Influence of ethanol concentration on the extraction of color and phenolic compounds from the skin and seeds of Tempranillo grapes at different stages of ripening

The aim of this paper is to study how grape ripeness and ethanol concentration affect the extraction of color and phenolic compounds from skins and seeds during the maceration/fermentation process. Simulated maceration assays were carried out with the grapes at three stages of berry development (vitis vinifera cv. Tempranillo) and different percentages of ethanol in the maceration media. Both ripeness and ethanol content have a considerable effect on the extraction of color and phenolic compounds. Of these two factors, ripeness increases the extractability most. The presence of ethanol in the medium facilitates anthocyanin and especially proanthocyanidin extraction, but it also decreases copigmentation phenomena, which can decrease the color intensity. The higher the ethanol concentration is in the maceration media, the higher the astringency of proanthocyanidins.     

Changes of ochratoxin A in grapes inoculated with Aspergillus carbonarius and subjected to chamber-drying under controlled conditions

The production pattern for ochratoxin A in grapes inoculated with Aspergillus carbonarius and changes in its concentration during raisining of Merlot, Syrah, Tempranillo, and Cabernet Sauvignon red grapes and Pedro Ximenez white grape were studied. Grapes were chamber-dried under controlled temperature and humidity conditions, with and without dipping pretreatments in alkaline emulsions of olive oil or ethyl oleate. Based on the results for the grapes that developed the fungus (Merlot and Pedro Ximenez), a temperature of 50 °C in the absence of dipping stopped ochratoxin A production and even degraded part of the toxin already formed. Both dipping pretreatments facilitated removal of the toxin and led to its virtually complete disappearance. However, dipping in the ethyl oleate emulsion caused substantial changes in the sensory characters of the musts obtained from the raisins, so it should be avoided to ensure the expected quality in the sweet wines elaborated from them.     

Changes in hydrophilic and lipophilic antioxidant activity in relation to their phenolic composition during the chamber drying of red grapes at a controlled temperature

The purpose of this work was to study the variation of phenol compounds, as measured by HPLC, during the chamber drying under controlled temperature conditions of red grapes of the Merlot and Tempranillo varieties in relation to antioxidant activity. Both lipophilic and hydrophilic antioxidant activities in these grapes increased during the drying process; the former was measured via proton transfer in the coupled oxidation reaction between linoleic acid and β-carotene, and the second via electron transfer in the DPPH assay. The hydrophilic component was invariably greater in Tempranillo grapes, and so was the lipophilic component in Merlot grapes. Only the increase in hydrophilic antioxidant activity obtained a significant correlation with the phenolic compounds during the drying process. However, based on the phenolic fraction analysis, this result was primarily due to phenolic polymers and, to a lesser extent, also to phenolic acids, flavans, and some flavonols and anthocyans.     

Influence of grape density and harvest date on changes in phenolic composition, phenol extractability indices, and instrumental texture properties during ripening

Changes in the phenolic composition, phenol extractability indices, and mechanical properties occur in grape berries during the ripening process, but the heterogeneity of the grapes harvested at different ripening stages affects the reliability of the results obtained. In this work, these changes were studied in Nebbiolo grapes harvested during five consecutive weeks and then separated according to three density classes. The changes observed in chemical and mechanical parameters through the ripening process are more related to berry density than harvest date. Therefore, the winemaker has to select the flotation density according to the objective quality properties of the wine to be elaborated. On the other hand, the stiffer grapes were associated with a higher accumulation of proanthocyanidins. The harder grapes provided the higher concentration and extractability of flavanols reactive to vanillin, whereas the thicker ones facilitated the extraction of proanthocyanidins.     

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.     

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.     

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.     

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.     

Chemical constituents and antioxidant activity of sweet cherry at different ripening stages

The development and ripening process of sweet cherry (Prunus avium L. cv. 4-70) on the tree was evaluated. For this purpose, 14 different stages were selected in accordance with homogeneous size and color. Some parameters related to fruit quality, such as color, texture, sugars, organic acids, total antioxidant activity, total phenolic compounds, anthocyanins, and ascorbic acid were analyzed. The results revealed that in sweet cherry, the changes in skin color, glucose and fructose accumulation, and softening process are initiated at early developmental stages, coinciding with the fast increase in fruit size. Also, the decrease in color parameter a was correlated with the greatest accumulation of total anthocyanins. Ascorbic acid, total antioxidant activity (TAA), and total phenolic compounds decreased during the early stages of sweet cherry development but exponentially increased from stage 8, which coincided with the anthocyanin accumulation and fruit darkening. TAA showed positive correlations (r(2) = 0.99) with both ascorbic acid and total phenolic compounds and also with the anthocyanin concentration from stage 8. Taking into account the reduced shelf life of sweet cherry and to ensure that these fruits reach consumers with the maximum organoleptic, nutritional, and functional properties, it is advisable to harvest sweet cherries at stage 12 of ripening.     

