Flavonoid Sulfation: Phytochemistry, Enzymology and Molecular Biology

  • Luc Varin
Part of the Recent Advances in Phytochemistry book series (RAPT, volume 26)


Sulfate ester formation is the most recently recognized conjugation reaction of flavonoid compounds. Although the first sulfated compound was reported as early as 1937,1 it was not until 1975 that flavonoid sulfate esters have been considered to be of common occurrence in a number of plant families.2-5 In a recent review,6 however, more than 100 sulfated flavonoids have been reported in 250 species belonging to 17 dicotyledon and 16 monocotyledon families. Most of these compounds are mono-to tetrasulfate esters of common hydroxyflavones and hydroxyflavonols or their methyl ethers, and less commonly of their glucosylated derivatives. In some flavonoid glycosides, the sulfate group may be linked to the 3- or 6-position of the sugar moiety. Because of instability of the sulfate ester bond, especially in acid media, many sulfated flavonoids may have escaped detection, and the sulfate esters of flavonoid classes other than flavones and flavonols have yet to be described.


Sulfate Group Sugar Moiety Sulfate Ester Sulfur Trioxide Sulfate Donor 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    Kawaguchi, R., Kim, K.W. 1937. The constituents of Persicaria hydropiper. J. Pharm. Sci. Japan 57:767–769.Google Scholar
  2. 2.
    Harborne, J.B. 1975. Flavonoid sulphates: a new class of sulphur compounds in higher plants. Phytochemistry 14:1147–1155.CrossRefGoogle Scholar
  3. 3.
    Harborne, J.B. 1977. Flavonoid sulphates: a new class of natural products of ecological significance in plants. In: Progress in Phytochemistry, Vol. 4. (L. Reinhold, J.B. Harborne, T. Swain, eds.) Pergamon Press, New York, pp. 189–208.Google Scholar
  4. 4.
    Harborne, J.B., Williams, C.A. 1982. Flavone and flavonol glycosides. In: The Flavonoids: Advances in Research. (J.B. Harborne, T.J. Mabry, eds.) Chapman and Hall, pp. 261–312.Google Scholar
  5. 5.
    Timmermann, B.N. 1980. Phytochemical investigations of the genus Brickellia (Compositae) emphasizing flavonoids. Ph.D. Thesis, University of Texas, Austin, TX.Google Scholar
  6. 6.
    Barron, D., Varin, L., Ibrahim, R.K., Harborne, J.B., Williams, A.C. 1988. Sulphated flavonoids-an update. Phytochemistry 27:2375–2395.CrossRefGoogle Scholar
  7. 7.
    MULDER, G.J. 1981. Sulfation of Drugs and Related Compounds. CRC Press, Boca Raton, FL.Google Scholar
  8. 8.
    Schildknecht, H., Meier-Augenstein, W. 1990. The Pulvinus: Motor Organ For Leaf Movement. (R.L. Satter, H.L. Gorton and T.C. Vogelmann, eds.) American Society of Plant Physiologists, Rockville, MD. pp. 205–213.Google Scholar
  9. 9.
    Truchet, G., Roche, P., Lerouge, P., Vasee, J., Camut, S., Debilly, F., Prome, J.C., Denarié, J. 1991. Sulphated lipooligosaccharide signals of Rhizobium meliloti elicit root nodule organogenesis in alfalfa. Nature 351:670–673.CrossRefGoogle Scholar
  10. 10.
    Barron, D. 1987. Advances in phytochemistry, organic synthesis, spectral analysis and enzymatic synthesis of sulfated flavonoids. Ph.D. Thesis, Concordia University, Montréal.Google Scholar
  11. 11.
    Varin, L., Barron, D., Ibrahim, R.K. 1986. Identification and biosynthesis of sulfated and glucosylated flavonoids in Flaveria bidentis. Z. Naturforsch. 41c:813–819.Google Scholar
  12. 12.
