Determination of stilbenes (delta-viniferin, trans-astringin, trans-piceid, cis- and trans-resveratrol, epsilon-viniferin) in Brazilian wines

Phenolics from grapes and wines can play a role against oxidation and development of atherosclerosis. Stilbenes have been shown to protect lipoproteins from oxidative damage and to have cancer chemopreventive activity. We describe a method for the direct determination of stilbenes in several red wines using high-performance liquid chromatography with UV detection. In a survey of 12 commercial wines from the south of Brazil (Rio Grande del Sul), levels of delta-viniferin are reported for the first time in different varieties of red wines. Brazilian red wine contains trans-astringin, trans-piceid, trans-resveratrol, cis-resveratrol (in high quantity: 5 times more than the trans form), epsilon-viniferin, and a compound isolated for the first time in wine, trans-delta-viniferin. Isolation and identification of delta-viniferin was achieved by NMR after extraction and fractionation of red wine phenolics. delta-Viniferin contributes, as well as cis-resveratrol and trans-piceid, to a significant proportion of stilbenes in wine dietary intake, particularly with Merlot varieties containing an average level of 10 mg/L for delta-viniferin, 15 mg/L for cis-resveratrol, and 13 mg/L for trans-piceid. The total stilbene intake from wine origin was estimated for the Brazilian population as 5.3 mg/day per person (on the basis of a regular wine consumption of 160 mL/day). delta-Viniferin can contribute to around 20% of total stilbenes in wine (average of 6.4 mg/L in red Brazilian wines). It would be important in the future to investigate the origins of the differences in wine stilbene levels in relation to the vine varieties, and the bioavailability of the newly extracted stilbene delta-viniferin in plasma after consumption of different types of wines.     

Foam aptitude of trepat and monastrell red varieties in cava elaboration. 2. Second fermentation and aging

The foam properties of sparkling wines (Cava) made from two red autochthonous grape varieties, Trepat and Monastrell, and coupages, including different percentages of them, were studied during second fermentation and aging. The effect of second fermentation on foam gave the highest decreases when the base wines had the highest foam values, while gave the lowest decreases or even increases for the base wines with the lowest foam characteristics. However, the greater the HM and Sigma of the base wine, the greater the foam values of the sparkling wine. Base wine determinations for quality control in cellars could provide information about future sparkling wine foaming. Acidity parameters, ethanol, sulfur, and polysaccharides contents were correlated to foam characteristics in the sparkling wines. In terms of color and foaming, wines made from the red varieties Trepat and Monastrell blended with white variety wines could be appropriate for elaborating "blanc de noirs" sparkling wines.     

Piceid, the major resveratrol derivative in grape juices

The levels of trans-piceid, cis-piceid, trans-resveratrol, and cis-resveratrol have been measured in 36 grape juices using an HPLC system with spectral analysis of eluting peaks. The piceid (glucosides) were the major component in the grape juices. In red grape juices the average concentrations were 3.38 mg/L for trans-piceid, 0.79 mg/L for cis-piceid, 0.50 mg/L for trans-resveratrol, and 0.06 mg/L for cis-resveratrol. In white grape juices the levels were, on average, 0.18 mg/L for trans-piceid, 0.26 mg/L for cis-piceid, and 0.05 mg/L for trans-resveratrol, and cis-resveratrol was not detected in any sample. Levels of total resveratrol (trans- and cis-resveratrol and -piceid) found in red and in white grape juices are similar to those described in Spanish red and white wines. Due to their resveratrol content, as well as other phenolics, grape juices may have a beneficial health effect of interest to those who cannot drink wine.     

Foam aptitude of trepat and monastrell red varieties in cava elaboration. 1. Base wine characteristics

The foam properties of base wines made from red autochthonous varieties (Trepat and Monastrell) were studied. Four wines of each variety were elaborated (fermented off skins at industrial scale in two consecutive harvests) and blended at different proportions with the white traditional variety (Macabeo, Xarel.lo, and Parellada) wines to elaborate Cava (closed-bottle-fermented sparkling wine). When crescent amounts of Trepat were added to the traditional white blend, the foamability and the color intensity (CI) of the wine increased polinomically. The increase of the CI depended on the year of harvest. Thus, oenologists could decide the blend proportion most suitable to elaborate either a "blanc de noirs" sparkling wine or a new type of Cava.     

