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ABSTRACT: Grenache red wines were produced following three different winemaking techniques, that is, small-scale standard experimental wines and industrial-scale wines by both double-mash fermentation and fermentation in Ganimede vats. Wines were analyzed for their color properties, as well as the anthocyanin, flavonol, hydroxycinnamic acid, and pyranoanthocyanin profiles following alcoholic and malolactic fermentation. The evolution of pyranoanthocyanins and their corresponding precursors in the experimental wines was monitored at 6 and 10 months of aging. Wines produced by double-mash fermentation exhibited superior color properties compared to Ganimede wines and the experimental red wines, due to better extraction of flavonols and anthocyanins as well as a lower degree of polymerization. Pyranoanthocyanin formation varied within the different classes of pigments. Vitisins A and B were formed only during alcoholic fermentation. Pinotin A (i.e., the reaction product from malvidin 3-glucoside and caffeic acid) formation took place only during the aging process, whereas formation of hydroxyphenyl-pyranoanthocyanins derived from p-coumaric and ferulic acid followed two different pathways, that is, an enzymatically assisted production during fermentation and a pure chemical formation during aging.
Journal of Agricultural and Food Chemistry 07/2007; 55(12):4883-8. · 2.82 Impact Factor
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ABSTRACT: Anthocyanins are dietary flavonoids, which can prevent carcinogen-induced colorectal cancer in rats. Here, the hypotheses were tested that Mirtoselect, an anthocyanin mixture from bilberry, or isolated cyanidin-3-glucoside (C3G), the most abundant anthocyanin in diet, interfere with intestinal adenoma formation in the Apc(Min) mouse, a genetic model of human familial adenomatous polyposis, and that consumption of C3G or Mirtoselect generates measurable levels of anthocyanins in the murine biophase. Apc(Min) mice ingested C3G or Mirtoselect at 0.03, 0.1 or 0.3% in the diet for 12 weeks, and intestinal adenomas were counted. Plasma, urine and intestinal mucosa were analyzed for presence of anthocyanins by high-pressure liquid chromatography with detection by UV spectrophotometry (520 nm) or tandem mass spectrometry (multiple reaction monitoring). Ingestion of either C3G or Mirtoselect reduced adenoma load dose-dependently. At the highest doses of C3G and Mirtoselect adenoma numbers were decreased by 45% (p < 0.001) or 30% (p < 0.05), respectively, compared to controls. Anthocyanins were found at the analytical detection limit in the plasma and at quantifiable levels in the intestinal mucosa and urine. Anthocyanin glucuronide and methyl metabolites were identified in intestine and urine. Total anthocyanin levels in mice on C3G or Mirtoselect were 43 ng and 8.1 microg/g tissue, respectively, in the intestinal mucosa, and 7.2 and 12.3 microg/ml in the urine. The efficacy of C3G and Mirtoselect in the Apc(Min) mouse renders the further development of anthocyanins as potential human colorectal cancer chemopreventive agents worthwhile.
International Journal of Cancer 12/2006; 119(9):2213-20. · 5.44 Impact Factor
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ABSTRACT: Anthocyanins are potent antioxidants that may possess chronic disease preventive properties. Here, rapid, reliable, and reproducible solid-phase extraction, high-performance liquid chromatography (HPLC), and mass spectrometry techniques are described for the isolation, separation, and identification of anthocyanins in human plasma and urine. Recoveries of cyanidin-3-glucoside (C3G) were 91% from water, 71% from plasma, and 81% from urine. Intra- and interday variations for C3G extraction were 9 and 9.1% in plasma and 7.1 and 9.1% in urine and were less than 15% for all anthocyanins from a standardized bilberry extract (mirtoselect). Analysis of mirtoselect by HPLC with UV detection produced spectra with 15 peaks compatible with anthocyanin components found in mirtoselect within a total run time of 15 min. Chromatographic analysis of human urine obtained after an oral dose of mirtoselect yielded 19 anthocyanin peaks. Mass spectrometric analysis employing multiple reaction monitoring suggests the presence of unchanged anthocyanins and anthocyanidin glucuronide metabolites.
