Metabolite profiling of grape: Flavonols and anthocyanins.

Flavonols are products of the flavonoid biosynthetic pathway, which also give rise to anthocyanins and condensed tannins in grapes. We investigated their presence in the berry skins of 91 grape varieties (Vitis vinifera L.), in order to produce a classification based on the flavonol profile. The presence of laricitrin 3-O-galactoside and syringetin 3-O-galactoside in red grapes is reported here for the first time. In red grapes, the main flavonol was quercetin (mean = 43.99%), followed by myricetin (36.81%), kaempferol (6.43%), laricitrin (5.65%), isorhamnetin (3.89%), and syringetin (3.22%). In white grapes, the main flavonol was quercetin (mean = 81.35%), followed by kaempferol (16.91%) and isorhamnetin (1.74%). The delphinidin-like flavonols myricetin, laricitrin, and syringetin were missing in all white varieties, indicating that the enzyme flavonoid 3',5'-hydroxylase is not expressed in white grape varieties. The pattern of expression of flavonols and anthocyanins in red grapes was compared, in order to gain information on the substrate specificity of enzymes involved in flavonoid biosynthesis.

[1]  Y. Mo,et al.  Analysis of Sweet cherry (Prunus avium L.) Leaves for Plant Signal Molecules That Activate the syrB Gene Required for Synthesis of the Phytotoxin, Syringomycin, by Pseudomonas syringae pv syringae , 1995, Plant physiology.

[2]  J. Espín,et al.  Varietal differences among the polyphenol profiles of seven table grape cultivars studied by LC-DAD-MS-MS. , 2002, Journal of agricultural and food chemistry.

[3]  F. Mattivi,et al.  Analytical Characterisation of Myrtle Berries, partially Processed Products ans Commercially Available Liqueurs. , 2002 .

[4]  T. Holton,et al.  Genetics and Biochemistry of Anthocyanin Biosynthesis. , 1995, The Plant cell.

[5]  M. Downey,et al.  The effect of bunch shading on berry development and flavonoid accumulation in Shiraz grapes , 2008 .

[6]  P. Boss,et al.  Anthocyanin composition and anthocyanin pathway gene expression in grapevine sports differing in berry skin colour , 1996 .

[7]  K. Norris,et al.  Co-pigmentation of anthocyanins in plant tissues and its effect on color , 1972 .

[8]  S. Flint,et al.  PLANT PROTECTIVE RESPONSE TO ENHANCED UV‐B RADIATION UNDER FIELD CONDITIONS: LEAF OPTICAL PROPERTIES and PHOTOSYNTHESIS , 1985 .

[9]  G. Hrazdina,et al.  CO‐PIGMENTATION OF ANTHOCYANINS UNDER PHYSIOLOGICAL CONDITIONS , 1978 .

[10]  C. Bailly,et al.  Characterization and activities of S-adenosyl-L-methionine:cyanidin 3-glucoside 3'-O-methyltransferase in relation to anthocyanin accumulation in Vitis vinifera cell suspension cultures , 1997 .

[11]  C. Tringali,et al.  Constituents of grape pomace from the Sicilian cultivar `Nerello Mascalese' , 2004 .

[12]  C. Mardones,et al.  Varietal authenticity verification of Cabernet sauvignon, Merlot and Carmenère wines produced in Chile by their anthocyanin, flavonol and shikimic acid profiles , 2005 .

[13]  C. Honda,et al.  Myb-related genes of the Kyoho grape (Vitis labruscana) regulate anthocyanin biosynthesis , 2002, Planta.

[14]  Mcdonald,et al.  Survey of the Free and Conjugated Myricetin and Quercetin Content of Red Wines of Different Geographical Origins. , 1998, Journal of agricultural and food chemistry.

[15]  Julie M. Tarara,et al.  Separation of Sunlight and Temperature Effects on the Composition of Vitis vinifera cv. Merlot Berries , 2002, American Journal of Enology and Viticulture.