Positive correlation between high levels of ochratoxin A and resveratrol-related compounds in red wines

The natural occurrence of ochratoxin A in red wines has been widely reported by several authors, as well as a that of group of stilbenes including cis- and trans-resveratrols and related glucosylated forms. In the present study 112 samples of retail red wines were collected from northern (17), central (46), and southern (49) Italy and were analyzed for both ochratoxin A and resveratrol-related stilbenes. The mean levels of total resveratrols and total piceids were 3.14 and 5.80 mg/L, respectively, whereas the ochratoxin A mean level was 0.64 microg/L. The Merlot wines showed the highest mean value of total stilbenes, followed by Negroamaro and Negroamaro blend, Aglianico, and Syrah, all with mean levels of >10 mg/L. Ochratoxin A was detected in 70, 59, and 100% of wine samples from northern, central, and southern Italy, with mean levels of 0.12, 0.07, and 1.36 microg/L, respectively. The highest values of ochratoxin A were recorded in Negroamaro- and Primitivo-based wine samples from southern Italy, showing also the highest content of stilbenes. In wine samples from southern Italy, a positive correlation was obtained between levels of ochratoxin A and total stilbenes (r = 0.74) as well as between ochratoxin A and total resveratrols (r = 0.50) and between ochratoxin A and total piceids (r = 0.74). These results suggest that toxic levels of ochratoxin A in red wine may be, at some extent, counterbalanced by the beneficial effects of resveratrol derivatives. Further investigation should be warranted in this regard.     

Effect of micro-oxygenation on color and anthocyanin-related compounds of wines with different phenolic contents

Several factors may affect the results obtained when micro-oxygenation is applied to red wines, the most important being the moment of application, the doses of oxygen, and the wine phenolic characteristics. In this study, three red wines, made from Vitis vinifera var. Monastrell (2005 vintage) and with different phenolic characteristics, were micro-oxygenated to determine as to how this technique affected the formation of new pigments in the wines and their chromatic characteristics. The results indicated that the different wines were differently affected by micro-oxygenation. In general, the micro-oxygenated wines had a higher percentage of new anthocyanin-derived pigments, being that this formation is more favored in the wines with the highest total phenol content. These compounds, in turn, significantly increased the wine color intensity. The wine with the lowest phenolic content was less influenced by micro-oxygenation, and the observed evolution in the degree of polymerization of tannins suggested that it might have suffered overoxygenation.     

Anthocyanin and proanthocyanidin content in selected white and red wines. Oxygen radical absorbance capacity comparison with nontraditional wines obtained from highbush blueberry

Antioxidant capacity, as measured by oxygen radical absorbance capacity (ORAC(PE)), total phenolic, total and individual anthocyanins, and proanthocyanidin fraction contents were evaluated in red and white wines from grapes. A comparison in terms of antioxidant capacity is made with nontraditional wines made from highbush blueberry. Blueberries are among fruits that are best recognized for their potential health benefits. In red wines, total oligomeric proanthocyanidin content, including catechins, was substantially higher (177.18 +/- 96.06 mg/L) than that in white wines (8.75 +/- 4.53 mg/L). A relative high correlation in red wines was found between ORAC(PE) values and malvidin compounds (r = 0.75, P < 0.10), and proanthocyanidins (r = 0.87, P < 0.05). In white wines, a significant correlation was found between the trimeric proanthocyanidin fraction and peroxyl radical scavenging values (r = 0.86, P < 0.10). A moderate drink (1 drink per day, about 140 mL) of red wine, or white wine, or wine made from highbush blueberry corresponds to an intake of 2.04 +/- 0.81 mmol of TE, 0.47 +/- 0.15 mmol of TE, and 2.42 +/- 0.88 mmol of TE of ORAC(PE)/day, respectively.     

