A., Day, B. W., Elsayed, N. M., and Kagan, V. E., 1997, NO-redox paradox: Direct oxidation of α-tocopherol and α-tocopherol mediated oxidation of ascorbate, Biochem. Biophys. Res. Commun. 219:835–841.

    Article  Google Scholar 

  • Grams, G. W., Eskins, K., and Inglett, G. E., 1971, Dye-sensitized photooxidation of alpha-tocopherol, J. Am. Chem. Soc. 93:866–868.

    Google Scholar 

  • Ha, Y. L., and Csallany, A. S., 1992, α-Tocopherol oxidation mediated by Superoxide anion. II. Identification of stable α-tocopheroi oxidation products, Lipids 27:201–205.

    Article  PubMed  CAS  Google Scholar 

  • Ham, A. J. L., and Liebler, D. C., 1995, Vitamin E oxidation in rat liver mitochondria, Biochemistry 34:5754–5761.

    Article  PubMed  CAS  Google Scholar 

  • Ham, A. J. L., and Liebler, D. C., 1997, Antioxidant reactions of vitamin E in the perfused rat liver: Product distribution and effect of dietary vitamin E supplementation, Arch. Biochem. Biophys. 339:157–164.

    Article  PubMed  CAS  Google Scholar 

  • Hayashi, T., Kanetoshi, A., Nakamura, M., Tamura, M., and Shirahama, H., 1992, Reduction of α-tocopherolquinone to α-tocopherolhydroquinone in rat hepatocytes, Biochem. Pharmacol. 44:489–493.

    Article  PubMed  CAS  Google Scholar 

  • Hogg, N., Darley-Usmar, V. M., Wilson, M. T., and Moncada, S., 1993, The oxidation of α-tocopherol in human low density lipoprotein by the simultaneous generation of superoxide and nitric oxide, FEBS Lett. 326:199–203.

    Article  PubMed  CAS  Google Scholar 

  • Hogg, N., Joseph, J., and Kalyanaraman, B., 1994, The oxidation of α-tocopherol and Trolox by peroxynitrite, Arch. Biochem. Biophys. 314:153–158.

    Article  PubMed  CAS  Google Scholar 

  • Hogg, N., Singh, R. J., Goss, P., and Kalyanaraman, B., 1996, The reaction between nitric oxide and α-tocopherol: A reappraisal, Biochem. Biophys. Res. Commun. 224:696–702.

    Article  PubMed  CAS  Google Scholar 

  • Hoglen, N. C., Waller, S. C., Sipes, I. G., and Liebler, D. C., 1997, Reactions of peroxynitrite with gamma-tocopherol, Chem. Res. Toxicol. 10:401–407.

    Article  PubMed  CAS  Google Scholar 

  • Kagan, V., Serbinova, E., and Packer, L., 1990a, Antioxidant effects of ubiquinones in microsomes and mitochondria are mediated by tocopherol recycling, Biochem. Biophys. Res. Commun. 169:851–857.

    Article  PubMed  CAS  Google Scholar 

  • Kagan, V. E., Serbinova, E. A., and Packer, L., 1990b, Recycling and antioxidant activity of tocopherol homologs of differing hydrocarbon chain lengths in liver microsomes, Arch. Biochem. Biophys. 282:221–225.

    Article  PubMed  CAS  Google Scholar 

  • Kaiser, S., Di Mascio, P., Murphy, M. E., and Sies, H., 1990, Physical and chemical scavenging of singlet molecular oxygen by tocopherols, Arch. Biochem. Biophys. 277:101–108.

    Article  PubMed  CAS  Google Scholar 

  • Kohar, I., Baca, M., Suarna, C., Stocker, R., and Southwell-Keely, P. T., 1995, Is α-tocopherol a reservoir for α-tocopherolhydroquinone? Free Radic. Biol. Med. 19:197–207.

    Article  PubMed  CAS  Google Scholar 

  • Kramer, K. A., and Liebler, D. C., 1997, UVB induced photooxidation of vitamin E, Chem. Res. Toxicol. 10:219–224.

    Article  PubMed  CAS  Google Scholar 

  • Liebler, D. C., 1993, The role of metabolism in the antioxidant function of vitamin E, Crit. Rev. Toxicol. 23:147–169.

    Article  PubMed  CAS  Google Scholar 

  • Liebler, D. C., 1994, Tocopherone and epoxytocopherone products of vitamin E oxidation, Meth. Enzymol. 234:310–316.

    Article  PubMed  CAS  Google Scholar 

  • Liebler, D. C., and Burr, J. A., 1992, Oxidation of vitamin E during iron-catalyzed lipid peroxidation: Evidence for electron-transfer reactions of the tocopheroxyl radical, Biochemistry 31:8278–8284.

