Aging effect on the pigment composition and color of Vitis vinifera L. Cv. Tannat wines. Contribution of the main pigment families to wine color

Red wines made from Vitis vinifera L. cv. Tannat grapes are known to possess high contents of tannins and intense color, features that are responsible for the originality of these wines. This work aimed to study the evolution of the pigment composition and CIELAB color parameters as Tannat wines become older, as well as to establish the contribution to wine color of the main pigment families. Tannat wines produced in Uruguay from grapes of the same vineyard in six consecutive vintages (1998-2003) and Tannat grapes of the 2003 harvest were analyzed by means of HPLC-DAD-MS and UV-vis spectrometric techniques. The correlations between the different pigment families and the CIELAB parameters revealed the importance of the variations of the percentage, found in anthocyanins and flavanol-anthocyanin acetaldehyde-mediated condensation products (decrease) and pyranoanthocyanins and direct condensation products (increase), in the modification of the color from purple-red hues to more orange-red ones. The color suffered qualitative rather than quantitative changes, that is, the hue (h*ab) increased, whereas the chroma (C*ab) and lightness (L) did not show a defined trend with time.     

Influence of different phenolic copigments on the color of malvidin 3-glucoside

The effectiveness of seven phenolic compounds (catechin, epicatechin, procyanidin B2, caffeic acid, p-coumaric acid, myricitrin, and quercitrin) as copigments of malvidin 3-glucoside, the major anthocyanin in red wines from Vitis vinifera, using a copigment/pigment molar ratio of 1:1 was assayed in model wine solutions under the same conditions (pH=3.6, 12% ethanol). The stability of the copigment-pigment complexes formed was studied during a storage period of 60 days at 25 degrees C. Tristimulus colorimetry was applied for color characterization of the copigmentation process, and HPLC-DAD-MS was used to monitor changes in the composition of the samples. Copigmentation has been found to occur in all cases despite the low copigment/pigment molar ratio used, although the effect was different depending on the compound. Flavan-3-ols appeared as the less effective copigments, procyanidin B2 being even worse than monomeric flavanols, whereas flavonols behaved as the best ones. These latter copigments also induced the most statistically significant bathochromic shift in lambdamax. In the colorimetric analysis, it was observed that the lightness L* of the copigmented solutions increased with time, chroma C*ab decreased, and the hue hab increased. The copigments that produced a greater increase in the hue angle were the monomeric flavan-3-ols, which therefore showed to be the least protective cofactors against browning of the anthocyanin solution during the storage. With the time of storage, the formation of new pigments was observed in the solutions containing flavanols (xanthylium structures) and hydroxycinnamic acids (pyranoanthocyanins), which explains some of the color modifications produced in these solutions. Another relevant observation was that the stability of the anthocyanin was not much improved by most of the assayed copigments, since quite similar degradation rates were observed in the presence and absence of those cofactors.     

Polyphenol content and total antioxidant activity of vini novelli (young red wines)

Eight commercial Italian vini novelli (red wines prepared by carbonic maceration and supposed to be consumed within three months from their wine-making) were evaluated for their total antioxidant activity. The wines had an average total phenol content (1605.4 +/- 337.4 mg/L gallic acid equivalents) lower than that of wines prepared by traditional maceration and consumable after aging (2057. 3 +/- 524.0 mg/L gallic acid equivalents). The average flavanol content (424.7 +/- 121.3 mg/L catechin equivalents) and the total antioxidant activity (16.8 +/- 3.8 mmol/L Trolox equivalents) of vini novelli were higher than the corresponding values (382.7 +/- 174.5 mg/L catechin equivalents and 12.3 +/- 3.3 mmol/L Trolox equivalents) found for aged wines. Three couples of experimental wines were prepared from the same grapes by traditional or carbonic maceration. These wines showed a different phenolic pattern, anthocyanins being more abundant in vini novelli. However, the average total antioxidant activities of the wines were similar, suggesting that aging (and not the wine-making technique) is the main factor influencing the antioxidant activity of red wines.     

Effect of different winemaking technologies on phenolic composition in Tinta Miúda red wines.