Plant foods and herbal sources of resveratrol

Stilbenes, in particular trans-resveratrol and its glucoside, are widely reported to be beneficial to health, having been shown to possess antioxidative, anticarcinogenic, and antitumor properties. Major dietary sources include grapes, wine, peanuts, and soy; however, they can also be introduced into the diet through Itadori tea, which has long been used in Japan and China as a traditional herbal remedy for heart disease and strokes. Analysis of grapes, peanuts, and Itadori tea shows that they contain mainly trans-resveratrol glucoside. In contrast, red wines are primarily a source of the aglycones cis- and trans-resveratrol. While peanuts and grapes contain low levels of the stilbenes, Itadori tea and red wine both supply relatively high concentrations of resveratrol. For people who do not consume alcohol, Itadori tea may be a suitable substitute for red wine. However, further study on the potential biological effects of other endogenous compounds in Itadori tea is required and there is also a need for more information on the absorption and in vivo biomedical actions of free and conjugated resveratrol.     

Levels of stilbene oligomers and astilbin in French varietal wines and in grapes during noble rot development

Phenolics from grapes and wines can play a role against oxidation and development of atherosclerosis. Stilbenes have been shown to have cancer chemopreventive activity and to protect lipoproteins from oxidative damage. A method for the direct determination of stilbene oligomers (viniferin and pallidol) as well as astilbin in different types of wine using high-performance liquid chromatography with UV detection is described. In a survey of 21 commercial wines from the south of France, levels of pallidol and viniferin are reported for the first time in different types of wines. Viniferin was found to be present only in red and botrytized sweet white wines with levels between 0.1 and 1.63 mg/L; pallidol was not found in dry and sweet white wines but only in wines made by maceration with stems, with levels between 0.38 and 2.22 mg/L. Highest levels of astilbin were found in Egiodola (15.13 mg/L), Merlot (11.61 mg/L), and Cabernet Sauvignon (8.24 mg/L) for red wines and in Sauvignon (5.04 mg/L) for white varietal wines. Astilbin levels are highest for recent vintages, but pallidol is not found in older vintages. During noble rot development in Sauvignon or Sémillon grapes from the Sauternes area, levels of trans-astringin, trans-resveratrol, trans-piceid, and pallidol are quite low (<0.5 mg/kg of grapes). Viniferin and astilbin levels become optimum at 2 and 30 mg/kg, respectively, during spot grape and speckle grape stages.     

Relationship among antioxidant activity, vasodilation capacity, and phenolic content of red wines

The relationship among antioxidant activity, based on the electron-spin resonance determination of the reduction of Fremy's radical, vasodilation activity, and phenolic content was investigated in 16 red wines. The wines were selected to provide a range of origins, grape varieties, and vinification methods. Sensitive and selective HPLC methods were used for the analysis of the major phenolics in red wine: free and conjugated myricetin, quercetin, kaempferol, and isorhamnetin; (+)-catechin, (-)-epicatechin, gallic acid, p-coumaric acid, caffeic acid, caftaric acid, trans-resveratrol, cis-resveratrol, and trans-resveratrol glucoside. Total anthocyanins were measured using a colorimetric assay. The total phenolic content of the wines was determined according to the Folin-Ciocalteu colorimetric assay and also by the cumulative measurements obtained by HPLC. The 16 wines exhibited a wide range in the values of all parameters investigated. However, the total phenol contents, measured both by HPLC and colorimetrically, correlated very strongly with the antioxidant activity and vasodilation activity. In addition, the antioxidant activity was associated with gallic acid, total resveratrol, and total catechin. In contrast, only the total anthocyanins were correlated with vasodilation activity. The results demonstrate that the different phenolic profiles of wines can produce varying antioxidant and vasodilatant activities, which opens up the possibility that some red wines may provide enhanced health benefits for the consumer.     

