Condensed tannin

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Schematic representation of a condensed tannin molecule. Condensed tannins can be linear (with 4→8 bounds) or branched (with 4→6 bounds - dotted line).

Condensed tannins (proanthocyanidins, polyflavonoid tannins, catechol-type tannins, pyrocatecollic type tannins, non-hydrolyzable tannins or flavolans) are polymers formed by the condensation of flavans. They do not contain sugar residues.[1]

Different types of condensed tannins exist such as the procyanidins, propelargonidins, prodelphinidins, profisetinidins, proguibourtinidins or prorobinetidins. They are called proanthocyanidins as they yield anthocyanidins when depolymerized under oxidative conditions.

Tannins of tropical woods tend to be of a catechin nature rather than of the gallic type present in temperate woods.[2]

One particular type of condensed tannin, found in grape are procyanidins, which are polymers of 2 to 50 (or more) flavan-3ol units joined by carbon-carbon bonds. These are not susceptible to being cleaved by hydrolysis.

While many hydrolyzable tannins and most condensed tannins are water soluble, several tannins are also highly octanol soluble.[3][4] Some large condensed tannins are insoluble. Differences in solubilities are likely to affect their biological functions.

Condensed tannins from Lithocarpus glaber leaves have a potent free radical scavenging activity.[5] Condensed tannins can be found in Prunus sp.[6]

Condensed tannins can be characterised by a number of techniques including depolymerisation, asymmetric flow field flow fractionation, small-angle X-ray scattering[7] and Maldi-TOF mass spectrometry.[8] Their interactions with proteins can be studied by isothermal titration calorimetry [9] and this provides information on the affinity constant, enthalpy and stoichiometry in the tannin-protein complex.

Condensed tannins can be extracted from different vegetable plants, such as quebracho wood (Schinopsis lorentzii), mimosa bark (Acacia mollissima), grapes seeds (Vitis vinifera), pine barks and spruce barks.[10] [11] [12]

Contents

Depolymerisation [edit]

Depolymerisation reactions are mainly analytical techniques but it is envisaged to use them as means to produce molecules for the chemical industry derived from waste products, such as bark from the wood industry[13] or pomaces from the wine industry.

Oxidative depolymerisation [edit]

The butanol–hydrochloric acid–iron assay[14] (Porter assay) is a colorimetric assay. It is based on acid catalysed oxidative depolymerization of condensed tannins into corresponding anthocyanidins.[15] The method has also been used for determination of bound condensed tannins, but has limitations.[16] This reagent has recently been improved considerably by inclusion of acetone.[17][1]

Non oxidative chemical depolymerisation [edit]

The condensed tannins can nevertheless undergo acid-catalyzed cleavage in the presence of (an excess of) a nucleophile[18] like phloroglucinol (reaction called phloroglucinolysis), benzyl mercaptan (reaction called thiolysis), thioglycolic acid (reaction called thioglycolysis) or cysteamine. These techniques are generally called depolymerisation and give informations such as average degree of polymerisation or percentage of galloylation. These are SN1 reactions, a type of substitution reaction in organic chemistry, involving a carbocation intermediate under strongly acidic conditions in polar protic solvents like methanol. The reaction leads to the formation of free and derivated monomers that can be further analyzed. The free monomers correspond to the terminal units of the condensed tannins chains. If thiolysis is done directly on plant material (rather than on purified tannins), it is, however, important to subtract naturally occurring free flavanol monomers from the concentration of terminal units that are released during depolymerisation.

Reactions are generally made in methanol, especially thiolysis, as benzyl mercaptan has a low solubility in water. They involve a moderate (40 to 90°C) heating for a few minutes. Epimerisation may happen.[19]

Phloroglucinolysis can be used for instance for proanthocyanidins characterisation in wine[20] or in the grape seed and skin tissues.[21]

Thioglycolysis can be used to study proanthocyanidins[22] or the oxidation of condensed tannins.[7] It is also used for lignin quantitation.[23] Reaction on condensed tannins from Douglas fir bark produces epicatechin and catechin thioglycolates.[13]

Condensed tannins from Lithocarpus glaber leaves have been analysed through acid-catalyzed degradation in the presence of cysteamine.[5]

References [edit]