The influence of different types of winemaking technology on the contents of catechins, proanthocyanidins, and anthocyanins in Tinta Miúda red wines was studied. The Tinta Miúda red wines were made by fermentation with carbonic maceration, fermentation with stem contact, and fermentation without stem contact, respectively. The analysis of individual catechins, procyanidins, and anthocyanins in these wines was performed by HPLC, and quantification of total catechins, total oligomeric proanthocyanidins, total polymeric proanthocyanidins, and total anthocyanins was carried out by spectrophotometric methods. The wine made by carbonic maceration contained the highest amounts of both catechins and oligomeric and polymeric proanthocyanidins, followed by the wine made by fermentation with stem contact, whereas the wine made by fermentation without stem contact contained the lowest of these compounds. On the other hand, the concentrations of total anthocyanins and nearly all individual anthocyanins in the carbonic maceration wine were lower than those in the wines made by fermentation with stem contact and fermentation without stem contact. These results indicated that, although the carbonic maceration technique could retain higher amounts of catechins and proanthocyanidins in wine, it did not favor retaining or stabilizing anthocyanins in wine.     

Color and phenolic compounds of a young red wine. Influence of wine-making techniques, storage temperature, and length of storage time

The purpose of this work was to determine the influence of vinification technique (maceration temperature and clarification method), storage temperature, and length of storage time on the phenolic compounds and color of young red wines. Multivariate analysis of variance and principal component analysis pointed to significant differences among all of the variables according to vinification technique and length of storage time. Storage temperature did not cause significant differences between some of the variables. The best color characteristics were obtained when low-temperature maceration wines were clarified with polyvinylpyrrolidone. Color quality also improved with lower storage temperature.     

The extraction of anthocyanins and proanthocyanidins from grapes to wine during fermentative maceration is affected by the enological technique

The effect of three enological techniques (low temperature prefermentative maceration, must freezing with dry ice, and the use of a maceration enzyme) on the extraction of anthocyanins and proanthocyanidins from must to wine during fermentative maceration was studied to determine the extent to which these compounds are extracted and to assess the changes on their qualitative composition due to enological technique applied. The results showed that the dry ice treatment led to wines with high color intensity and high anthocyanin content, the maximum rate of extraction being observed the first 6 days of fermentative maceration. Regarding the effect of the different techniques on the quantitative and qualitative composition of proanthocyanidins, only the dry ice treatment seemed to favor the extraction of high molecular weight skin proanthocyanidins. The low temperature prefermentative maceration treatment led to the highest concentration of proanthocyanidins at the moment of pressing; however, this treatment, contrary to expectations, led to wines with the highest content of seed-derived proanthocyanidins. The use of the maceration enzyme also increased the concentration of proanthocyanidins during all of the fermentative process, as compared to a control wine, although the increase was not only due to skin proanthocyanidins but also seed proanthocyanidins. We have demonstrated in this study that maceration enzymes also facilitate seed phenolic extraction.     

Anthocyanins, flavonols, and free radical scavenging activity of Chinese bayberry (Myrica rubra) extracts and their color properties and stability

Characterization of anthocyanins and flavonols and radical scavenging activity assays of extracts from four Chinese bayberry (Myrica rubra) varieties with different fruit colors were carried out. One dominant anthocyanin and three major flavonols were isolated by HPLC, and cyanidin-3-O-glucoside and two of three flavonols, myricetin and quercetin-3-O-rutinoside, were identified by cochromatography with authentic standards. Both DPPH* and ABTS*(+) cation assays indicated that the black varieties (Biji and Hunan) demonstrated much higher radical scavenging activities than the pink (Fenhong) and yellow (Shuijing) varieties, which may be attributed to much higher levels of anthocyanins, flavonoids, and total phenolics in the black varieties. Biji and Hunan had 6.49 and 6.52 mM Trolox equivalent antioxidant capacity (TEAC) per 100 g of fresh weight, whereas the pink (Fenhong) and yellow (Shuijing) bayberries had 1.32 and 1.31 mM TEAC/100 g. Different fruit color was reflected by the surface color and pigment extract color. Color stability of the pigment was dependent on pH, and the pigment was more stable at low pH (pH approximately 1.5). The lightness (L) increased while the chroma (C value) decreased with increase of pH until pH 5, but higher pH caused a small decrease for L and an increase for C.     