Postharvest UV-C-irradiated grapes as a potential source for producing stilbene-enriched red wines

The use of postharvest controlled irradiation by UV pulses is proposed as a potential method to produce stilbene-enriched red wine. "Monastrell" grapes were UV-C-irradiated to increase stilbene content. The main inducible stilbenes were resveratrol and piceatannol, which are molecules with reported health-beneficial activities. The evolution of both compounds was followed in the different steps of an "analytical" traditional maceration wine-making process. The final wine made from UV-C-irradiated grapes was enriched about 2- and 1.5-fold in resveratrol and piceatannol, respectively, when compared to the control wine. In addition, no difference was detected regarding the standard enological parameters (color, acidity, etc.). It is strongly suggested that, with the use of more susceptible wine grapes to induce bioactive stilbenes upon UV-C irradiation, the stilbene-enrichment of wine can be much higher.     

Antioxidant capacities and phenolics levels of French wines from different varieties and vintages.

Phenolics from grapes and wines can play a role against oxidation and development of atherosclerosis. Levels of phenolics, major catechins [(+)-catechin, (-)-epicatechin, procyanidin dimers B1, B2, B3, and B4], phenolic acids (gallic acid and caffeic acid), caftaric acid, malvidin-3-glucoside, peonidin-3-glucoside, and cyanidin-3-glucoside were quantified by HPLC with UV detection for 54 French varietal commercial wines taken from southern France to study the antioxidant capacity and the daily dietary intake of these compounds for the French population. The highest antioxidant capacity was obtained with red wines and ranged from 12.8 mmol/L (Grenache) to 25.2 mmol/L (Pinot Noir). For white wines, Chardonnay enriched in phenolics by special wine-making was found to have an antioxidant capacity of 13.8 mmol/L, comparable to red wine values. For red wines classified by vintages (1996-1999) antioxidant capacities were approximately 20 mmol/L and then decreased to 13.4 mmol/L for vintages 1995-1991. Sweet white wines have 1.7 times more antioxidant capacity (3.2 mmol/L) than dry white wines (1.91 mmol/L). On the basis of a still significant French wine consumption of 180 mL/day/person, the current daily intake of catechins (monomers and dimers B1, B2, B3, and B4) averaged 5 (dry white wine), 4.36 (sweet white wines), 7.70 (rosé wines), 31.98 (red wines), and 66.94 (dry white wine enriched in phenolic) mg/day/resident for the French population. Red wine, and particularly Pinot Noir, Egiodola, Syrah, Cabernet Sauvignon, and Merlot varieties, or Chardonnay enriched in phenolics during wine-making for white varieties contribute to a very significant catechin dietary intake.     

Postharvest stilbene-enrichment of red and white table grape varieties using UV-C irradiation pulses

The red table grape varieties Flame, Red Globe, Crimson, and Napoleon, as well as the white varieties Superior, Dominga, and Moscatel Italica, were irradiated with a previously optimized UV-C postharvest irradiation protocol (510 W, 40 cm, 60 s). The induction kinetics of the stilbenes trans-resveratrol, trans-piceid, trans-piceatannol, trans-astringin, and viniferins was followed by using HPLC-DAD/MS/MS. The most inducible stilbenes were trans-resveratrol, trans-piceatannol, and viniferins. Both quantitative and qualitative differences were observed in both the stilbene induction kinetics and stilbene content in the seven table grapes analyzed here. The total resveratrol content ranged from 0.69 mg/100 g fw (Dominga) to 2.3 mg/100 g fw (Red Globe). The net resveratrol induction ranged from 3.4-fold (Flame) to 2315-fold (Red Globe). The highest viniferins content was observed in the variety Flame (0.73 mg/100 g fw), although the variety Red Globe presented the highest viniferins induction (175-fold). The highest content and induction of piceatannol (0.17 mg/100 g fw and 173-fold, respectively) was observed in the variety Flame. It should be stressed that taking into account the health-beneficial effects claimed for stilbenes, the UV-C irradiated table grapes can be considered as new functional fruits that can supply (a serving of unpeeled 200 g table grapes) the resveratrol content (depending on the variety) equivalent to more than seven glasses of red wine ( approximately 1.5 L) with high resveratrol content.     

