Grenache, Syrah, Carignan Noir, Mourvèdre, Counoise and Alicante Bouchet grape seeds and skins, harvested in 2009 and 2010 in the Rh？ne valley area of France, and their respective pomaces remaining after vinification, were analyzed for their phenolic composition and antioxidant activity. The polyphenol content was quantified by HPLC and the Folin-Ciocalteu assay. The antioxidant potential was measured with four different assays: ORAC, FRAP, ABTS and DPPH. Seeds contained higher amounts of total polyphenols, up to 44.5 mg of gallic acid equivalent [GAE]/g dry weight in Alicante pomace, than skin extracts. The maximum total phenolic in skins was 31.6 mg GAE/g dry weight detected in 2010 Alicante pomace. Seeds also had the highest antioxidant capacity. HPLC analysis revealed that, despite the vinification process, pomaces still contained an appreciable amount of proanthocyanidins as well as several anthocyanin glycosides. Alicante and Syrah proved to be the varieties of most interest in terms of their potential development for nutraceutical purposes.
References
[1]
OIV. World Statistics. In Proceedings of the 9th General Assembly of the OIV Porto, Paris, France, 20–27 June 2011.
[2]
FAO. Statistical Databases (Electronical Resource). FAO: Paris, France, 2010. Available online: http://faostat.fao.org (accessed on1 November 2012).
[3]
Buffin, J.C. Educvin: Votre Talent de la Dégustation. (in French); Oenoplurime？dia: Chaintre, France, 2000.
[4]
Llobera, A.; Ca？ellas, J. Dietary fibre content and antioxidant activity of Manto Negro red grape (Vitis vinifera): Pomace and stem. Food Chem. 2007, 101, 659–666, doi:10.1016/j.foodchem.2006.02.025.
[5]
Laufenberg, G.; Kunz, B.; Nystroem, M. Transformation of vegetable waste into value added products: (A) the upgrading concept; (B) practical implementations. Bioresour. Technol. 2003, 87, 167–198, doi:10.1016/S0960-8524(02)00167-0.
[6]
Ruberto, G.; Renda, A.; Daquino, C.; Amico, V.; Spatafora, C.; Tringali, C.; Tommasi, N.D. Polyphenol constituents and antioxidant activity of grape pomace extracts from five Sicilian red grape cultivars. Food Chem. 2007, 100, 203–210, doi:10.1016/j.foodchem.2005.09.041.
[7]
Kammerer, D.; Claus, A.; Carle, R.; Schieber, A. Polyphenol screening of pomace from red and white grape varieties (Vitis vinifera L.) by HPLC-DAD-MS/MS. J. Agric. Food Chem. 2004, 52, 4360–4367, doi:10.1021/jf049613b.
[8]
Alonso, á.M.; Guillén, D.A.; Barroso, C.G.; Puertas, B.; García, A. Determination of antioxidant activity of wine byproducts and its correlation with polyphenolic content. J. Agric. Food Chem. 2002, 50, 5832–5836, doi:10.1021/jf025683b.
[9]
Louli, V.; Ragoussis, N.; Magoulas, K. Recovery of phenolic antioxidants from wine industry by-products. Bioresour. Technol. 2004, 92, 201–208, doi:10.1016/j.biortech.2003.06.002.
[10]
Negro, C.; Tommasi, L.; Miceli, A. Phenolic compounds and antioxidant activity from red grape marc extracts. Bioresour. Technol. 2003, 87, 41–44, doi:10.1016/S0960-8524(02)00202-X.
[11]
Xu, Y.; Simon, J.E.; Welch, C.; Wightman, J.D.; Ferruzzi, M.G.; Ho, L.; Passinetti, G.M.; Wu, Q. Survey of polyphenol constituents in grapes and grape-derived products. J. Agric. Food Chem. 2011, 59, 10586–10593.
[12]
Lafka, T.I.; Sinanoglou, V.; Lazos, E.S. On the extraction and antioxidant activity of phenolic compounds from winery wastes. Food Chem. 2007, 104, 1206–1214, doi:10.1016/j.foodchem.2007.01.068.