Journal of Agricultural and Food Chemistry 10/2006; 54(19):7009-13. · 2.82 Impact Factor
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ABSTRACT: The prefermentation addition of copigments led to significantly different red wines according to the copigment structure (flavonol or hydroxycinnamic acid) and the grape cultivar [Tempranillo (= Cencibel) or Cabernet Sauvignon]. The flavonol rutin enhanced copigmentation and anthocyanin extraction, improving the red color, but the hydroxycinnamic acids (especially caffeic acid) had converse results. The above effects were higher in Cabernet Sauvignon wines, particularly if rutin or p-coumaric acid was used. These wines showed the highest copigmentation as they contained more anthocyanins and flavonols, whereas the coumaroylated anthocyanins of Tempranillo wines could have prevented the action of the added copigments. After 21 months, the main pyranoanthocyanins found were the malvidin-3-glucoside 4-vinylphenol and the malvidin-3-glucoside 4-vinylcatechol (pinotin A) adducts. The results suggested that the former adduct was primarily generated following enzymatic decarboxylation of p-coumaric acid during fermentation, whereas pinotin A was formed through a pure chemical reaction, which depended on the concentration of free caffeic acid during aging.
Journal of Agricultural and Food Chemistry 11/2005; 53(21):8372-81. · 2.82 Impact Factor
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ABSTRACT: The prefermentation addition of copigments led to significantly different red wines according to the copigment structure (flavonol or hydroxycinnamic acid) and the grape cultivar [Tempranillo (= Cencibel) or Cabernet Sauvignon]. The flavonol rutin enhanced copigmentation and anthocyanin extraction, improving the red color, but the hydroxycinnamic acids (especially caffeic acid) had converse results. The above effects were higher in Cabernet Sauvignon wines, particularly if rutin or p-coumaric acid was used. These wines showed the highest copigmentation as they contained more anthocyanins and flavonols, whereas the coumaroylated anthocyanins of Tempranillo wines could have prevented the action of the added copigments. After 21 months, the main pyranoanthocyanins found were the malvidin-3-glucoside 4-vinylphenol and the malvidin-3-glucoside 4-vinylcatechol (pinotin A) adducts. The results suggested that the former adduct was primarily generated following enzymatic decarboxylation of p-coumaric acid during fermentation, whereas pinotin A was formed through a pure chemical reaction, which depended on the concentration of free caffeic acid during aging. Keywords: Vitis vinifera; red wine; Cabernet Sauvignon; tempranillo; cencibel; anthocyanins; pyranoanthocyanins; aging products; copigmentation; rutin; caffeic acid; coumaric acid; pinotin A; vinylphenol
09/2005;
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ABSTRACT: A red wine, made from Cabernet Sauvignon (60%) and Tannat (40%) cultivars, was fractionated by high speed countercurrent chromatography (HSCCC). The biphasic solvent system consisting of tert-butyl methyl ether/n-butanol/acetonitrile/water (2/2/1/5, acidified with 0.1% trifluoroacetic acid) was chosen for its demonstrated efficiency in separating anthocyanins. The different native and derived anthocyanins were identified on the basis of their UV-visible spectra, their elution time on reversed-phase high-performance liquid chromatography (HPLC), and their mass spectra, before and after thiolysis. The HSCCC method allowed the separation of different families of anthocyanin-derived pigments that were eluted in different fractions according to their structures. The hydrosoluble fraction was almost devoid of native anthocyanins. Further characterization (glucose quantification, UV-visible absorbance measurements) indicated that it contained flavanol and anthocyanin copolymers in which parts of the anthocyanin units were in colorless forms. Pigments in the hydrosoluble fraction showed increased resistance to sulfite bleaching and to the nucleophilic attack of water.