Changes during storage in conventional and ecological wine: phenolic content and antioxidant activity

Polyphenol content, free radical scavenging capacity, and changes during storage over 7 months in the dark were studied in ecological and conventional red and white wines. In red wines, the most changeable components during storage were the anthocyanins since during storage anthocyanins content decreased 88% in conventional wine and 91% in ecological wine. Initially, the total flavonol contents of the conventional and ecological red wines were 163.88 +/- 2.69 and 153.58 +/- 1.71 mg/L, respectively, and no significant variations occurred during storage. No differences in hydroxycinnamic acid derivatives content between conventional and ecological red and white wines were observed. The flavonol level in white wines was very low, as expected since these compounds are found in grape skin. The initial antioxidant activity was 5.37 +/- 0.14 and 5.82 +/- 0.31 mM equivalents Trolox for conventional and ecological red wines, respectively; no significant differences were observed (p = 0.2831), and these values were 7-8 times higher than the antioxidant activity observed in conventional and ecological white wine. In contrast with other studies, the total concentrations of phenolic compounds in conventional and ecological red and white wines were not related to antioxidant activity (p > 0.05). In red wines, no significant differences were observed in the antioxidant activity of ecological and conventional red wine (p = 0.28), while in white wine significant differences were observed in the antioxidant activity between conventional and ecological white wine (p = 0.006).     

Influence of oak wood on the aromatic composition and quality of wines with different tannin contents

The aromatic compounds associated with aging in wood have been studied in Monastrell wines containing different quantities of tannin. Analyses were carried out before and after a six month period in wooden barrels (225 L) of American and French (Allier) medium-toasted oak. Three classes of wine were made: one from a free-run must; one to which enological tannin was added; and one to which was added the wine obtained by pressing the grape pomaces. The aromas were determined by GC-MS, and the quality was evaluated by a group of expert tasters. The aromatic compounds, some of which came from the wines themselves and others which came from the wood, all increased in concentration by the end of the aging process. The ratio between cis- and trans-whiskylactone contents in wines reflected the different types of oak wood used. The note "vanilla" used by the tasters is probably not totally due to the presence of vanillin. The wines of best quality were those with a natural tannin content which had been aged in American oak, whereas the wines to which enological tannin had been added but aged in the same wood were considered the worst. An equalizing effect on the sensorial wines qualities was seen to result from the use of French oak. The furfural, eugenol, and cis-, and in some cases trans-, whiskylactone contents identified the wines from the different classes of wood. The wood from which the barrels were made had a greater effect on wines differentiation than the tannin content.     

Direct HPLC analysis of quercetin and trans-resveratrol in red wine,grape, and winemaking byproducts

A simple and fast reversed-phase HPLC method using diode array detection was developed and validated for the simultaneous determination of trans-resveratrol and quercetin in Sicilian red wine from the Nero d'Avola red grape variety. Investigation was also extended to the quantitative determination of resveratrol and quercetin in grape skins and winemaking byproducts obtained from the same cultivar. Samples were eluted using a C18 narrow-bore column under isocratic conditions in less than 20 min. Quantification of trans-resveratrol and quercetin in red wine was performed without any sample pretreatment, whereas the determination of these phenolic compounds in grape skins and wine pomage required a solvent extraction procedure. Linearity was demonstrated over the 0.39-12.5 and 0.45-57.6 microg/mL range for trans-resveratrol and quercetin, respectively. Detection limits in real samples were in the low ppm level (0.07 mg/L for trans-resveratrol and 0.12 mg/L for quercetin). The HPLC-UV/DAD method was applied for the routine analyses of red wine and grape skin and winemaking byproduct extracts to evaluate their trans-resveratrol and quercetin content. In particular, a very high content of quercetin was found in wine pomace, suggesting the use of this wine byproduct as a potential source of this health-promoting phenolic compound.     

