Polyphenols are the biggest group of phytochemicals, and many of them have been found in plant-based foods. Polyphenol-rich diets have been linked to many health benefits. This paper is intended to review the chemistry and biochemistry of polyphenols as related to classification, extraction, separation and analytical methods, their occurrence and biosynthesis in plants, and the biological activities and implications in human health. The discussions are focused on important and most recent advances in the above aspects, and challenges are identified for future research.
References
[1]
Milner, J.A. Reducing the risk of cancer. In Functional Foods: Designer Foods, Pharmafoods, Nutraceuticals; Goldberg, I., Ed.; Chapman & Hall: New York, NY, USA, 1994; pp. 39–70.
[2]
Duthie, G.G.; Brown, K.M. Reducing the risk of cardiovascular disease. In Functional Foods: Designer Foods, Pharmafoods, Nutraceuticals; Goldberg, I., Ed.; Chapman & Hall: New York, NY, USA, 1994; pp. 19–38.
[3]
Williams, R.J.; Spencer, J.P.; Rice-Evans, C. Flavonoids: Antioxidants or signaling molecules? Free Radic. Biol. Med.?2004, 36, 838–849, doi:10.1016/j.freeradbiomed.2004.01.001. 15019969
[4]
Dong, Z.; Surh, Y.-J.; Packer, L.; Cadenas, E. Dietary Modulation of Cell Signaling Pathways; CRC Press, Taylor & Francis Group: Boca Raton, FL, USA, 2009.
[5]
Harborne, J.B.; Williams, C.A. Advances in flavonoid research since 1992. Phytochemistry?2000, 55, 481–504, doi:10.1016/S0031-9422(00)00235-1. 11130659
[6]
Bravo, L. Polyphenols: Chemistry, Dietary Sources, Metabolism, and Nutritional Significance. Nutr. Rev.?1998, 56, 317–333, doi:10.1111/j.1753-4887.1998.tb01670.x. 9838798
[7]
Cheynier, V. Polyphenols in foods are more complex than often thought. Am. J. Clin. Nutr.?2005, 81, 223S–229S. 15640485
[8]
Kim, K.-H.; Tsao, R.; Yang, R.; Cui, S.W. Phenolic acid profiles and antioxidant activities of wheat bran extracts and the effect of hydrolysis conditions. Food Chem.?2006, 95, 466–473, doi:10.1016/j.foodchem.2005.01.032.
[9]
Adom, K.K.; Liu, R.H. Antioxidant activity of grains. J. Agric. Food Chem.?2002, 50, 6182–6187, doi:10.1021/jf0205099. 12358499
[10]
Chandrasekara, A.; Shahidi, F. Content of insoluble bound phenolics in millets and their contribution to antioxidant capacity. J. Agric. Food Chem.?2010, 58, 6706–6714, doi:10.1021/jf100868b. 20465288
[11]
Wang, H.; Murphy, P.A. Isoflavone content in commercial soybean foods. J. Agric. Food Chem.?1994, 42, 1666–1673, doi:10.1021/jf00044a016.
[12]
Mazur, W.M.; Duke, J.A.; Wahala, K.; Rasku, S.; Adlercreutz, H. Isoflavonoids and lignans in legumes: Nutritional and health aspects in Humans. J. Nutr. Biochem.?1998, 9, 193–200, doi:10.1016/S0955-2863(97)00184-8.
[13]
Tsao, R.; Papadopoulos, Y.; Yang, R.; Young, J.C.; McRae, K. Isoflavone profiles of red clovers and their distribution in different parts harvested at different growing stages. J. Agric. Food Chem.?2006, 54, 5797–5805, doi:10.1021/jf0614589. 16881680
[14]
Garazd, M.M.; Garazd, Y.L.; Khilya, V.P. Neoflavones. 1. Natural distribution and spectral and biological properties. Chem. Nat. Comp.?2003, 39, 54–121, doi:10.1023/A:1024140915526.
[15]
Tsao, R.; Yang, R.; Young, J.C.; Zhu, H. Polyphenolic profiles in eight apple cultivars using high–performance liquid chromatography (HPLC). J. Agric. Food Chem.?2003, 51, 6347–6353, doi:10.1021/jf0346298. 14518966
[16]
Zhao, F.; Watanabe, Y.; Nozawa, H.; Daikonnya, A.; Kondo, K.; Kitanaka, S. Prenylflavonoids and phloroglucinol derivatives from Hops (Humulus lupulus). J. Nat. Prod.?2005, 68, 43–49, doi:10.1021/np0499113. 15679315
[17]
Tsao, R.; McCallum, J. Chemistry of Flavonoids. In Fruit and Vegetable Phytochemicals: Chemistry, Nutritional Value and Stability; de la Rosa, L.A., Alvarez-Parrilla, E., Gonzalez–Aguilar, G., Eds.; Blackwell Publishing: Ames, IA, USA, 2009; Chapter 5, pp. 131–153.