[13]
Teissedre, P.L.; Frankel, E.N.; Waterhouse, A.L.; Peleg, H.; German, J.B. Inhibition of in vitro human LDL-oxidation by phenolic antioxidants from grapes and wines. J. Sci. Food Agric. 1996, 70, 55–61, doi:10.1002/(SICI)1097-0010(199601)70:1<55::AID-JSFA471>3.0.CO;2-X.
[14]
Natella, F.; Ghiselli, A.; Guidi, A.; Ursini, F.; Scaccini, C. Red wine mitigates the postprandial increase of LDL susceptibility to oxidation. Free Radic. Biol. Med. 2001, 30, 1036–1044, doi:10.1016/S0891-5849(01)00504-4.
[15]
Gorelik, S.; Ligumsky, M.; Kohen, R.; Kanner, J. A novel function of red wine polyphenols in humans: Prevention of absorption of cytotoxic lipid peroxidation products. FASEB J. 2008, 22, 41–46.
[16]
Bagchi, D.; Bagchi, M.; Stohs, S.J.; Das, D.K.; Ray, S.D.; Kuszynski, C.A.; Joshi, S.S.; Pruess, H.G. Free radicals and grape seed proanthocyanidin extract: Importance in human health and disease prevention. Toxicology 2000, 148, 187–197, doi:10.1016/S0300-483X(00)00210-9.
[17]
Castilla, P.; Echarri, R.; Dávalos, A.; Cerrato, F.; Ortega, H.; Teruel, J.L.; Lucas, M.F.; Gómez-Coronado, D.; Ortu？o, J.; Lasunción, M.A. Concentrated red grape juice exerts antioxidant, hypolipidemic, and antiinflammatory effects in both hemodialysis patients and healthy subjects. Am. J. Clin. Nutr. 2006, 84, 252–262.
[18]
Sano, A.; Uchida, R.; Saito, M.; Shioya, N.; Komori, Y.; Tho, Y.; Hashizume, N. Beneficial effects of grape seed extract on malondialdehyde-modified LDL. J. Nutr. Sci. Vitaminol. 2007, 53, 174–182, doi:10.3177/jnsv.53.174.
[19]
Arts, I.C.; Hollman, P.C. Polyphenols and disease risk in epidemiologic studies. Am. J. Clin. Nutr. 2005, 81, 317S–325S.
[20]
Shanmuganayagam, D.; Beahm, M.R.; Osman, H.E.; Krueger, C.G.; Reed, J.D.; Folts, J.D. Grape seed and grape skin extracts elicit a greater antiplatelet effect when used in combination than when used individually in dogs and humans. J. Nutr. 2002, 132, 3592–3598.
[21]
Dr？ge, W. Free radicals in the physiological control of cell function. Physiol. Rev. 2002, 82, 47–95.
[22]
Halliwell, B. Free radicals, antioxidants, and human disease: Curiosity, cause, or consequence? Lancet 1994, 344, 721–724, doi:10.1016/S0140-6736(94)92211-X.
[23]
Monagas, M.; Gómez-Cordovés, C.; Bartolomé, B.; Laureano, O.; da Silva, R.J.M. Monomeric, oligomeric, and polymeric flavan-3-ol composition of wines and grapes from Vitis vinifera L. Cv. Graciano, Tempranillo, and Cabernet Sauvignon. J. Agric. Food Chem. 2003, 51, 6475–6481, doi:10.1021/jf030325+.
[24]
Vidal, S.; Francis, L.; Guyot, S.; Marnet, N.; Kwiatkowski, M.; Gawel, R.; Cheynier, V.; Waters, E.J. The mouth-feel properties of grape and apple proanthocyanidins in a wine-like medium. J. Sci. Food Agric. 2003, 83, 564–573, doi:10.1002/jsfa.1394.
[25]
Jensen, J.S.; Demiray, S.; Egebo, M.; Meyer, A.S. Prediction of wine color attributes from the phenolic profiles of red grapes (Vitis vinifera). J. Agric. Food Chem. 2008, 56, 1105–1115, doi:10.1021/jf072541e.
