Skip to main content

Advertisement

Official Journal of the Japan Wood Research Society

Journal of Wood Science Cover Image
We’d like to understand how you use our websites in order to improve them. Register your interest.

Antioxidative activity of tree phenolic constituents 1: Radical-capturing reaction of flavon-3-ols with radical initiator

Abstract

The present work was undertaken from the standpoint of radical-capturing ability with regard to the antioxidative ability of flavonoids, especially flavonols distributed widely in woody plants. In regard to the flavonols, six methyl derivatives were initially prepared from quercetin and its litinoside. Their radical-capturing constants were determined strictly by the stopped-flow spectroscopic method. It was proved that the radical-capturing ability of quercetin mainly involves the vicinal C3. and C4, hydroxyl groups and the C3 hydroxyl group. To clarify the reaction mechanism begun at the C3 hydroxyl group of quercetin, 5,7,3′,4′-tetramethylquercetin (TMQ), flavon-3-ol (F30) and so on were treated with 2,2′-azo-bis-(2,4-dimethylvaleronitrile) (AMVN). Six products (1–6) containing one depside and its two hydrolytic products, two valeronitrile adducts, and others were isolated from the reaction mixture of TMQ and their structures determined by instrumental analyses. Similarly, F30 gave four products, 7–10, which corresponded to the above products 1–3 and 5 (one depside, its two hydrolytic products, and one adduct), respectively. 3,5,7,3′,4′-Pentamethylquercetin (PMQ) and flavon-3-O-methylate (F3M) gave no products. The quantitative change of the products with reaction time was determined spectroscopically. An initial reaction pathway for the radical-capturing reaction of flavon-3-ols with AMVN was proposed based on the products and their amounts. The main route — formation of depside and its hydrolytic products via ketohydroperoxide (3″) or ketohydroperoxy radical (4″) - was similar to that of the oxidation reaction of quercetin with quercetinase and light.

References

  1. 1.

    Frankle EN (1991) Recent advances in lipid oxidation. J Sci Food Agric 54:495–511

  2. 2.

    Hamilton RJ, et al. (1997) Chemistry of free radicals in lipids. Food Chem 60:193–199

  3. 3.

    Uchiyama M, Matsuo M, Sagai M (1988) Peroxidized lipids and living body (in Japanese). Gakkai Shuppan Center, Tokyo, pp 79–313

  4. 4.

    Terao J (1993) Effects of a-tocopherol (in Japanese). Shokuhin to Kaihatsu 28:10–13

  5. 5.

    Pryor WA, Strickland T, Church DF (1988) Comparison of the efficiencies of several natural and synthetic antioxidants in aqueous sodium dodecyl sulfate micelle solution. J Am Chem Soc 110:2224–2229

  6. 6.

    Rios JL, et al. (1992) Antioxidant activity of flavonoids fromSidertis javalambrensis. Phytochemistry 31:1947–1950

  7. 7.

    Kikuzaki H, Kakatani N (1993) Antioxidant effects of some ginger constituents. J Food Sci 58:1407–1410

  8. 8.

    Rabe C, et al. (1994) Phenolic metabolites from rooibos tea (Aspalathus linearis). Phytochemistry 35:1559–1565

  9. 9.

    Javanovic SV, et al. (1994) Flavonoids as antioxidants. J Am Chem Soc 116:4846–4851

  10. 10.

    Igile GO, et al. (1994) Flavonoids fromVernonia amygdalina and their antioxidant activities. J Agric Food Chem 42:2445–2448

  11. 11.

    Vinson JA, Houtz B (1995) Phenol antioxidant index: comparative antioxidant effectiveness of red and white wines. J Agric Food Chem 43:401–403

  12. 12.

    Marinova EM, Yanishlieva N (1996) Antioxidative activity of phenolic acids on triacylglycerols and fatty acid methyl ethers from olive oil. Food Chem 56:139–145

  13. 13.

    Ogata M, et al. (1997) Antioxidant activity of magnolol, hinokiol and related phenolic compound. J Am Oil Chem Soc 74:557–562

  14. 14.

    Cuvelier M, Richard H, Berset C (1992) Comparison of the antioxidative activity of some acid phenols. Biosci Biotech Biochem 56:324–325

  15. 15.

    Maoka T, et al. (1997) Comparison of antioxidative activity of phenolic compounds inBoreava orientalis and their related compound. J Jpn Oil Chem Soc 46:1399–1402

  16. 16.

    Kawagishi S (1996) Research method of bioactive compounds in foodstuffs (in Japanese). Gakkai Shuppan Center, Tokyo, pp 722

  17. 17.

    Kawase S, et al. (1993) Antioxidative activity of asadanin and its homologs (in Japanese). In: Abstracts of the 43rd annual meeting of the Japan Wood Research Society, p 344

  18. 18.

    Kawase S, et al. (1994) Study on the antioxidative activity of tree phenols. I. Comparison of antioxidative ability by improved Wills method (in Japanese). In: Abstracts of the 44th annual meeting of the Japan Wood Research Society, p 257

  19. 19.

    Zhongli C, Yongkc H, Jilan W (1996) Study of baicalin scavenging hydroxyethyl peroxy radicals by radiolysis of aerated ethanolbaicalin system. Radiat Phys Chem 47:869–871

  20. 20.

