Skip to main content
SpringerLink
Log in

Structure of Procyanidin Oligomers Isolated From Grape Seeds in Relation to Some of their Chemical Properties

  • Chapter
Plant Polyphenols

Part of the book series: Basic Life Sciences ((BLSC,volume 59))

Abstract

A micro-method using thiolysis followed by HPLC monitoring of the degradation products was developed to determine the structure of procyanidin oligomers available in small quantities (≤ 0.1 mg). It was successfully applied to a series of procyanidins isolated from grape seeds, allowing the identification of procyanidins dimers B5 to B8 linked by C4 → C6 bonds, six procyanidin trimers with C4 → C8 and C4 → C6 linkages, and six galloylated dimers and trimers, along with the four C4 → C8 linked dimers, Bl to B4. The influence of procyanidin structural variations on their interactions with proteins, free radical scavenging effect, and oxidation was studied using these compounds. Protein-procyanidin interactions increased with the degree of polymerization, the number of galloyl substituents, and the extent of C4→ C6 linkages. Galloylation increased scavenger capacity of procyanidin dimers for Superoxide anion (O2 -•) and hydroxyl (su•OH) radicals. The type of C → C linkage and the esterification position were also important. None of the molecules tested was oxidizable by grape polyphenoloxidase, but they were all oxi-dized by the enzymically generated caffeoyl tartaric acid o-quinones. In addition, galloylated procyanidins seemed to undergo condensation reactions faster than the corresponding non-galloylated ones, even though their rate of oxidation was similar.

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

Access this chapter

Log in via an institution

Subscribe and save

Springer+ Basic
$34.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or eBook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 259.00
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 329.00
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD 329.99
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.

Similar content being viewed by others

References

  1. Bourzeix, M. The leucoanthocyanins of grapes and white wines. C.R. Acai. Agric. Fr. 56:983 (1970).

    CAS  Google Scholar 

  2. Weinges, K.; Piretti, M.V. Isolation of procyanidin Bl from grapes. Liebigs Ann. Chem. 748:218 (1971).

    Article  CAS  Google Scholar 

  3. Lea, A.G.H.; Bridle, P.; Timberlake, C.F.; Singleton, V.L. The procyanidins of white grapes and wines. Am. J. Enol. Vitic. 30:289 (1979).

    CAS  Google Scholar 

  4. Czochanzka, Z.; Foo, L.Y.; Porter, L.J. Compositional changes in lower molecular weight flavans during grape maturation. Phytochemistry 18:1819 (1979).

    Article  Google Scholar 

  5. Haslam, E. In vino veritas: oligomeric procyanidins and the ageing of red wines. Phytochtmistry 19:2577 (1980).

    Article  CAS  Google Scholar 

  6. Singleton, V.L.; Noble, A.C. Bitterness and astringency of phenolic fractions in wine. J. Agric. Food Chem. 28:675 (1980).

    Article  Google Scholar 

  7. Romeyer, F.M.; Macheix, J.J.; Sapis, J.C. Changes and importance of oligomeric procyanidins during maturation of grape seeds. Phytochemistry 25:219 (1986).

    Article  CAS  Google Scholar 

  8. Bourzeix, M.; Weyland, D.; Heredia, N. Etude des catéchines et des procyanidols de la grappe de raisin, du vin et d’autres dérivés de la vigne. Bull. O.I.V. 669:1171 (1986).

    Google Scholar 

  9. Lee, C.Y.; Jaworski, A.W. Phenolic compounds in white grapes grown in New York. Am. J. Enol. Vitic. 38:277 (1987).

    CAS  Google Scholar 

  10. Boukharta, M. Etude des flavonoides de Vitis vinifera: structure des proanthocyanidines des pépins de raisin, des sarments et des feuilles de vigne. PhD. Dissertation, I.N.P.L., Nancy, France (1988).

    Google Scholar 

  11. Oszmianski, J.; Sapis, J.C. Fractionation and identification of some low molecular weight grape seed phenolics. J. Agric. Food Chem. 37:1293 (1989).

    Article  CAS  Google Scholar 

  12. Lee, C.Y.; Jaworski, A.W. Identification of some phenolics in white grapes. Am. J. Enol. Vitic. 41:87 (1990).

    CAS  Google Scholar 

  13. White, T. Tannins: their occurrence and significance. J. Sci. Food Agric. 8:377 (1957).

    Article  CAS  Google Scholar 

  14. Gramshaw, J.W. Phenolic constituents of beer and brewing materials. The role of polyphenols in the formation of non-biological haze. J. Inst. Brew. 73:455 (1967).

    Article  CAS  Google Scholar 

  15. Eastmond, R; Gardner, R. J. Effect of various polyphenols on the rate of haze formation in beer. J. Inst. Brew. 80:192 (1974).