[26]
Ribéreau-Gayon, P.; Glories, Y.; Maujean, A.; Dubourdieu, D. Phenolic Compounds. In Handbook of Enology: The Chemistry of Wine.Stabilization and Treatments; John Wiley & Sons, Ltd: West Sussex, UK, 2006; pp. 141–203.
[27]
Lorrain, B.; Chira, K.; Teissedre, P.L. Phenolic composition of Merlot and Cabernet-Sauvignon grapes from Bordeaux vineyard for the 2009-vintage: Comparison to 2006, 2007 and 2008 vintages. Food Chem. 2011, 126, 1991–1999, doi:10.1016/j.foodchem.2010.12.062.
[28]
Prieur, C.; Rigaud, J.; Cheynier, V.; Moutounet, M. Oligomeric and polymeric procyanidins from grape seeds. Phytochemistry 1994, 36, 781–784, doi:10.1016/S0031-9422(00)89817-9.
[29]
Souquet, J.-M.; Cheynier, V.; Brossaud, F.; Moutounet, M. Polymeric proanthocyanidins from grape skins. Phytochemistry 1996, 43, 509–512, doi:10.1016/0031-9422(96)00301-9.
[30]
Bordiga, M.; Travaglia, F.; Locatelli, M.; Co？sson, J.D.; Arlorio, M. Characterisation of polymeric skin and seed proanthocyanidins during ripening in six Vitis vinifera L. cv. Food Chem. 2011, 127, 180–187, doi:10.1016/j.foodchem.2010.12.141.
[31]
Spranger, I.; Sun, B.; Mateus, A.M.; Freitas, V.D.; Ricardo-da-Silva, J.M. Chemical characterization and antioxidant activities of oligomeric and polymeric procyanidin fractions from grape seeds. Food Chem. 2008, 108, 519–532, doi:10.1016/j.foodchem.2007.11.004.
[32]
Chira, K.; Schmauch, G.; Saucier, C.; Fabre, S.; Teissedre, P.L. Grape variety effect on proanthocyanidin composition and sensory perception of skin and seed tannin extracts from Bordeaux wine grapes (cabernet Sauvignon and merlot) for two consecutive vintages (2006 and 2007). J. Agric. Food Chem. 2009, 57, 545–553, doi:10.1021/jf802301g.
[33]
Liang, Z.; Wu, B.; Fan, P.; Yang, C.; Duan, W.; Zheng, X.; Liu, C.; Li, S. Anthocyanin composition and content in grape berry skin in Vitis germplasm. Food Chem. 2008, 111, 837–844, doi:10.1016/j.foodchem.2008.04.069.
[34]
Romero-Cascales, I.; Ortega-Regules, A.; López-Roca, J.M.; Fernández-Fernández, J.I.; Gómez-Plaza, E. Differences in anthocyanin extractability from grapes to wines according to variety. Am. J. Enol. Viticul. 2005, 56, 212–219.
[35]
Hermosin Gutierrez, I.; Garcia-Romero, E. Anthocyanins of red wine grape cultivars grown in the Spanish region of La Mancha: Characteristic cultivar patterns of grapes and single cultivar wines, and evolution during the ripening of the berry. Alimentaria 2004, 41, 127–139.
[36]
García-Beneytez, E.; Revilla, E.; Cabello, F. Anthocyanin pattern of several red grape cultivars and wines made from them. Eur. Food Res. Technol. 2002, 215, 32–37, doi:10.1007/s00217-002-0526-x.
[37]
Fournand, D.; Vicens, A.; Sidhoum, L.; Souquet, J.-M.; Moutounet, M.; Cheynier, V. Accumulation and extractability of grape skin tannins and anthocyanins at different advanced physiological stages. J. Agric. Food Chem. 2006, 54, 7331–7338, doi:10.1021/jf061467h.
[38]
Lee, J.-E.; Hwang, G.-S.; van Den Berg, F.; Lee, C.-H.; Hong, Y.-S. Evidence of vintage effects on grape wines using 1H NMR-based metabolomic study. Anal. Chim. Acta 2009, 648, 71–76, doi:10.1016/j.aca.2009.06.039.