    Article  PubMed  CAS  Google Scholar 

  • Liebler, D. C., and Burr, J. A., 1995, Antioxidant stoichiometry and the oxidative fate of vitamin E in peroxyl radical scavenging reactions, Lipids 30:789–793.

    Article  PubMed  CAS  Google Scholar 

  • Liebler, D. C., Kaysen, K. L., and Kennedy, T. A., 1989, Redox cycles of vitamin E: Hydrolysis and ascorbic acid dependent reduction of 8a-(alkyldioxy)tocopherones, Biochemistry 28:9772–9777.

    Article  PubMed  CAS  Google Scholar 

  • Liebler, D. C., Baker, P. F., and Kaysen, K. L., 1990, Oxidation of vitamin E: Evidence for competing autoxidation and peroxyl radical trapping reactions of the tocopheroxyl radical, J. Am. Chem. Soc. 112:6995–7000.

    Article  CAS  Google Scholar 

  • Liebler, D. G., Kaysen, K. L., and Burr, J. A., 1991, Peroxyl radical trapping and autoxidation reactions of alpha-tocopherol in lipid bilayers, Chem. Res. Toxicol. 4:89–93.

    Article  PubMed  CAS  Google Scholar 

  • Liebler, D. C., Matsumoto, S., Iltaka, Y., and Matsuo, M., 1993, Reactions of vitamin E and its model compound 2,2,5,7,8-pentamethylchroman-6-ol with ozone, Chem. Res. Toxicol. 6:69–74.

    Article  PubMed  CAS  Google Scholar 

  • Liebler, D. C., Burr, J. A., Philips, L., and Ham, A. J. L., 1996, Gas chromatography-mass spectrometry analysis of vitamin E and its oxidation products, Anal. Biochem. 236:27–34.

    Article  PubMed  CAS  Google Scholar 

  • Mackenzie, J. B., and Mackenzie, C. G., 1958, The effect of α-tocopherol, α-tocopherylhydroquinone and their esters on experimental muscular dystrophy in the rat, J. Nutr. 67:223–235.

    Google Scholar 

  • Mackenzie, J. B., and Mackenzie, C. G., 1960, The antisterility activity of alpha-tocohydroquinone in the female rat, J. Nutr. 72:322–324.

    PubMed  CAS  Google Scholar 

  • Maiorino, M., Coassin, M., Roveri, A., and Ursini, F., 1989, Microsomal lipid peroxidation: Effect of vitamin E and its functional interaction with phospholipid hydroperoxide glutathione peroxidase, Lipids 24:721–726.

    Article  PubMed  CAS  Google Scholar 

  • Matsuo, M., Matsumoto, S., and Iltaka, Y., 1987, Oxygenations of vitamin E (alpha-tocopherol) and its model compound 2,2,5,7,8-pentamethylchroman-6-ol in the presence of the Superoxide radical solubilized in aprotic solvents: Unique epoxidations and recyclizations, J. Org. Chem. 52:3514–3520.

    Article  CAS  Google Scholar 

  • Matsuo, M., Matsumoto, S., Iltaka, Y., and Niki, E., 1989, Radical scavenging reactions of vitamin E and its model compound, 2,2,5,7,8-pentamethylchroman-6-ol, in a tertbutylperoxyl radical generating system, J. Am. Chem. Soc. 111:7179–7185.

    Article  CAS  Google Scholar 

  • Mehlhorn, R. J., Sumida, S., and Packer, L., 1989, Tocopheroxyl radical persistence and tocopherol consumption in liposomes and in vitamin E-enriched rat liver mitochondria and microsomes, J. Biol. Chem. 264:13448–13452.

    PubMed  CAS  Google Scholar 

  • Miyazawa, T., Yamashita, T., and Fujimoto, K., 1992, Chemiluminescence detection of 8a-hydroperoxytocopherone in photooxidized α-tocopherol, Lipids 27:289–294.

    Article  PubMed  CAS  Google Scholar 

  • Moore, A. N. J., and Ingold, K. U., 1997, α-Tocopheryl quinone is converted into vitamin E in man, Free Radic. Biol. Med. 22:931–934.

    Article  PubMed  CAS  Google Scholar 

  • Nishikimi, M., Yamada, H., and Yagi, K., 1980, Oxidation by Superoxide of tocopherols dispersed in aqueous media with deoxycholate, Biochim. Biophys. Acta 627:101–108.

    Article  PubMed  CAS  Google Scholar 

  • Packer, J. E., Slater, T. F., and Willson, R. L., 1979, Direct observation of a free radical interaction between vitamin E and vitamin C., Nature 278:737–738.