    Article  CAS  Google Scholar 

  16. Simpson, R.F. Factors affecting oxidative browning of white wine. Vitis 21:233 (1982).

    CAS  Google Scholar 

  17. Asano, K.; Ohtsu, K.; Shinagawa, K.; Hashimoto, N. Affinity of proanthocyanidins and their oxidation products for haze-forming proteins of beer and the formation of chill haze. Agric. Biol. Chem. 48:1139 (1984).

    Article  CAS  Google Scholar 

  18. Beart, E.; Lilley, T.L.; Haslam, E. Polyphenol interactions. Part 2. Covalent binding of procyanidins to proteins during acid-catalyzed decomposition; observations on some polymeric proanthocyanidins. J. Chem. Soc., Perkin Trans 2:1439 (1985).

    Google Scholar 

  19. Cheynier V.; Rigaud, J.; Souquet, J.M.; Barillore, J.M.; Moutounet, M. Effect of pomace contact and hyperoxidation on the phenolic composition and quality of Grenache and Chardonnay wines. Am. J. Enol. Vitic. 40:36 (1989).

    Google Scholar 

  20. Bate-Smith, E.C. Astringency in foods. Food 23:124 (1954).

    CAS  Google Scholar 

  21. Joslyn, M.A.; Goldstein, J.L. Astringency of fruit and fruit products in relation to phenolic contents. Adv. Food Res. 13:179 (1964).

    Article  PubMed  CAS  Google Scholar 

  22. Bate-Smith, E.C. Haemanalysis of tannins: The concept of relative astringency. Phytochtmistry 12:907 (1973).

    Article  CAS  Google Scholar 

  23. Haslam, E.; Lilley, T.H. Natural astringency in foodstuffs. A molecular interpretation. Crit. Rev. Food Sci. Nv.tr. 27:1 (1988).

    Article  CAS  Google Scholar 

  24. Tamir, M.; Alumot, E. Inhibition of digestive enzymes by condensed tannins from green and ripe carobs. J. Agric. Food Chem. 26:784 (1969).

    Google Scholar 

  25. Milic, B.L.; Stojanovic, S.; Vucrevic, N. Lucerne tannins. II. Isolation of tannins from lucerne, their nature and influence on digestive enzymes in vitro. J. Sci. Food. Agric. 23:1157 (1972).

    Article  CAS  Google Scholar 

  26. Oh, HJ.; Hoff, J.E. Effect of condensed grape tannins on the in vitro activity of digestive proteases and activation of their zymogens. J. Food Sci. 51:577 (1986).

    Article  CAS  Google Scholar 

  27. Asquith, T.N.; Uhlig, J.; Mehansho, H.; Putman, L.; Carlson, D.M.; Butler, L. Binding of condensed tannins to salivary proline-rich glycoproteins: the role of carbohydrate. J. Agric. Food Chem. 35:331 (1987).

    Article  CAS  Google Scholar 

  28. Hara, Y.; Honda, M. The inhibition of α-amylase by tea polyphenols. Agric. Biol. Chem. 54:1939 (1990).

    Article  CAS  Google Scholar 

  29. Rhoades, D.F.; Gates, R.G. Towards a general theory of plant antiherbivore chemistry. In: Wallace, J.W.; Mansell, R.L. (eds) Biochemical interaction between plants and insects. (Recent Advances in Biochemistry) Plenum Press, New York (1976).

    Google Scholar 

  30. Kumar, R.; Singh, M. Tannins-their adverse role in ruminant nutrition. J. Agric. Food Chem. 32:447 (1984).

    Article  CAS  Google Scholar 

  31. Butler, L.G. Effects of condensed tannin on animal nutrition. In: Hemingway, R.W.; Karchesy, J. J. (eds) Chemistry and significance of condensed tannins. Plenum Press, New York (1989).

    Google Scholar 

  32. Pierpoint, W.S.; Ireland, R.J.; Carpenter, J.M. Modification of proteins during the oxidation of leaf phenols: reaction of potato virus X with chlorogenoquinone. Phytochemistry 16:29 (1977).

    Article  CAS  Google Scholar 

  33. Takechi, M.; Tanaka, Y.; Nonaka, G.I.; Nishioka, I. Structure and antiherpetic activity among the tannins. Phytochemistry 24:2245 (1985).

    Article  CAS  Google Scholar 

  34. Uchida, S.; Edamatsu, R.; Hiramatsu, M.; Mori, A.; Nonaka, G.I.; Nishioka, I.; Niwa, M.; Ozaki, M. Condensed tannins scavenge active oxygen free radicals. Med. Sci. Res. 15: 831 (1987).

    CAS  Google Scholar 

  35. Ariga, T.; Hamano, M. Radical scavenging action and its mode in procyanidin B-l and B-3 from azuki beans to peroxyl radicals. Agric. Biol. Chem. 54:2499 (1990).