[39]
Van Leeuwen, C.; Friant, P.; Choné, X.; Tregoat, O.; Koundouras, S.; Dubourdieu, D. Influence of climate, soil, and cultivar on terroir. Am. J. Enol. Viticul. 2004, 55, 207–217.
[40]
Pereira, G.E.; Gaudillere, J.-P.; Leeuwen, C.V.; Hilbert, G.; Maucourt, M.; Deborde, C.; Moing, A.; Rolin, D. 1H NMR metabolite fingerprints of grape berry: Comparison of vintage and soil effects in Bordeaux grapevine growing areas. Anal. Chim. Acta 2006, 563, 346–352, doi:10.1016/j.aca.2005.11.007.
[41]
Gagné, S.; Lacampagne, S.; Claisse, O.; Gény, L. Leucoanthocyanidin reductase and anthocyanidin reductase gene expression and activity in flowers, young berries and skins of Vitis vinifera L. cv. Cabernet-Sauvignon during development. Plant Physiol. Biochem. 2009, 47, 282–290, doi:10.1016/j.plaphy.2008.12.004.
[42]
Chorti, E.; Guidoni, S.; Ferrandino, A.; Novello, V. Effect of different cluster sunlight exposure levels on ripening and anthocyanin accumulation in Nebbiolo grapes. Am. J. Enol. Viticul. 2010, 61, 23–30.
[43]
Cortell, J.M.; Kennedy, J.A. Effect of shading on accumulation of flavonoid compounds in (Vitis vinifera L.) Pinot Noir fruit and extraction in a model system. J. Agric. Food Chem. 2006, 54, 8510–8520, doi:10.1021/jf0616560.
[44]
Downey, M.O.; Harvey, J.S.; Robinson, S.P. The effect of bunch shading on berry development and flavonoid accumulation in Shiraz grapes. Aust. J. Grape Wine Res. 2004, 10, 55–73.
[45]
Roginsky, V.; Lissi, E.A. Review of methods to determine chain-breaking antioxidant activity in food. Food Chem. 2005, 92, 235–254, doi:10.1016/j.foodchem.2004.08.004.
[46]
Huang, D.; Ou, B.; Prior, R.L. The chemistry behind antioxidant capacity assays. J. Agric. Food Chem. 2005, 53, 1841–1856, doi:10.1021/jf030723c.
[47]
Bozan, B.; Tosun, G.; ？zcan, D. Study of polyphenol content in the seeds of red grape (Vitis vinifera L.) varieties cultivated in Turkey and their antiradical activity. Food Chem. 2008, 109, 426–430, doi:10.1016/j.foodchem.2007.12.056.
[48]
Dudonné, S.; Vitrac, X.; Coutière, P.; Woillez, M.; Mérillon, J.M. Comparative study of antioxidant properties and total phenolic content of 30 plant extracts of industrial interest using DPPH, ABTS, FRAP, SOD, and ORAC assays. CORD Conf. Proc. 2009, 57, 1768–1774.
[49]
Ma, X.; Wu, H.; Liu, L.; Yao, Q.; Wang, S.; Zhan, R.; Xing, S.; Zhou, Y. Polyphenolic compounds and antioxidant properties in mango fruits. Sci. Horticul. 2011, 129, 102–107, doi:10.1016/j.scienta.2011.03.015.
[50]
Jord？o, A.M.; Correia, A.C.; Gon？alves, F.J. Evolution of antioxidant capacity in seeds and skins during grape maturation and their association with proanthocyanidin and anthocyanin content. Vitis 2012, 51, 137–139.
[51]
Plumb, G.W.; de Pascual-Teresa, S.; Santos-Buelga, C.; Cheynier, V.; Williamson, G. Antioxidant properties of catechins and proanthocyanidins: Effect of polymerisation, galloylation and glycosylation. Free Rad. Res. 1998, 29, 351–358, doi:10.1080/10715769800300391.
[52]
Es-Safi, N.-E.; Guyot, S.; Ducrot, P.-H. NMR, ESI/MS, and MALDI-TOF/MS analysis of pear juice polymeric proanthocyanidins with potent free radical scavenging activity. J. Agric. Food Chem. 2006, 54, 6969–6977, doi:10.1021/jf061090f.