Improving grape phenolic content and wine chromatic characteristics through the use of two different elicitors: methyl jasmonate versus benzothiadiazole

Benzothiadiazole (BTH) and methyl jasmonate (MeJ) have been described as exogenous elicitors of some plant defense compounds, polyphenols among them. The objective of this study was to determine whether the application of BTH or MeJ to grape clusters at the beginning of the ripening process had any effect on the accumulation of the main flavonoid compounds in grapes (anthocyanins, flavonols, and flavanols) and the technological significance of these treatments in the resulting wines. The results obtained after a 2 year experiment indicated that both treatments increased the anthocyanin, flavonol, and proanthocyanidin content of grapes. The wines obtained from the treated grapes showed higher color intensity and total phenolic content than the wines made from control grapes. The exogenous application of these elicitors, as a complement to fungicide treatments, could be an interesting strategy for vine protection, increasing, at the same time, the phenolic content of the grapes and the resulting wines.     

Phenolic composition of the Brazilian seedless table grape varieties BRS Clara and BRS Morena

The detailed phenolic composition (anthocyanins, flavonols, hydroxycinnamic acid derivatives, stilbenes, and flavan-3-ols) in the skin and flesh of the new BRS Clara and BRS Morena seedless table grapes has been studied using HPLC-DAD-ESI-MS/MS. The two grapes, especially BRS Morena, contained high amounts of phenolic compounds, mainly located in their skins and qualitatively not different from those found in Vitis vinifera grapes. In addition, BRS Morena (a teinturier variety) showed qualitatively different phenolic compositions in its skin and flesh, mainly affecting the anthocyanin and flavonol profiles. Consistent with high phenolic contents, high antioxidant capacity values were registered for both grape varieties, especially for BRS Morena. Proanthocyanidins and hydroxycinnamoyl-tartaric acids were the major phenolic compounds found in BRS Clara and were also important in BRS Morena, although anthocyanins were the main phenolic compounds in the latter case. These results suggest that the entire grapes, including the skin, may potentially possess properties that are beneficial to human health. In this context, the BRS Morena grape can be considered as a high resveratrol producer.     

Effect of flash release treatment on phenolic extraction and wine composition

The flash release (FR) process, consisting of rapidly heating the grapes and then applying strong vacuum, has been proposed to increase the polyphenol content of red wines. Its impact on polyphenol extraction kinetics and on the polyphenol composition of red juice and wines was studied over two seasons on different grape varieties (Grenache, Mourvedre, Carignan). The FR process allows fast extraction of all phenolic compounds (hydroxycinnamic acids, flavonols, anthocyanins, catechins, proanthocyanidins) and can be used to produce polyphenol-enriched grape juices. However, the concentration of all polyphenols dramatically decreased throughout fermentation when pressing was achieved immediately after FR. The FR wines made with pomace maceration were also enriched in polyphenols compared to the corresponding control wines. Increasing the duration of high-temperature exposure in the FR treatment further increased extraction of phenolic compounds but also accelerated their conversion to derived species. The tannin-to-anthocyanin ratio was particularly low in the wine fermented in the liquid phase, higher after FR than in the control, and even higher after longer heating. FR resulted in an increased tannin-to-anthocyanin ratio and an increased conversion of anthocyanins to tannin-anthocyanin adducts showing the same color properties as anthocyanins. The tannin-to-anthocyanin ratio was particularly low in the wine fermented in the liquid phase that also contained larger amounts of orange sulfite bleaching-resistant pigments.     