[16]  S. Price,et al.  Cluster Sun Exposure and Quercetin in Pinot noir Grapes and Wine , 1995, American Journal of Enology and Viticulture.

[17]  F. Mattivi,et al.  Stable free radicals and peroxyl radical trapping capacity in red wines. , 2004, Journal of agricultural and food chemistry.

[18]  E. Peterlunger,et al.  Colour variation in red grapevines (Vitis vinifera L.): genomic organisation, expression of flavonoid 3'-hydroxylase, flavonoid 3',5'-hydroxylase genes and related metabolite profiling of red cyanidin-/blue delphinidin-based anthocyanins in berry skin , 2006, BMC Genomics.

[19]  V. Cheynier,et al.  HPLC Separation and Characterization of Flavonols in the Skins ofVitis viniferavar. Cinsault , 1986, American Journal of Enology and Viticulture.

[20]  G. Mazza,et al.  Anthocyanins in grapes and grape products. , 1995, Critical reviews in food science and nutrition.

[21]  Fulvio Mattivi,et al.  Quantitation of polyphenols in different apple varieties. , 2004, Journal of agricultural and food chemistry.

[22]  Gary Williamson,et al.  Bioavailability and bioefficacy of polyphenols in humans. I. Review of 97 bioavailability studies. , 2005, The American journal of clinical nutrition.

[23]  Liliana Jiménez,et al.  Polyphenols: food sources and bioavailability. , 2004, The American journal of clinical nutrition.

[24]  R. Boulton.  The Copigmentation of Anthocyanins and Its Role in the Color of Red Wine: A Critical Review , 2001, American Journal of Enology and Viticulture.

[25]  R. Ibrahim,et al.  cDNA cloning and characterization of a 3′/5′-O-methyltransferase for partially methylated flavonols from Chrysosplenium americanum , 1996, Plant Molecular Biology.

[26]  A. Ebadi,et al.  Identification of the Flavonoid Hydroxylases from Grapevine and Their Regulation during Fruit Development1 , 2005, Plant Physiology.

[27]  Hirohiko Hirochika,et al.  Retrotransposon-Induced Mutations in Grape Skin Color , 2004, Science.

[28]  F. Mattivi,et al.  Characterization of grapes cultivated in sardinia chemometric methods applied to the anthocyanic fraction , 1992 .

[29]  Haibo Wang,et al.  Anthocyanin transformation in Cabernet Sauvignon wine during aging. , 2003, Journal of agricultural and food chemistry.

[30]  M. Downey,et al.  Synthesis of flavonols and expression of flavonol synthase genes in the developing grape berries of Shiraz and Chardonnay (Vitis vinifera L.) , 2003 .

[31]  C. Tonelli,et al.  Cloning and molecular analysis of structural genes involved in flavonoid and stilbene biosynthesis in grape (Vitis vinifera L.) , 1994, Plant Molecular Biology.

[32]  S. Delrot,et al.  Isogene specific oligo arrays reveal multifaceted changes in gene expression during grape berry (Vitis vinifera L.) development , 2004, Planta.

[33]  N. Goto-Yamamoto,et al.  Organ-Specific Transcription of Putative Flavonol Synthase Genes of Grapevine and Effects of Plant Hormones and Shading on Flavonol Biosynthesis in Grape Berry Skins , 2006, Bioscience, biotechnology, and biochemistry.

[34]  N. Goto-Yamamoto,et al.  A Skin Color Mutation of Grapevine, from Black-Skinned Pinot Noir to White-Skinned Pinot Blanc, Is Caused by Deletion of the Functional VvmybA1 Allele , 2006, Bioscience, biotechnology, and biochemistry.

[35]  M. Esaka,et al.  Expression of the flavonoid 3′-hydroxylase and flavonoid 3′,5′-hydroxylase genes and flavonoid composition in grape (Vitis vinifera) , 2006 .

[36]  Kazuki Saito,et al.  Recent advances in the biosynthesis and accumulation of anthocyanins. , 2003, Natural product reports.