[53]
Rockenbach, I.I.; Gonzaga, L.V.; Rizelio, V.M.; Gon？alves, A.E.D.S.S.; Genovese, M.I.; Fett, R. Phenolic compounds and antioxidant activity of seed and skin extracts of red grape (Vitis vinifera and Vitis labrusca) pomace from Brazilian winemaking. Food Res. Int. 2011, 44, 897–901, doi:10.1016/j.foodres.2011.01.049.
[54]
Prior, R.L.; Cao, G. In vivo total antioxidant capacity: Comparison of different analytical methods. Free Radic. Biol. Med. 1999, 27, 1173–1181, doi:10.1016/S0891-5849(99)00203-8.
[55]
Tarascou, I.; Barathieu, K.; André, Y.; Pianet, I.; Dufourc, E.J.; Fouquet, E. An improved synthesis of procyanidin dimers: Regio- and stereocontrol of the interflavan bond. Eur. J. Organ. Chem. 2006, 23, 5367–5377.
[56]
Sriram, G.; Surendranath, C.; Sureshkumar, G.K. Kinetics of anthocyanin extraction from fresh and dried grape waste. Separ. Sci. Technol. 1999, 34, 683–697, doi:10.1081/SS-100100674.
[57]
Singleton, V.L.; Rossi, J.A. Colorimetry of total phenolics with phosphomolybdic-phosphotungstic acid reagents. Am. J. Enol. Viticul. 1965, 16, 144–158.
[58]
Ribéreau Gayon, P.; Stonestreet, E. Le dosage des tanins dans le vin rouge et détermination de leur structure. Chim. Anal. 1966, 48, 188–196.
[59]
Ribéreau Gayon, P.; Stonestreet, E. Le dosage des anthocyanes dans le vin rouge. Bull. Soc. Chim. France 1965, 9, 2649–2652.
[60]
Silva, M.A.; Ky, I.; Jourdes, M.; Teissedre, P.L. Rapid and simple method for the quantification of flavan-3-ols in wine. Eur. Food Res. Technol. 2012, 234, 361–365, doi:10.1007/s00217-011-1628-0.
[61]
Drinkine, J.; Lopes, P.; Kennedy, J.A.; Teissedre, P.L.; Saucier, C. Analysis of ethylidene-bridged flavan-3-ols in wine. J. Agric. Food Chem. 2007, 55, 1109–1116, doi:10.1021/jf0626258.
[62]
Ou, B.; Hampsch-Woodill, M.; Prior, R.L. Development and validation of an improved oxygen radical absorbance capacity assay using fluorescein as the fluorescent probe. J. Agric. Food Chem. 2001, 49, 4619–4626, doi:10.1021/jf010586o.
[63]
Dávalos, A.; Gómez-Cordovés, C.; Bartolomé, B. Extending applicability of the oxygen radical absorbance capacity (ORAC-Fluorescein) assay. J. Agric. Food Chem. 2004, 52, 48–54, doi:10.1021/jf0305231.
[64]
Benzie, I.F.F.; Strain, J.J. The ferric reducing ability of plasma (FRAP) as a measure of antioxidant power: The FRAP assay. Anal. Biochem. 1996, 239, 70–76, doi:10.1006/abio.1996.0292.
[65]
Re, R.; Pellegrini, N.; Proteggente, A.; Pannala, A.; Yang, M.; Rice-Evans, C. Antioxidant activity applying an improved ABTS radical cation decolorization assay. Free Radic. Biol. Med. 1999, 26, 1231–1237, doi:10.1016/S0891-5849(98)00315-3.
[66]
Brand-Williams, W.; Cuvelier, M.E.; Berset, C. Use of a free radical method to evaluate antioxidant activity. LWT-Food Sci. Technol. 1995, 28, 25–30, doi:10.1016/S0023-6438(95)80008-5.
[67]
Miliauskas, G.; Venskutonis, P.R.; van Beek, T.A. Screening of radical scavenging activity of some medicinal and aromatic plant extracts. Food Chem. 2004, 85, 231–237, doi:10.1016/j.foodchem.2003.05.007.