    Jovanovic SV, et al. (1996) Reduction potentials of flavonoid and model phenoxyl radicals: which ring in flavonoids is responsible for antioxidant activity? J Chem Soc Perkin Trans 2:2497–2504

  21. 21.

    Gadow A, Joubert E, Hausmann CF (1997) Comparison of the antioxidative activity of aspalthin with that of other plant phenols of Rooibos tea (Aspalathus linearis). J Agric Food Chem 45:632–638

  22. 22.

    Nagaratnam P, Ratty AK (1986) Effects of flavonoids on induced non-enzymic lipid peroxidation. In: Cody V, et al (eds) Plant flavonoids in biology and medicines. Liss, New York, pp 243–247

  23. 23.

    Frankel EN, et al. (1994) Interfacial phenomena in the evaluation of antioxidant, bulk oils vs emulsions. J Agric Food Chem 42:1054–1059

  24. 24.

    Mukai K, et al. (1986) Stopped-flow investigation of antioxidant activity of tocopherols. Bull Chem Soc Jpn 59:3113–3116

  25. 25.

    Mukai K, Okabe K, Hosoe H (1989) Synthesis and stopped-flow investigation of antioxidant activity of tocopherol. J Org Chem 54:557–560

  26. 26.

    Kawase S, et al. (1994) Study on the antioxidative activity of tree phenols 2 (in Japanese). In: Abstracts of the 44th annual meeting of the Japan Wood Research Society, p 258

  27. 27.

    Kawase S, et al. (1995) Study on the antioxidative activity of tree phenols 3 (in Japanese). In: Abstracts of the 45th annual meeting of the Japan Wood Research Society, p 409

  28. 28.

    Harborne JB (1989) Natural products of woody plants I. In: Rowe JW (ed) Springer, Berlin, pp 533–570

  29. 29.

    Wollenweber E (1993) Flavones and flavonols. In: Harborne JB (ed) The flavonoid. Chapman & Hall, London, pp 259–335

  30. 30.

    Yamauchi R, et al. (1990) Reaction product of a-tocopherol with methyl linoleate-peroxyradicals. Lipid 25:152–158

  31. 31.

    Koga T, Terao J (1995) Phospholipids increase radical-scavenging activity of vitamin E in a bulk oil model system. J Agric Food Chem 43:1450–1454

  32. 32.

    Yamauchi R, Kato K, Ueno Y (1995) Free-radical scavenging reactions of a-tocopherol during the antioxidation of methyl finoleate in bulk phase. J Agric Good Chem 43:1455–1461

  33. 33.

    Blois M (1958) Antioxidant determinations by the use of a stable free radical. Nature 4617:1199–1200

  34. 34.

    Kyogoku T, et al. (1996) Study on the antioxidative activity of tree phenols. 4. (in Japanese). In: Abstracts of the 46th annual meeting of the Japan Wood Research Society, p 421

  35. 35.

    Kyogoku T, et al. (1997) Study on the antioxidative activity of tree phenols. 5. (in Japanese). In: Abstracts of the 47th annual meeting of the Japan Wood research Society, p 415

  36. 36.

    Matsuura T, Matsushima H, Nakashima R (1970) Photoinduced reactions. XXXV1. Photosensitized oxygenation of 3-hydroxyflavones as a nonenzymatic model for quercetinase. Tetrahedron 26:435–443

  37. 37.

    Hirose Y, Fujita T, Nakayama M (1996) Reaction products of quercetin with radical initiator (in Japanese). In: Abstracts of the 35th annual meeting of the Japan Oil Chemistry Society, p 146

  38. 38.

    Feigl F (1966) 1,2-Dioxo compounds. In: Spot tests in organic analysis. Elsevier, Amsterdam, pp 325–327

  39. 39.

    Terao J, et al. (1981) Structural analysis of hydroperoxide formed by oxidation of phosphatidylcholine with singlet oxygen. Lipid 16:427–432

  40. 40.

    Hirose Y, Yamaoka H, Nakayama M (1991) A novel quasi-dimeric oxidation product of (+)-catechin from lipid peroxidation. J Am Oil Chem Soc 68:131–132

  41. 41.

    Hirose Y, et al. (1992) A novel intramolecular cyclization product of (+)-catechin under radical reaction. Chem Lett 2361–2362

  42. 42.

    Nakayama M, Hirose Y (1994) Antioxidant activity of catechins and an approach to antioxidant mechanism based on the oxidation product (in Japanese). Foods Food Ingred J Jpn 161:4–12

Download references

Author information

Affiliations

Authors

Corresponding author

Correspondence to Hideo Ohashi.

Additional information

Part of this paper was presented at the 46th and 47th annual meetings of the Japan Wood Research Society, Kumamoto and Kouchi, April 1996 and 1997

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Ohashi, H., Kyogoku, T., Ishikawa, T. et al. Antioxidative activity of tree phenolic constituents 1: Radical-capturing reaction of flavon-3-ols with radical initiator. J Wood Sci 45, 53–63 (1999). https://doi.org/10.1007/BF00579524

Download citation

Key words

  • Antioxidative activity
  • Radical-capturing ability
  • Flavonol
  • 2,2′-Azo-bis-(2,4-dimethylvaleronitrile) (AMVN)
  • Reaction mechanism