    Article  CAS  Google Scholar 

  36. Ricardo da Silva, J.M.; Rigaud, J.; Cheynier, V.; Cheminat, A.; Moutounet, M. Procyanidin dimers and trimers from grape seeds. Phytochemistry 30:1259 (1990).

    Article  Google Scholar 

  37. Thompson, R.S.; Jacques, D.; Haslam, E.; Tanner, R.J.N. Plant proanthocyanidins. Part I. Introduction. The isolation, structure, and distribution in nature of plant procyanidins. J. Chem. Soc, Perkin Trans. 1:1387 (1972).

    Article  Google Scholar 

  38. Foo, L.Y.; Karchesy, J.J. Procyanidin dimers and trimers from Douglas-fir inner bark. Phytochemistry 28:1743 (1989).

    Article  CAS  Google Scholar 

  39. Flechter, A.C.; Porter, L.J.; Haslam, E.; Gupta, R.K. Plant proanthocyanidins. Part 3. Conformational and configurational studies of natural procyanidins. J. Chem. Soc., Perkin Trans. 1:1628 (1977).

    Google Scholar 

  40. Foo L.Y.; Porter, L.J. Synthesis and conformation of procyanidin diastereoisomers. J. Chem. Soc., Perkin Trans. 1:1535 (1983).

    Article  Google Scholar 

  41. Hemingway, R.W.; Karchesy, J.J.; McGraw, G.W.; Wielsek, R.A. Heterogeneity of inter-flavanoid bond location in Loblolly pine bark procyanidins. Phytochemistry 22:275 (1983).

    Article  CAS  Google Scholar 

  42. Kolodziej, H. Synthesis and characterization of procyanidin dimers as their peracetates and octamethyl ether derivatives. Phytochemistry 25:1209 (1986).

    Article  CAS  Google Scholar 

  43. Hemingway, R.W.; McGraw, G.M. Kinetics of acid-catalyzed cleavage of procyanidins. J. Wood Chem. Technol. 3:421 (1983).

    Article  CAS  Google Scholar 

  44. Morimoto, S.; Nonaka, G.-L; Nishioka, I. Tannins and related compounds. XXXVIII. Isolation and characterization of flavan-3-ol glucosides and procyanidin oligomers from Cassia bark (Cinnamomum cassia Blume). Chem. Pharm. Bull. 34:633(1986).

    Article  CAS  Google Scholar 

  45. Kolodziej, H. Thiolysis of birch bark procyanidins: structural dependence in formation of 2,3-cis-3,4-cis-flavan-4-benzylthioethers from procyanidins. Phytochemistry 29:1671 (1990).

    Article  CAS  Google Scholar 

  46. Rigaud, J.; Perez-IIzarbe, J.; Ricardo da Silva, J.M.; Cheynier, V. Micro method for the identification of proanthocyanidin using thiolysis monitored by high-performance chromatography. J. Chromatogr. 540:401 (1991).

    Article  CAS  Google Scholar 

  47. McManus, J.P.; Davis, K.G.; Beart, J.E.; Gaffney, S.H.; Lilley, T.H.; Haslam, E. Polyphenol interactions. Part 1. Introduction. Some observations on the reversible complexation of proteins and polysaccharide. J. Chem. Soc., Perkin Trans. 2:1429(1985).

    Google Scholar 

  48. Hagerman, A.E. Chemistry of tannin-protein complexation. In: Hemingway, R.W.; Karchesy, J.J. (eds.) Chemistry and significance of condensed tannins. Plenum Press, New York (1989).

    Google Scholar 

  49. Ya, C; Gaffney, S.H.; Lilley, T.H.; Haslam, E. Carbohydrate-polyphenol complexation. In: Hemingway, R.W.; Karchesy, J.J. (eds.) Chemistry and significance of condensed tannins. Plenum Press, New York (1989).

    Google Scholar 

  50. Ricardo da Silva, J.M.; Cheynier, V.; Souquet, J.M.; Moutounet, M.; Cabanis, J.C.; Bourzeix, M. Interaction of grape seed procyanidins with various proteins. Effects in a red wine. J. Sci. Food Agric. 57:111 (1991).

    Article  CAS  Google Scholar 

  51. Saulnier, L.; Brillouet, J.M. An arabinogalactan-protein from the pulp of grape berries. Carbohydrate Research 188:137 (1989).

    Article  CAS  Google Scholar 

  52. Hagerman, A.E.; Butler, L.G. The specificity of proanthocyanidin-protein interactions. J. Biol. Chem. 259:4494 (1981).

    Google Scholar 

  53. Haslam, E. Polyphenol-protein interactions. Biochem. J. 139:285 (1974).

    PubMed  CAS  Google Scholar 

  54. Porter, L.J.; Woodruffe, J. Haemanalysis: the relative astringency of proanthocyanidin polymers. Phytochemistry 23:1255 (1984).