    Barron, D., Ibrahim, R.K. 1987. 6-Methoxykaempferol 3-monosulfates from Flaveria chloraefolia. Phytochemistry 26:2085–2088.CrossRefGoogle Scholar
  13. 13.
    Barron, D., Ibrahim, R.K. 1987. Quercetin and patuletin 3,3’disulfates from Flaveria chloraefolia. Phytochemistry 26:1181–1184.CrossRefGoogle Scholar
  14. 14.
    Nawwar, M.A.M., Buddrus, J. 1981. A gossypetin glucuronide sulfate from the leaves of Malva sylvestris. Phytochemistry 20:2446–2448.CrossRefGoogle Scholar
  15. 15.
    Tomas-Barberan, F.A., Harborne, J.B., Self, R. 1987. Twelve 6-oxygenated flavone sulphates from Lippia nodiflora and L. canescens. Phytochemistry 26:2281–2285.CrossRefGoogle Scholar
  16. 16.
    Mues, R., Timmermann, B.N., Ohno, M., Mabry, T.J. 1979. 6-Methoxyflavonoids from Brickellia californica. Phytochemistry 18:1379–1383.CrossRefGoogle Scholar
  17. 17.
    Barron, D., Colebrook, L., Ibrahim, R.K. 1986. An equimolar mixture of quercetin 3-sulfate and patuletin 3-sulfate from Flaveria chloraefolia. Phytochemistry 25:1719–1721.CrossRefGoogle Scholar
  18. 18.
    Williams, C.A., Harborne, J.B., Clifford, H.T. 1973. Negatively charged flavones and tricin as chemosystematic markers in the Palmae. Phytochemistry 12:2417–2430.CrossRefGoogle Scholar
  19. 19.
    Harborne, J.B., ed. 1989. Methods in Plant Biochemistry. Vol. 1. Academic Press, New York.Google Scholar
  20. 20.
    Markham, K.R. 1982. Techniques of Flavonoid Identification. Academic Press, London.Google Scholar
  21. 21.
    Barron, D., Ibrahim, R.K. 1988. Synthesis of flavonoid sulfates. II. The use of aryl sulfatase in the synthesis of flavonol 3-sulfates. Z. Naturforsch. 43c:625–630.Google Scholar
  22. 22.
    Barron, D., Ibrahim, R.K. 1988. Hydrochloric acid and aryl sulfatase as reagents for UV spectral detection of 3- and 4’-sulfated flavonoids. Phytochemistry 27:2335–2338.CrossRefGoogle Scholar
  23. 23.
    Barron, D., Ibrahim, R.K. 1988. Synthesis of flavonoid sulfates. III. Synthesis of 3’,4’-o-disulfates using sulfur trioxide-trimethylamine complex, and of 3-sulfates using aryl sulfatase. Z. Naturforsch. 43c:631–635.Google Scholar
  24. 24.
    Barron, D., Ibrahim, R.K. 1987. Synthesis of flavonoid sulfates. I. Stepwise sulfation of positions 3, 7, and 4’ using N,N’-dicyclohexylcarbodiimide and tetrabutylammonium hydrogen sulfate. Tetrahedron 43:5197–5202.CrossRefGoogle Scholar
  25. 25.
    Hannoufa, A., Varin, L., Ibrahim, R.K. 1991. Spatial distribution of flavonoid conjugates in relation to glucosyltransferase and sulfotransferase activities in Flaveria bidentis. Plant Phys. 97:259–263.CrossRefGoogle Scholar
  26. 26.
    Roy, A.B. 1981. Sulfotransferases. In: Sulfation of Drugs and Related Compounds. (G.J. Mulder, ed.) CRC Press, Boca Raton, FL, pp. 83–130.Google Scholar
  27. 27.
    Hobkirk, R. 1985. Steroid sulfotransferases and steroid sulfate sulfatases: characteristics and biological roles. Can. J. Biochem. Cell Biol. 63:1127–1144.PubMedCrossRefGoogle Scholar
  28. 28.
    Varin, L., Barron, D., Ibrahim, R.K. 1987. Enzymatic synthesis of sulfated flavonols in Flaveria spp. Phytochemistry 26:135–138.CrossRefGoogle Scholar
  29. 29.
    Varin, L. 1990. Enzymology of flavonoid sulfation: purification, characterization and molecular cloning of a number of flavonol sulfotransferases from Flaveria spp. Ph.D. Thesis, Concordia University, Montréal.Google Scholar