Effects of solvent and temperature on pressurized liquid extraction of anthocyanins and total phenolics from dried red grape skin

Pressurized liquid extraction (PLE) was used to extract anthocyanins from the freeze-dried skin of a highly pigmented red wine grape with six solvents at 50 degrees C, 10.1 MPa, and 3 x 5 min extraction cycles. Temperature (from 20 to 140 degrees C in 20 degrees C increments) effects on anthocyanin recovery by acidified water and acidified 60% methanol were also studied. Acidified methanol extracted the highest levels of total monoglucosides and total anthocyanins, whereas the solvent mixture (40:40:20:0.1 methanol/acetone/water HCl) extracted the highest levels of total phenolics and total acylated anthocyanins. Acidified water extracts obtained by PLE at 80-100 degrees C had the highest levels of total monoglucosides, total acylated anthocyanins, total anthocyanins, total phenolics, and ORAC values. Acidified methanol extracts obtained by PLE at 60 degrees C had the highest levels of total monoglucosides and total anthocyanins, whereas extracts obtained at 120 degrees C had the highest levels of total phenolics. High-temperature PLE (80-100 degrees C) using acidified water, an environmentally friendly solvent, was as effective as acidified 60% methanol in extracting anthocyanins from grape skins.     

Optimizing the process of making sweet wines to minimize the content of ochratoxin A

During the drying process of raisins, the grapes are subjected to climatic variations that can result in heavy infections of some fungal species that produce ochratoxin A (OTA), a powerful toxic metabolite, whose maximum permitted content is set by the European Union at 2.0 μg/L for grapes, wine and other drinks derived from the grape. The aim of this paper is to optimize the process of making sweet wines in order to minimize the content of ochratoxin A. The results reflect a reduction of the OTA content in grapes dried under controlled conditions in a climatic chamber up to 24% compared to those sunned in the traditional way. A decrease of the concentrations of OTA is also observed during the processes of vinification. Those wines with prefermentative maceration reached a higher OTA content than the wines without maceration, but unexpectedly were not those preferred from a sensorial point of view. In addition, the process of aging in oak casks has been shown to serve as a natural method for reducing the OTA content of these wines.     

Anthocyanin composition of black carrot (Daucus carota ssp. sativus var. atrorubens Alef.) cultivars Antonina, Beta Sweet, Deep Purple, and Purple Haze

This study aimed to identify the pigment composition of black carrot (Daucus carota ssp. sativus var. atrorubens Alef.) cultivars Antonina, Beta Sweet, Deep Purple, and Purple Haze. Cyanidin 3-xylosyl(glucosyl)galactosides acylated with sinapic acid, ferulic acid, and coumaric acid were detected as major anthocyanins by high-performance liquid chromatography with diode array detection (HPLC-DAD) and with electrospray ionization multiple mass spectrometry (HPLC-ESI-MS(n)) analyses. The preparative isolation of these pigments was carried out by means of high-speed countercurrent chromatography (HSCCC). The color activity concept was applied to the isolated anthocyanins at three pH values. Cyanidin 3-xylosyl(sinapoylglucosyl)galactoside was found to exhibit a lower visual detection threshold and a higher pH stability than cyanidin 3-xylosyl(feruloylglucosyl)galactoside and cyanidin 3-xylosyl(coumaroylglucosyl)galactoside. The color parameters of the fresh roots of the four cultivars were described by the CIELab coordinates L* (lightness), C* (chroma), and h(ab) (hue angles). Total phenolics varied among the cultivars and ranged from 17.9 to 97.9 mg gallic acid equivalents (GAE)/100 g fresh weight (fw). For the content of monomeric anthocyanins, values between 1.5 and 17.7 mg/100 g fw were determined.     

Prediction of wine color attributes from the phenolic profiles of red grapes (Vitis vinifera)

Knowledge about the relation between grape and wine phenolics is of key interest for the wine industry with respect to being able to predict wine quality from analyses of grapes. Prediction of the phenolic composition and color of experimentally produced red wines from the detailed phenolic composition of the corresponding grapes was investigated using a multivariate approach. Grape extracts and wines were produced from 55 different grape samples, covering 8 different Vitis vinifera cultivars: Alicante, Merlot, Syrah, Cinsault, Grenache, Carignan, Cabernet Sauvignon, and Mourvedre. The phenolic composition of the grapes and wines showed that the average ratios between wine and grape phenolics ranged from 0.25 to 7.9 for the different phenolic compounds. Most interestingly, the average ratios were low for anthocyanins (0.31) and tannins (0.32), intermediate for (+)-catechin (0.75) and polymeric pigments (0.98), and high for gallic acid (7.9). Individual wine phenolics in general correlated well with several grape phenolics, indicating that a multivariate approach might be advantageous for prediction of wine phenolics from grape phenolics analysis. However the use of multivariate prediction of individual wine phenolics from the complete grape phenolic composition only improved the prediction of wine polymeric pigments, whereas wine anthocyanins were predicted with the same precision as from the direct relation with grape anthocyanins. Prediction of color attributes of pH normalized experimental wines from the phenolic profiles of grapes was accomplished using a multivariate approach. The correlation between predicted and measured total wine color was high ( r = 0.958) but was very similar to the correlation coefficient obtained for the direct relation between grape anthocyanins and total wine color ( r = 0.961). Color due to copigmentation, color due to anthocyanins, and color intensity were also predicted well.     