    Article  CAS  Google Scholar 

  55. Jouve, C; Cabanis, J.C.; Bourzeix, M.; Hérédia, N.; Rosec, J.P.; Vialatte, C. Teneure en catéchines et procyanidols de vins blancs et rosés. Effets du collage par la caséine. Rev. F. Oenol. 117:14 (1989).

    CAS  Google Scholar 

  56. Lee, C.Y.; Jaworski, A.W. Phenolics and browning potential of white grapes grown in New York. Am. J. Enol. Vitic. 39:337 (1988).

    CAS  Google Scholar 

  57. Rigaud, J.; Cheynier, V.; Souquet, J.M.; Moutounet, M. Influence of must composition on phenolic oxidation kinetics. J. Sci. Food Agric. 54:55(1991).

    Article  Google Scholar 

  58. Cheynier, V.; Ricardo da Silva, J.M. Oxidation of grape procyanidins in model solutions containing trans-caffeoyltartaric acid and polyphenoloxidase. J. Agric. Food Chem. 39:1047 (1991).

    Article  CAS  Google Scholar 

  59. Cheynier, V.; Osse, C; Rigaud, J. Oxidation of grape juice phenolic compounds in model solutions. J. Food Sci. 53:1729 (1988).

    Article  CAS  Google Scholar 

  60. Cheynier, V.; Basire, N.; Rigaud, J. Mechanism of trans-caffeoyltartaric acid and catechin oxidation in model solutions containing grape polyphenoloxidase. J. Agric. Food Chem. 37:1069 (1989).

    Article  CAS  Google Scholar 

  61. Cheynier, V.; Rigaud, J.; Moutounet, M. High-performance liquid Chromatographic determination of the free o-quinones of trans-caffeoyltartaric acid, 2-S-glutathionylcaffeoyltartaric acid, and catechin in grape must. J. Chromatogr. 472:428 (1989).

    Article  CAS  Google Scholar 

  62. Ariga, T; Koshiyama, I.; Fukushima, D. Antioxidative properties of procyanidin Bl and B3 from Azuki beans in aqueous systems. Agric. Biol. Chem. 52:2717 (1988).

    Article  CAS  Google Scholar 

  63. Masquelier, J. Physiological effects of wine. His share in alcoholism. Bull. O.I. V. 689:554 (1988).

    Google Scholar 

  64. Ricardo da Silva, J.M.; Darmon, N.; Fernandez, Y.; Mitjavila, S. Oxygen free radical scavenger capacity in aqueous models of different procyanidins from grape seeds. J. Agric. Food Chem. 39:1549 (1991).

    Article  Google Scholar 

  65. Fridovich, I. Quantitative aspects of the production of Superoxide radical anion radical by milk xanthine oxidase. J. Biol. Chem. 245:4053 (1970).

    PubMed  CAS  Google Scholar 

  66. Halliwell, B; Gutteridge, J.M.C.; Aruoma, O.I. The deoxyribose method: a simple “testtube” assay for determination of rate constants for reactions of hydroxyl radicals. Anal. Biochem. 165:215 (1987).

    Article  PubMed  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Institute for Wine Products, National Institute for Agriculture Research, 34060, Montpellier, France

    Véronique Cheynier & Jacques Rigaud

  2. Institute of Agronomy, Technical University of Lisboa, 1399, Lisboa Codex, Portugal

    Jorge M. Ricardo da Silva

Authors
  1. Véronique Cheynier
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jacques Rigaud
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jorge M. Ricardo da Silva
    View author publications

    You can also search for this author in PubMed Google Scholar

Editor information

Editors and Affiliations

  1. United States Department of Agriculture, Forest Service, Pineville, Louisiana, USA

    Richard W. Hemingway

  2. Institute of Wood Research, Houghton, Michigan, USA

    Peter E. Laks

Rights and permissions

Reprints and permissions

Copyright information

© 1992 Springer Science+Business Media New York

About this chapter

Cite this chapter

Cheynier, V., Rigaud, J., da Silva, J.M.R. (1992). Structure of Procyanidin Oligomers Isolated From Grape Seeds in Relation to Some of their Chemical Properties. In: Hemingway, R.W., Laks, P.E. (eds) Plant Polyphenols. Basic Life Sciences, vol 59. Springer, Boston, MA. https://doi.org/10.1007/978-1-4615-3476-1_16

Download citation

  • DOI: https://doi.org/10.1007/978-1-4615-3476-1_16

  • Publisher Name: Springer, Boston, MA

  • Print ISBN: 978-1-4613-6540-2

  • Online ISBN: 978-1-4615-3476-1

  • eBook Packages: Springer Book Archive

Publish with us

Policies and ethics

Search

Navigation