Content of the flavonols myricetin, quercetin, and kaempferol in finnish berry wines

The amounts of myricetin, quercetin, and kaempferol were analyzed in 16 red and 2 white berry and grape wines after acid hydrolysis using an RP-HPLC method with diode array detection. The red berry wines analyzed were made mainly from black currant, crowberry, and bog whortleberry, i.e., berries rich in flavonols. The red grape wines were made mainly from Cabernet Sauvignon or Merlot grapes in several countries. The white wines studied were gooseberry and white currant wines and Chardonnay and Riesling wines. The amount of myricetin ranged from 3.8 to 22.6 mg L(-1) in red berry wines and from 0 to 14.6 mg L(-1) in red grape wines. The amount of quercetin was from 2.2 to 24.3 mg L(-1) red berry wines and from <1.2 to 19.4 mg L(-1) in red grape wines. Low levels of kaempferol were found in all red berry wines and in 9 red grape wines. The total concentration of these flavonols was from 6 to 46 mg L(-1) (mean 20 mg L(-1)) in red berry wines and from 4 to 31 mg L(-1) (mean 15 mg L(-1)) in red grape wines. Small amounts of quercetin were found in white currant and gooseberry wines, whereas no flavonols were detected in white grape wines. These results demonstrate that the contents of flavonols in red     

Effect of red grapes co-winemaking in polyphenols and color of wines

The red grapes co-winemaking effect on phenolic fraction and wine color has been studied for the first time, where Monastrell was comacerated and cofermentated with Cabernet Sauvignon and Merlot. Changes in the relative abundance of anthocyanins were observed as well as hyperchromic shifts at 530 and 620 nm; these effects remain constant after aging. Co-winemaking also favored copigmentation, giving way to more stable anthocyanins and facilitating their polymerization. With regard to color evolution, the mixture of Monastrell with Merlot grapes was more appropriate than with Cabernet Sauvignon for aging wines in oak barrels. The extent of copigmentation was more important in young wines than in aged wines. This is mainly due to the self-anthocyanin monomer reactions in the case of young wines, whereas in aged wines copigmentation is mainly due to the reaction between the anthocyanins and other polyphenolic cofactors. Discriminant analysis showed the possibility of differentiating wines according to the aging time and the type of wine, with color parameters (color intensity, OD 620 nm, and OD 520 nm) being the most important discrimination variables in the first case and petunidin-3-glucoside and peonidin-3-glucoside contents in the second case.     

Determination of free proline and monosaccharides in wine samples by high-performance anion-exchange chromatography with pulsed amperometric detection (HPAEC-PAD)

A sensitive and selective analytical method for the simultaneous separation and quantitative determination of proline and free monosaccharides in wine samples by high-performance anion-exchange chromatography coupled with pulsed amperometric detection is described. Under optimized experimental conditions, a complete separation was obtained in less than 30 min, using an isocratic elution with 10 mM NaOH and 1 mM Ba(OAc)(2). No postcolumn addition of strong bases to the eluent for enhancing detection sensitivity was needed. Upon 25-fold sample dilution and purification to avoid interference of tannins, pigments, and phenolic compounds, the fingerprinting of common monosaccharides (i.e., arabinose, glucose, fructose, galactose, and xylose) and proline in wines, musts, and vinegars can be easily accomplished. The method allows high recovery and satisfies the necessary requirements for accuracy, repeatability, and sensitivity. Values obtained for proline content ranged from 470 to 1190 mg/L in "Aglianico" red wines (mean value, 870 +/- 192 mg/L, n = 21) and from 168 to 286 mg/L in white wines (mean value, 208 +/- 32 mg/L, n = 11). Lower levels were found in musts of red and white grapes, 550 and 87 mg/L, respectively. The lowest content of proline, ca. 10 mg/L, was found both in white and red vinegars.