Anthocyanins, phenolics, and color of Cabernet Franc, Merlot, and Pinot Noir wines from British Columbia.

Changes in phenolics (anthocyanins, flavonols, tartaric esters, and total phenolics) during ripening of grapes and in phenolics and color during vinification and aging of Cabernet Franc, Merlot, and Pinot Noir wines were studied. Anthocyanins in grape skins showed variations in accumulation pattern, concentration, and distribution depending on variety and to a lesser extent on season. During vinification, colorless phenolics increased during alcoholic fermentation, reached maximum values at pressing, and remained stable during malolactic fermentation and subsequent storage. Anthocyanins and color density, on the other hand, increased during the early stages of alcoholic fermentation, reached maximum values 2-3 days after the start of fermentation, decreased during malolactic fermentation, and slowly declined during subsequent storage. Viticultural practices that increased cluster sun exposure generally led to higher phenolics and color density of wines, whereas changing yeasts used for fermentation had minimal effects.     

Influence of grape maturity and maceration length on color, polyphenolic composition, and polysaccharide content of cabernet sauvignon and tempranillo wines

The aim of this paper was to study how maturity and maceration length affect color, phenolic compounds, polysaccharides, and sensorial quality of Cabernet Sauvignon and Tempranillo wines at three stages of grape ripening. Ripeness increased color extractability, phenolic compounds, and polysaccharide concentrations. Moreover, the proanthocyanidin mean degree of polymerization (mDP) and the percentage of prodelphinidins also increased with maturity, whereas the percentage of galloylation decreased. In general, wines from riper grapes contain higher proportions of skin proanthocyanidins. Color and anthocyanin concentration decreased when the maceration was longer, whereas polysaccharide and proanthocyanidin concentrations did the opposite. It was also detected that the mDP and the percentage of prodelphinidins decreased when the maceration was extended, whereas the percentage of galloylation increased. These data seem to indicate that proanthocyanidin extraction from seeds is clearly increased throughout the maceration time.     

Evolution of flavanols, anthocyanins, and their derivatives during the aging of red wines elaborated from grapes harvested at different stages of ripening

Several red wines were elaborated to assess the effect of the degree of grape ripening on wine color and on the levels of flavanol and anthocyanin compounds, which are chiefly responsible for the wine color attributes. Two different cultivars and three different degrees of ripening were studied in two consecutive years. The wines were aged for 1 year in American oak barrels of medium-high char followed by 6 months in the bottle. The results showed that the wines made from more mature grapes had generally higher free anthocyanin content, and during aging the decrease of the free anthocyanins and flavanols took place in conjunction with an increase in the levels of the anthocyanin derivatives or "new pigments", which are responsible for maintaining color intensity and adding violet hues in aged wines. From the results obtained, it seems to be clear that the characteristics and composition of grapes harvested later (7-8 days in this region and for these varieties) than the usual time are quite beneficial to obtaining quality aged wines. The phenolic composition of wines made from the last harvested grapes is mainly responsible for the stability of their color, which is extremely important in product acceptance with a significant increase hence of product quality.     

Use of dehydrated waste grape skins as a natural additive for producing rosé wines: study of extraction conditions and evolution

Dehydrated waste grape skins from the juice industry were used as an additive to produce rosé wines. Maceration time, particle size, dosage, alcoholic content, and maceration temperature were first studied in model wine solutions using two different dehydrated waste grape skins. Full factorial experimental designs together with Factor Analysis and Multifactor ANOVA allowed for the evaluation of each parameter according to the composition of color and phenolic and aroma compounds. Higher maceration time favored the extraction of anthocyanins; phenolic compound release was influenced by dosage independent from other factors studied. Rosé wines were produced by direct addition of dehydrated waste grape skins, according to selected parameters in two different white wines, achieving characteristics equivalent to commercial rosé wines. After three months of storage, rosé wine composition was stable.     