[18]
Valant-Vetschera, K.M.; Wallenweber, E. Flavones and Flavonols. In Flavonoids: Chemistry, Biochemistry and Applications; Anderson, O.M., Markham, K.R., Eds.; CRC Press/Taylor & Francis Group: Boca Raton, FL, USA, 2006; pp. 618–748.
[19]
Williams, C.A. Flavone and flavonol O-glycosides. In Flavonoids: Chemistry, Biochemistry and Applications; Anderson, O.M., Markham, K.R., Eds.; CRC Press/Taylor & Francis Group: Boca Raton, FL, USA, 2006; pp. 749–856.
[20]
Grayer, R.J.; Veitch, N.C. Flavanones and dihydroflavonols. In Flavonoids: Chemistry, Biochemistry and Applications; Anderson, O.M., Markham, K.R., Eds.; CRC Press/Taylor & Francis Group: Boca Raton, FL, USA, 2006; pp. 918–1002.
[21]
Kawaii, S.; Tomono, Y.; Katase, E.; Ogawa, K.; Yano, M. Quantitation of flavonoid constituents in citrus fruits. J. Agric. Food Chem.?1999, 47, 3565–3571, doi:10.1021/jf990153+. 10552686
[22]
Si, W.; Gong, J.; Tsao, R.; Kalab, M.; Yang, R.; Yin, Y. Bioassay-guided purification and identification of antimicrobial components in Chinese green tea extract. J. Chromatogr. A?2006, 1125, 204–210, doi:10.1016/j.chroma.2006.05.061. 16797571
[23]
Prior, R.L.; Lazarus, S.A.; Cao, G.; Muccitelli, H.; Hammerstone, J.F. Identification of procyanidins and anthocyanins in blueberries and cranberries (Vaccinium spp.) using high–performance liquid chromatography/mass spectrometry. J. Agric. Food Chem.?2001, 49, 1270–1276, doi:10.1021/jf001211q. 11312849
[24]
Anderson, O.M.; Jordheim, M. The anthocyanins. In Flavonoids: Chemistry, Biochemistry and Applications; Anderson, O.M., Markham, K.R., Eds.; CRC Press/Taylor & Francis Group: Boca Raton, FL, USA, 2006; pp. 472–551.
[25]
McCallum, J.L.; Yang, R.; Young, J.C.; Strommer, J.N.; Tsao, R. Improved high performance liquid chromatographic separation of anthocyanin compounds from grapes using a novel mixed–mode ion-exchange reversed-phase column. J. Chromatogr. A?2007, 1148, 38–45, doi:10.1016/j.chroma.2007.02.088. 17382950
[26]
Davis, C.B.; Markey, C.E.; Busch, M.A.; Busch, K.W. Determination of capsaicinoids in habanero peppers by chemometric analysis of UV spectral data. J. Agric. Food Chem.?2007, 55, 5925–5933, doi:10.1021/jf070413k. 17608494
[27]
Bratt, K.; Sunnerheim, K.; Bryngelsson, S.; Fagerlund, A.; Engman, L.; Andersson, R.E.; Dimberg, L.H. Avenanthramides in oats (Avena sativa L.) and structure-antioxidant activity relationships. J. Agric. Food Chem.?2003, 51, 594–600. 12537428
[28]
Knaggs, A.R. The biosynthesis of shikimate metabolites. Nat. Prod. Rep.?2001, 18, 334–355, doi:10.1039/b001717p. 11476485
[29]
Fatland, B.L.; Ke, J.; Anderson, M.D.; Mentzen, W.I.; Cui, L.W.; Allred, C.C.; Johnston, J.L.; Nikolau, B.J.; Wurtele, E.S. Molecular characterization of a heteromeric ATP-citrate lyase that generates cytosolic acetyl-Coenzyme A in Arabidopsis. Plant Physiol.?2004, 130, 740–756.
[30]
Bohm, B.A. Introduction to Flavonoids; Harwood Academic Publishers: Amsterdam, The Netherlands, 1998.
[31]
Tsao, R.; Khanizadeh, S.; Dale, A. Designer fruits and vegetables with enriched phytochemicals for human health. Can. J. Plant Sci.?2006, 86, 773–786, doi:10.4141/P05-138.
[32]
Tsao, R.; Deng, Z. Separation Procedures for naturally occurring antioxidant phytochemicals. J. Chromatogr. B?2004, 812, 85–99.
[33]
Stalikas, C.D. Extraction, separation, and detection methods for phenolic acids and flavonoids. J. Sep. Sci.?2007, 30, 3268–3295, doi:10.1002/jssc.200700261. 18069740
[34]
Stalikas, C.D. Phenolic acids and flavonoids: occurrence and analytical methods. Methods Mol. Biol.?2010, 610, 65–90. 20013173
[35]
Santos-Buelga, C.; Williamson, G. Method in Polyphenol Analysis; The Royal Society of Chemistry: Cambridge, UK, 2003.