Journal of Agricultural and Food Chemistry 07/2005; 53(11):4536-46. · 2.82 Impact Factor
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ABSTRACT: Anthocyanins from blood orange [Citrus sinensis (L.) Osbeck] juices were isolated and purified by means of high-speed countercurrent chromatography and preparative high-performance liquid chromatography. Structures of the pigments were then elucidated by electrospray ionization multiple mass spectrometry and nuclear magnetic resonance (NMR) spectroscopy. The major anthocyanins of the juice were characterized as cyanidin 3-glucoside and cyanidin 3-(6"-malonylglucoside). Furthermore, six minor anthocyanins were detected and identified as cyanidin 3,5-diglucoside, delphinidin 3-glucoside, cyanidin 3-sophoroside, delphinidin 3-(6"-malonylglucoside), peonidin 3-(6"-malonylglucoside), and cyanidin 3-(6"-dioxalylglucoside). The occurrence of the latter compound in blood oranges is reported here for the first time, together with full NMR spectroscopic data. Further investigations revealed the presence of four anthocyanin-derived pigments, which are formed through a direct reaction between anthocyanins and hydroxycinnamic acids during prolonged storage of the juice. These novel pyranoanthocyanins were identified as the 4-vinylphenol, 4-vinylcatechol, 4-vinylguaiacol, and 4-vinylsyringol adducts of cyanidin 3-glucoside through comparison of their mass spectrometric and chromatographic properties with those of synthesized reference compounds.
Journal of Agricultural and Food Chemistry 01/2005; 52(24):7331-8. · 2.82 Impact Factor
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ABSTRACT: Six novel pyranoanthocyanins were identified by HPLC-ESI-MSn in black carrot (Daucus carota L. ssp. sativus var. atrorubens Alef.) juice. The two major compounds, namely, the vinylcatechol adducts of cyanidin 3-O-(6-O-feruloyl-beta-D-glucopyranosyl)-(1-->6)-[beta-D-xylopyranosyl-(1-->2)]-beta-D-galactopyranoside and cyanidin 3-O-[beta-D-xylopyranosyl-(1-->2)]-beta-D-galactopyranoside, respectively, were isolated by a combination of high-speed countercurrent chromatography with semipreparative HPLC. Their structures were fully elucidated by means of one- and two-dimensional NMR spectroscopy and high-resolution mass spectrometry. The four remaining pigments were characterized as the vinylphenol and vinylguaiacol adducts of cyanidin 3-O-[beta-D-xylopyranosyl-(1-->2)]-beta-D-galactopyranoside, the vinylguaiacol adduct of cyanidin 3-O-(6-O-feruloyl-beta-D-glucopyranosyl)-(1-->6)-[beta-D-xylopyranosyl-(1-->2)]-beta-D-galactopyranoside, and the vinylcatechol adduct of cyanidin 3-O-(6-O-sinapoyl-beta-d-glucopyranosyl)-(1-->6)-[beta-D-xylopyranosyl-(1-->2)]-beta-D-galactopyranoside. These compounds are formed during storage of the juice through the direct reaction of either caffeic, ferulic, or coumaric acid with the respective genuine anthocyanins.
Journal of Agricultural and Food Chemistry 09/2004; 52(16):5095-101. · 2.82 Impact Factor
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ABSTRACT: Pinotage red wines were found to contain a reaction product of malvidin 3-glucoside and caffeic acid, the so-called pinotin A. A total of 50 Pinotage wines from the vintages 1996-2002 were analyzed for the content of pinotin A, malvidin 3-glucoside, caffeic acid, and caftaric acid. Statistical analyses were performed to reveal variations in the content of these compounds and to determine the factors that influence pinotin A formation during wine aging. An exponential increase of the concentration of this aging product was observed with prolonged storage time. The most rapid synthesis of pinotin A was observed in 2.5-4 year old wines, although at this age malvidin 3-glucoside is already degraded to a large extent. This phenomenon is explained by the increased ratio of caffeic acid/malvidin 3-glucoside, which strongly favors the formation of pinotin A and makes side reactions less likely. Pinotin A formation proceeds as long as a certain level of malvidin 3-glucoside is maintained in the wines. In wines >5-6 years old degradation or polymerization of pinotin A finally exceeds the rate of its de novo synthesis.
Journal of Agricultural and Food Chemistry 02/2004; 52(3):498-504. · 2.82 Impact Factor
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ABSTRACT: Vitisin A was prepared from malvidin 3-glucoside and pyruvic acid in model wine medium, isolated by countercurrent chromatography, and purified by preparative high-performance liquid chromatography (HPLC). The synthesized compound was used as a reference standard to quantify vitisin A in Chilean wines from Vitis vinifera cv. Cabernet Sauvignon, including a vertical row of wines from the same vineyard over 16 years. Maximum vitisin A content was reached within the first year of storage. Importantly, up to half of the initial amount of vitisin A in young wines was still present in 15 year old wines. Although vitisin A was found to be much more stable as compared to other monomeric C-4 underivatized anthocyanins, it also slowly degrades after reaching its peak concentration. The "color activity concept" was applied to vitisin A, malvidin 3-glucoside, malvidin 3-(6' '-acetylglucoside), and polymeric pigments isolated by countercurrent chromatography in order to estimate their contribution toward the overall color expression of wines. It was found that vitisin A is only a minor contributor to the visually perceived color of aged red wines (color contribution approximately 5%). The major contributor is the polymeric fraction (color contribution approximately 70-90%).