Effect of copigments and grape cultivar on the color of red wines fermented after the addition of copigments

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.     

Evolution and stability of anthocyanin-derived pigments during Port wine aging.

For three years, the evolution of the three major anthocyanidin monoglucosides (malvidin 3-glucoside, malvidin 3-acetylglucoside, and malvidin 3-coumaroylglucoside) and their anthocyanin-pyruvic acid adducts was monitored in Port wines stored in oak barrels. The degradation reactions of all pigments followed first-order kinetics in all the wines studied. The degradation rate constants of the anthocyanin-pyruvic acid adducts were much lower than those of the anthocyanidin monoglucosides. The results of both anthocyanins and pyruvic acid adducts show that acylation on the sugar moiety of all the pigments decreased their stability in wine. The levels of malvidin 3-glucoside-pyruvic acid adduct and its acylated forms increased right after wine fortification with wine spirit before starting to decrease around 100 days. The initial formation of anthocyanin-pyruvic acid adducts was concurrent with the degradation of anthocyanidin monoglucosides.     

Analysis of wine components in Cynthiana and Syrah wines

Red wine is composed of a complex matrix of compounds that can interfere with analysis. A high-performance liquid chromatography (HPLC) procedure was developed to efficiently analyze organic acids, sugars, glycerol, and ethanol in Cynthiana (Vitis aestivalis) wine. Standard laboratory procedures (pH, titratable acidity, and color attributes) and HPLC were found reproducible for Cynthiana wine. HPLC recovery efficiency was determined by analysis of spiked and unspiked samples (model, Cynthiana, and Syrah (Vitis vinifera) wines). Although recovery of components was greater in the model wine, recovery in Cynthiana and Syrah wine was comparable. The HPLC procedure was further compared to commercial rapid enzyme analysis tests using model, Cynthiana, and Syrah wines. HPLC analyses were more accurate than enzymatic tests for determining components in the model, Cynthiana, and Syrah wines. Considering the complexity of the wines analyzed, reproducibility and recovery of the HPLC procedure was demonstrated and showed improvement and precision when compared to existing methods.     

Pulsed electric field-assisted vinification of aglianico and piedirosso grapes

Pulsed electric field (PEF) treatments were applied to increase the polyphenolic content of fresh red wines made from Aglianico and Piedirosso grapes. Prior to the fermentation/maceration step, the grape skins were treated at different PEF intensities (field strengths from 0.5 to 1.5 kV/cm and energy inputs from 1 to 50 kJ/kg), with their permeabilization being characterized by electrical impedance measurements. Furthermore, the release kinetics of the total polyphenols and anthocyanins were characterized during the maceration stage by spectroscopic and Folin-Ciocalteu colorimetric methods, respectively. Finally, the fresh wine, obtained after pressing, was characterized for total acidity, pH, reducing sugar, color intensity, total polyphenols, anthocyanins content, antioxidant activity, and volatile compound composition. PEF treatment on Aglianico grapes induced a significantly higher release of polyphenols (+20%) and anthocyanins (+75%), thus improving the color intensity (+20%) and the antioxidant activity of the wine (+20%) while preserving the other organoleptic characteristics. In contrast, there was only a minor impact on the polyphenolic release kinetics of Piedirosso grapes, despite the significant degree of cell membrane permeabilization.     

Drying of Pedro Ximenez grapes in chamber at controlled temperature and with dipping pretreatments. Changes in the color fraction

The drying of Pedro Ximenez grapes in chamber at a controlled temperature of 40 or 50 degrees C is studied. Compared to traditional sun-drying, the chamber-drying shortened the drying time by about 40% at 50 degrees C. In color terms, the musts obtained from grapes dried at 50 degrees C were closer in CIELab coordinates to those obtained by sun-dried grapes, with similar h(ab) values and slightly lower L* and C(ab)*. To shorten further the drying times at 50 degrees C, the grapes were dipped in olive oil or ethyl oleate emulsions containing potassium carbonate. The ethyl oleate pretreatment shortened additionally the drying time by about 25%, providing musts with chroma, lightness, and hue similar to those without grape pretreatment. In general, except for the phenolic compounds corresponding to the drying with ethyl oleate pretreatment, most of these compounds in the remainding conditions studied increased to a lesser extent than expected because of water losses of the grapes during drying, revealing degradation reactions.