[36]
Tsao, R.; Yang, R.; Xie, S.; Sockovie, E.; Khanizadeh, S. Which polyphenolic compounds contribute to the total antioxidant activities of apple? J. Agric. Food Chem.?2005, 53, 4989–4995, doi:10.1021/jf048289h. 15941346
[37]
Chun, O.K.; Kim, D.O.; Moon, H.Y.; Kang, H.G.; Lee, C.Y. Contribution of individual polyphenolics to total antioxidant capacity of plums. J. Agric. Food Chem.?2003, 51, 7240–7245, doi:10.1021/jf0343579. 14640564
[38]
Pongsuwan, W.; Bamba, T.; Harada, K.; Yonetani, T.; Kobayashi, A.; Fukusaki, E. High–throughput technique for comprehensive analysis of Japanese green tea quality assessment using ultra–performance liquid chromatography with time-of-flight mass spectrometry (UPLC/TOF MS). J. Agric. Food Chem.?2008, 56, 10705–10708, doi:10.1021/jf8018003. 18973299
[39]
Oleszek, W.; Stochmal, A.; Janda, B. Concentration of isoflavones and other phenolics in the aerial parts of Trifolium species. J. Agric. Food Chem.?2007, 55, 8095–8100, doi:10.1021/jf072024w. 17848086
[40]
Tsao, R.; Yang, R. Optimisation of a new mobile phase to know the complex and real polyphenolic composition: Towards a total phenolic index using HPLC. J. Chromatogr. A?2003, 1018, 29–40, doi:10.1016/j.chroma.2003.08.034. 14582624
[41]
Li, L.; Tsao, R.; Yang, R.; Liu, C.; Zhu, H.; Young, J.C. Polyphenolic profiles and antioxidant activities of heartnut (Juglans ailanthifolia Var. cordiformis) and Persian walnut (Juglans regia L.). J. Agric. Food Chem.?2006, 54, 8033–8040. 17032006
[42]
Wang, H.; Cao, G.; Prior, R.L. Total antioxidant capacity of fruits. J. Agric. Food Chem.?1996, 44, 701–705, doi:10.1021/jf950579y.
[43]
Rice-Evans, C.A.; Miller, N.J.; Paganga, G. Structure-antioxidant activity relationships of flavonoids and phenolic acids. Free Radic. Biol. Med.?1996, 20, 933–956, doi:10.1016/0891-5849(95)02227-9. 8743980
[44]
Pietta, P.G. Flavonoids as antioxidants. J. Nat. Prod.?2000, 63, 1035–1042, doi:10.1021/np9904509. 10924197
[45]
Guo, J.-J.; Hsieh, H.-Y.; Hu, C.-H. Chain-breaking activity of carotenes in lipid peroxidation: A theoretical study. J. Phys. Chem. B?2009, 113, 15699–15708, doi:10.1021/jp907822h. 19886649
[46]
Perron, N.R.; Brumaghim, J.L. A review of the antioxidant mechanisms of polyphenol compounds related to iron binding. Cell Biochem. Biophys.?2009, 53, 75–100, doi:10.1007/s12013-009-9043-x. 19184542
[47]
Zhou, B.; Wu, L.-M.; Yang, L.; Liu, Z.-L. Evidence for alpha-tocopherol regeneration reaction of green tea polyphenols in SDS micelles. Free Radic. Biol. Med.?2005, 38, 78–84, doi:10.1016/j.freeradbiomed.2004.09.023. 15589374
[48]
Prior, R.L.; Wu, X.; Schauch, K. Standardized methods for the determination of antioxidant capacity and phenolics in foods and dietary supplements. J. Agric. Food Chem.?2005, 53, 4290–4302, doi:10.1021/jf0502698. 15884874
[49]
Halliwell, B. Are polyphenols antioxidants or pro-oxidants? What do we learn from cell culture and in vivo studies? Arch. Biochem. Biophys.?2008, 476, 107–112, doi:10.1016/j.abb.2008.01.028. 18284912
[50]
Disilvestro, R.A. Flavonoids as Antioxidants. In Handbook of Nutraceuticals and Functional Foods; Wildman, R.E.C., Ed.; CRC Press: Boca Raton, FL, USA, 2001; Chapter 8, pp. 127–142.
[51]
Du, Y.; Guo, H.; Lou, H. Grape seed polyphenols protect cardiac cells from apoptosis via induction of endogenous antioxidant enzymes. J. Agric. Food Chem.?2007, 55, 1695–1701, doi:10.1021/jf063071b. 17295515
[52]
Manach, C.; Donovan, J.L. Pharmacokinetics and metabolism of dietary flavonoids in humans. Free Radic. Res.?2004, 38, 771–785, doi:10.1080/10715760410001727858. 15493450
[53]
Williamson, G.; Barron, D.; Shimoi, K.; Terao, J. In vitro biological properties of flavonoid conjugates found in vivo. Free Radic. Res.?2005, 39, 457–469, doi:10.1080/10715760500053610. 16036321
[54]
Rechner, A.R.; Kuhnle, G.; Bremner, P.; Hubbard, G.P.; Moore, K.P.; Rice-Evans, C.A. The metabolic fate of dietary polyphenols in humans. Free Radic. Biol. Med.?2002, 33, 220–235, doi:10.1016/S0891-5849(02)00877-8. 12106818