  1. ^ Teresa K. Attwood and Richard Cammack (2006). Oxford dictionary of biochemistry and molecular biology. ISBN 0198529171. 
  2. ^ Les tannins dans les bois tropicaux (Tannin in tropical woods), by Jacqueline Doat, Revue bois et forêts des tropiques, 1978, n° 182 (French)
  3. ^ Mueller-Harvey, I., Mlambo, V., Sikosana, J.L.N., Smith, T., Owen, E., Brown, R.H. Octanol-water partition coefficients for predicting the effects of tannins in ruminant nutrition. J. Agric. Food Chem. 2007, 55, 5436-5444. DOI: 10.1021/jf070308a
  4. ^ Mueller-Harvey, I. Unravelling the conundrum of tannins in animal nutrition and health. J. Sci. Food Agric. 86, 2006, 2010-2037. DOI: 10.1002/jsfa.2577
  5. ^ a b Zhang, L. L.; Lin, Y. M. (2008). "HPLC, NMR and MALDI-TOF MS Analysis of Condensed Tannins from Lithocarpus glaber Leaves with Potent Free Radical Scavenging Activity". Molecules 13 (12): 2986–2997. doi:10.3390/molecules13122986. PMID 19052523.  edit
  6. ^ Feucht, W.; Nachit, M. (1977). "Flavolans and Growth-Promoting Catechins in Young Shoot Tips of Prunus Species and Hybrids". Physiologia Plantarum 40 (4): 230. doi:10.1111/j.1399-3054.1977.tb04063.x.  edit
  7. ^ a b Vernhet, A.; Dubascoux, S. P.; Cabane, B.; Fulcrand, H. L. N.; Dubreucq, E.; Poncet-Legrand, C. L. (2011). "Characterization of oxidized tannins: Comparison of depolymerization methods, asymmetric flow field-flow fractionation and small-angle X-ray scattering". Analytical and Bioanalytical Chemistry 401 (5): 1559–1569. doi:10.1007/s00216-011-5076-2. PMID 21573842.  edit
  8. ^ Stringano, E., Cramer, R., Hayes, W., Smith, C., Gibson, T., Mueller-Harvey, I. Deciphering the complexity of sainfoin (Onobrychis viciifolia) proanthocyanidins by MALDI-TOF mass spectrometry with a judicious choice of isotope patterns and matrices. Anal. Chem. 2011, 83, 4147-4153. DOI: 10.1021/ac2003856
  9. ^ Dobreva, M.A., Frazier, R.A., Mueller-Harvey, I., Clifton, L.A., Gea A., Green, R.J. Binding of pentagalloyl glucose to two globular proteins occurs via multiple surface sites. Biomacromolecules 2011, 12, 710-715. DOI: 10.1021/bm101341s
  10. ^ Haslam E. Plant Polyphenols, Vegetable Tannins Revisited. Cambridge University Press, Cambridge, UK (1989).
  11. ^ Condensed tannins on www.silvateam.com.
  12. ^ Ping, L, Laurent Chrusciel, L, Navarrete, P, Pizzi, A. Extraction of condensed tannins from grape pomace for use as wood adhesives. Industrial Crops and Products, Volume 33, Issue 1, January 2011, Pages 253–257. http://dx.doi.org/10.1016/j.indcrop.2010.10.007.
  13. ^ a b Douglas-Fir Bark: Characterization of a Condensed Tannin Extract, by Hong-Keun Song, A thesis submitted to Oregon State University in partial fulfillment of the requirements for the degree of Master of Science, December 13, 1984
  14. ^ Acid butanol assy for proanthocyanidins. by Ann E. Hagermann, 2002 (article)
  15. ^ The conversion of procyanidins and prodelphinidins to cyanidin and delphinidin. Lawrence J. Porter, Liana N. Hrstich and Bock G. Chana, Phytochemistry, 23 December 1985, Volume 25, Issue 1, Pages 223–230, doi:10.1016/S0031-9422(00)94533-3
  16. ^ Makkar, H. P. S.; Gamble, G.; Becker, K. (1999). "Limitation of the butanol–hydrochloric acid–iron assay for bound condensed tannins". Food Chemistry 66: 129. doi:10.1016/S0308-8146(99)00043-6.  edit
  17. ^ Grabber J., Zeller, W.E., Mueller-Harvey, I. 2013. Acetone enhances the direct analysis of procyanidin- and prodelphinidin-based condensed tannins in Lotus species by the butanol-HCl-iron assay. J. Agric. Food Chem. http://pubs.acs.org/doi/abs/10.1021/jf304158m
  18. ^ Method for Estimation of Proanthocyanidins Based on Their Acid Depolymerization in the Presence of Nucleophiles. Sara Matthews, Isabelle Mila, Augustin Scalbert, Brigitte Pollet, Catherine Lapierre, Catherine L. M. Hervé du Penhoat, Christian Rolando and Dervilla M. X. Donnelly, J. Agric. Food Chem., 1997, 45 (4), pp. 1195–1201, doi:10.1021/jf9607573
  19. ^ Gea, A., Stringano, E., Brown, R.H., Mueller-Harvey, I. In situ analysis and structural elucidation of sainfoin (Onobrychis viciifolia) tannins for high throughput germplasm screening. J. Agric. Food Chem. 2011, 59, 495-503 (DOI: 10.1021/jf103609p)
  20. ^ Analysis of Tannins in Red Wine Using Multiple Methods: Correlation with Perceived Astringency by mean of depolymerisation. James A. Kennedy, Jordan Ferrier, James F. Harbertson and Catherine Peyrot des Gachons, Am. J. Enol. Vitic. 57:4, 2006, pp. 481-485
  21. ^ Analysis of Proanthocyanidin Cleavage Products Following Acid-Catalysis in the Presence of Excess Phloroglucinol. James A. Kennedy and Graham P. Jones, J. Agric. Food Chem., 2001, 49 (4), pp. 1740–1746, doi:10.1021/jf001030o
  22. ^ Cleavage of proanthocyanidins with thioglycollic acid. Karl D. Sears and Ronald L. Casebier, Chem. Commun. (London), 1968, pp. 1437-1438, doi:10.1039/C19680001437
  23. ^ Elicitor-Induced Spruce Stress Lignin (Structural Similarity to Early Developmental Lignins). B. M. Lange, C. Lapierre and H. Sandermann Jr, Plant Physiology, July 1995, vol. 108, no. 3, pp. 1277-1287, doi:10.1104/pp.108.3.1277
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