  30. 30.
    Varin, L., Barron, D., Ibrahim, R.K. 1987. Enzymatic assay for flavonol sulfotransferase. Anal. Biochem. 161:176–180.Google Scholar
  31. 31.
    Varin, L., Ibrahim, R.K. 1989. Partial purification and characterization of three flavonol-specific sulfotransferases from Flaveria chloraefolia. Plant Physiol. 90:977–981.PubMedCrossRefGoogle Scholar
  32. 32.
    Varin, L., Ibrahim, R.K. 1991. Partial purification and some properties of flavonol 7-sulfotransferase from Flaveria bidentis. Plant Physiol. 95:1254–1258.PubMedCrossRefGoogle Scholar
  33. 33.
    Powell, G.M., Olavesen, A.H. 1981. The fate of sulfate esters in vitro. In: Sulfation of Drugs and Related Compounds (GJ. Mulder, ed.) CRC Press, Boca Raton, FL, pp. 187–212.Google Scholar
  34. 34.
    Dodgson, K.S., White, G.F., Fitzgerald, J.W. 1982. The Arylsulfatases. In: Sulfatases of Microbial Origin. (K.S. Dodgson, ed.) CRC Press, Boca Raton, FL, pp. 103–168.Google Scholar
  35. 35.
    Varin, L., Ibrahim, R.K. 1992. Novel flavonol 3-sulfotransferase: purification, kinetic properties and partial amino acid sequence. J. Biol. Chem. 267:1858–1863.PubMedGoogle Scholar
  36. 36.
    Falany, C.N., Vazquez, M.E., 1989. Purification and characterization of human liver dehydroepiandrosterone sulfotransferase. Biochem. J. 260:641–646.PubMedGoogle Scholar
  37. 37.
    Ibrahim, R.K., Deluca, V., Khouri, H., Latchinian, L., Brisson, L., Barron, D. Charest, P.M. 1987. Enzymology and compartmentation of polymethylated flavonol glucosides in Chrysosplenium americanum. Phytochemistry 26:1237–1245.CrossRefGoogle Scholar
  38. 38.
    Ogura, K., Kajita, J., Narihata, H., Watabe, T., Ozawa, S., Nagata, K., Yamazoe, Y. Kato, R. 1989. Cloning and sequence analysis of a rat liver cDNA encoding hydroxysteroid sulfotransferase. Biochem. Biophys. Res. Commun. 165:168–174.Google Scholar
  39. 39.
    S., Nagata, K., Yamazoe, Y. Kato, R. 1990. cDNA cloning of the hydroxysteroid sulfotransferase ST sharing a strong homology in amino acid sequence with the senescence marker protein SMP-2 in rat livers. Biochem. Biophys. Res. Commun. 166:1494–1500.Google Scholar
  40. 40.
    Nash, A., Glenn, W.K., Moore, S.S., Kerr, J., Thompson, A.R., Thompson, E.O.P. 1988. Oestrogen sulfotransferase: Molecular cloning and sequencing of cDNA for the bovine placental enzyme. Aust. J. Biol. Sci. 41:507–516.PubMedGoogle Scholar
  41. 41.
    Falany, C.N., Vazquez, M.E., Heroux, J.A. Roth, J.A. 1990. Purification and characterization of human liver phenol-sulfating phenol sulfotransferase. Arch. Biochem. Biophys. 278:312–318.Google Scholar
  42. 42.
    Varin, L., Deluca, V., Ibrahim, R.K., Brisson, N. 1992. Molecular characterization of two plant flavonol sulfotransferases Proc. Natl. Acad. Sci. (USA) (in press).Google Scholar
  43. 43.
    Chatterjee, B., Majumdar, D., Ozbilen, O., Murty, R., Roy, A.K. 1987. Molecular cloning and characterization of cDNA for androgen-repressible rat liver protein SMP-2’ J. Biol. Chem. 262:822–825.Google Scholar
  44. 44.
    Lefebvre, D.D. 1990. Expression of mammalian metallothionein suppresses glucosinolate synthesis in Brassica campestris. Plant Physiol. 93:522–524.PubMedCrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 1992

Authors and Affiliations

  • Luc Varin
    • 1
  1. 1.Department of BiochemistryUniversity of MontréalMontréalCanada

Personalised recommendations