    Article  PubMed  CAS  Google Scholar 

  • Packer, L., and Kagan, V. E., 1993, Vitamin E: The antioxidant harvesting center of membranes and lipoproteins, in Vitamin E in Health and Disease (L. Packer and J. Fuchs, eds.), pp. 179–192, Marcel Dekker, New York.

    Google Scholar 

  • Siegel, D., Bolton, E. M., Burr, J. A., Liebler, D. C., and Ross, D., 1997, The reduction of α-tocopherolquinone by human NAD(P)H:quinone oxidoreductase: The role of α-tocopherolhydroquinone as a cellular antioxidant, Mol. Pharmacol. 52:300–305.

    PubMed  CAS  Google Scholar 

  • Skinner, W. A., and Alqaupovic, P., 1963, Oxidation products of vitamin E and its model 6-hydroxy-2,2,5,7,8-pentamethylchroman. V. Studies of the products of alkaline ferricyanide oxidation, J. Org. Chem. 28:2854–2858.

    Article  CAS  Google Scholar 

  • Suarna, C., and Southwell-Keely, P. T., 1988, New oxidation products of alpha-tocopherol, Lipids 23:137–139.

    Article  CAS  Google Scholar 

  • Suarna, C., Craig, D. C., Cross, K. J., and Southwell-Keely, P. T., 1988, Oxidations of vitamin E (alpha-tocopherol) and its model compound 2,2,5,7,8-pentamethyl-6-hydroxychroman. A new dimer, J. Org. Chem. 53:1281–1284.

    Article  CAS  Google Scholar 

  • Suarna, C., Baca, M., and Southwell-Keely, P. T., 1992, Oxidation of the α-tocopherol model compound 2,2,5,7,8-pentamethyl-6-chromanol in the presence of alcohols, Lipids 27:447–453.

    Article  CAS  Google Scholar 

  • Winterle, J., Dulin, D., and Mill, T., 1984, Products and stoichiometry of reaction of vitamin E with alkylperoxy radicals, J. Org. Chem. 49:491–495.

    Article  CAS  Google Scholar 

  • Yamauchi, R., Matsui, T., Kato, K., and Ueno, Y., 1989a, Reaction of alpha-tocopherol with 2,2′-azobis(2,4-dimethylvaleronitrile) in benzene, Agric. Biol. Chem. 12:3257–3262.

    Article  Google Scholar 

  • Yamauchi, R., Matsui, T., Satake, Y., Kato, K., and Ueno, Y., 1989b, Reaction products of alpha-tocopherol with a free radical initiator, 2,2′-azobis(2,4-dimethylvaleronitrile), Lipids 24:204–209.

    Article  PubMed  CAS  Google Scholar 

  • Yamauchi, R., Matsui, T., Kato, K., and Ueno, Y., 1990, Reaction products of α-tocopherol with methyl linoleate-peroxyl radicals, Lipids 25:152–158.

    Article  CAS  Google Scholar 

  • Yamauchi, R., Yagi, Y., and Kato, K., 1994, Isolation and characterization of addition products of α-tocopherol with peroxyl radicals of dilinoleoylphosphatidylcholine in liposomes, Biochim. Biophys. Acta 1212:43–49.

    Article  PubMed  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Pharmacology and Toxicology, College of Pharmacy, University of Arizona, Tucson, Arizona, 85721-0207, USA

    Daniel C. Liebler

Authors
  1. Daniel C. Liebler
    View author publications

    You can also search for this author in PubMed Google Scholar

Editor information

Editors and Affiliations

  1. King’s College London, University of London, London, UK

    Peter J. Quinn

  2. Department of Environmental and Occupational Health, and Department of Pharmacology, University of Pittsburgh, Pittsburgh, Pennsylvania, USA

    Valerian E. Kagan

Rights and permissions

Reprints and permissions

Copyright information

© 1998 Springer Science+Business Media New York

About this chapter

Cite this chapter

Liebler, D.C. (1998). Antioxidant Chemistry of α-Tocopherol in Biological Systems. In: Quinn, P.J., Kagan, V.E. (eds) Fat-Soluble Vitamins. Subcellular Biochemistry, vol 30. Springer, Boston, MA. https://doi.org/10.1007/978-1-4899-1789-8_13

Download citation

  • DOI: https://doi.org/10.1007/978-1-4899-1789-8_13

  • Publisher Name: Springer, Boston, MA

  • Print ISBN: 978-1-4899-1791-1

  • Online ISBN: 978-1-4899-1789-8

  • eBook Packages: Springer Book Archive

Publish with us

Policies and ethics

Search

Navigation