Journal of Agricultural and Food Chemistry 11/2003; 51(21):6261-7. · 2.82 Impact Factor
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ABSTRACT: On the basis of observations from Vitis vinifera cv. Pinotage wines and experiments performed in model wine medium, a new chemical pathway responsible for the formation of anthocyanin-vinylphenol adducts in red wines is described. Until now, these pigments have been considered to be reaction products of anthocyanins and vinylphenols, the latter being generated during fermentation by enzymatic decarboxylation of the respective cinnamic acids. The mechanism of the novel pathway, involving intact hydroxycinnamic acid and anthocyanin, is explained. Only cinnamic acids with electron-donating substituents on the aromatic ring, such as coumaric acid, ferulic acid, caffeic acid, and sinapic acid, undergo this conversion, as they stabilize an intermediately formed carbenium ion. Decarboxylation and oxidation of the pyran moieties are the final steps in the generation of the corresponding 4-vinylphenol, 4-vinylguaiacol, 4-vinylcatechol, and 4-vinylsyringol adducts of anthocyanins in red wine.
Journal of Agricultural and Food Chemistry 07/2003; 51(12):3682-7. · 2.82 Impact Factor
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ABSTRACT: The paper reports the use of anthocyanins as natural food colorants and their potential health benefits regarding coronary heart disease and cancer prevention. The principles of countercurrent chromatography are described and several applications dealing with the isolation of anthocyanins from Tradescantia pallida leaves, purple corn, elderberry juice, red wine and blackberries are presented. Several hundred milligrams of pure anthocyanins were obtained within a single CCC run. Isolated pigments include monoglycosylated, acylated and highly glycosylated derivatives of anthocyanins. Purity and identity of the isolated anthocyanins were confirmed by HPLC with diode array detection, HPLC-electrospray ionization multiple mass spectrometry and nuclear magnetic resonance spectroscopy.
Biochemical Engineering Journal.
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ABSTRACT: Little is known about the content and development of pyranoanthocyanins, pigments mainly formed during red wine ageing, in commercial wines. Some of the major pyranoanthocyanins in a wide selection of 1–10 years-old Spanish Tempranillo wines and also in a 29 years wide-vertical series of Tempranillo wines from an individual cellar have been determined. Great variability in pyranoanthocyanin concentrations was found (range, mg/l): vitisin A, 0–10.76; pinotin A, 0–4.26; and malvidin 3-glucoside-4-vinylphenol, 0.03–1.37. Vitisin A and malvidin 3-glucoside-4-vinylphenol were already present in 1–2 years-old wines, whereas pinotin A was only detectable in a few of the 1 and 2 years-old wines. Vitisin A tended to decrease with wine age, while hydroxyphenyl-pyranoanthocyanins showed the reverse trend. However, the aforementioned trends were interrupted by various temporary maxima, most likely due to some “refreshment” of the oldest wines (i.e., addition of young wine), as suggested by unexpected high concentrations of malvidin 3-glucoside, in contrast to the results found in the wine vertical series. The effects of addition of young wine on aged wine pyranoanthocyanin concentrations were confirmed by wine refreshment experiments.
Food Chemistry. 119(4):1426-1434.
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ABSTRACT: Since the identification of a new class of anthocyanin-derived pigments in red wine, the so-called pyranoanthocyanins, a lot of scientific information have been published dealing with different aspects of these pigments. Depending on their origin as well as different pathways of formation in foodstuff, the pyranoanthocyanins possess varying chemical structures. This report presents an overview of different classes of pyranoanthocyanins, their formation, occurrence, and their relevance for the color and analysis of aged fruit juices and wines.
Trends in Food Science & Technology.