Application of FT-MIR spectroscopy for fast control of red grape phenolic ripening

The content of phenolic compounds determines the state of phenolic ripening of red grapes and is a key criterion in setting the harvest date to produce quality red wines. In this study, the feasibility of Fourier transform mid-infrared (FT-MIR) spectroscopy combined with partial least-squares (PLS) regression to quantify phenolic compounds is reported. The reference methods used for quantifying these compounds (which were evaluated as total phenolic compounds, total anthocyanins, and condensed tannins) were the usual ones used in cellars that employed UV-vis spectroscopy. To take into account the high natural variability of grapes when building the calibration models, fresh grapes from six varieties, at different phenolic ripening states were harvested during three vintages. Destemmed and crushed grapes were subjected to an accelerated extraction process and used as calibration standards. A total of 192 extracts (objects) were obtained, and these were divided into a training set (106 objects) and a test set (86 objects) to evaluate the predictive ability of the models. Among the different MIR regions of the extract raw spectra, those that provided the highest variability on the absorption were selected. The results showed that the best PLS regression model was the one obtained when working in the region of 1168-1457 cm(-1) because it gave the most accurate and robust prediction for total phenolic compounds (RMSEP%=4.3 and RPD=4.5), total anthocyanins (RMSEP%=5.9 and RPD=3.5), and condensed tannins (RMSEP%=5.8 and RPD=3.8). Therefore, it can be concluded that FT-MIR spectroscopy can be a fast and reliable technique for monitoring the phenolic ripening in red grapes during the harvest period.     

Study of low molecular weight phenolic compounds during the aging of sparkling wines manufactured with red and white grape varieties

Thirty-two phenolic compounds of low molecular weight were identified in 36 white, blanc de noir, and rosé sparkling wines by using HPLC with photodiode array and mass spectrometry detection. Some of the identified compounds, such as cis- and trans-ethylcaftaric, cis- and trans-ethylcaffeic, and cis- or trans-ethyl-p-coumaric acids, 2R,3R-dihydroquercetin, 2R,3R-dihydrokaempferol 3-O-beta-d-glucoside, and a lignan derivative are described for the first time in sparkling wines manufactured with grapes of red varieties. This is also the first time that cis- or trans-diethylfertaric acids have been identified in wines. When cluster analysis was applied to the data of 19 of the 32 identified compounds, the greatest differences found in the low molecular weight phenolic compounds in sparkling wines were due to the grape variety from which they were manufactured, whereas aging time did not significantly influence phenolic composition. Nine phenolic compounds, that is, trans-p-coumaric and trans-caftaric acids, trans-resveratrol glucoside, cis-coutaric, trans-coutaric, cis-p-coumaric, and cis-caftaric acids, tryptophol, and syringic acid, permit the wines to be classified correctly in accordance with the grape variety from which they were manufactured.     

Phenolic compositions of grapes and wines from cultivar cabernet sauvignon produced in chile and their relationship to commercial value

The phenolic composition of wine depends on, among other factors, the grapes used to make it. In this sense, knowledge of the chemical composition of grapes and its association with the resulting wines is an important tool to determine if there is a relationship between the phenolic composition of grapes and the price that these wines obtain in the market. For this purpose, grape skins and seeds from the cultivar Cabernet Sauvignon from the central region of Chile, in 2009 and 2010 vintages from two ripening points, were subjected to chemical and phenolic analyses, as were the wines made from these grapes. Grapes and the corresponding wines from three retail price wine categories, U.S. $6-8, U.S. $28-30, and U.S. $150-160, were evaluated. No differences were found across the price categories in the chemical analysis of grapes. Berry skins and wines from the higher price categories presented a higher concentration only of total tannins, and the differences in their concentrations were only among the different fractions of proanthocyanidins in the skins, seeds, and wines; there were no differences in their proportions. A seasonal effect influenced the concentrations of certain compounds in grapes and led to a decrease in the concentration of total phenols, total tannins, and total anthocyanins between sampling dates as harvesting moved toward the common commercial grape harvest in Chilean viticulture.     

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.     

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 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.     

Influence of vineyard location and vine water status on fruit maturation of nonirrigated cv. Agiorgitiko (Vitis vinifera L.). Effects on wine phenolic and aroma components

The influence of site on grape and wine composition was investigated for Vitis vinifera L. cv. Agiorgitiko in the Nemea appellation area in southern Greece. Three nonirrigated plots were studied during the 1997 and 1998 vintages, which were typically very hot and without summer rainfall. Vines were subjected to different water regimens as a result of the variation of soil water-holding capacity and evaporative demand. Vine water status was determined by means of predawn leaf water potential. Differences in vine water status between sites were highly correlated with the earliness of shoot growth cessation and veraison. Grape composition was monitored during fruit ripening. Water deficit accelerated sugar accumulation and malic acid breakdown in the juice. Early water deficit during the growth period was demonstrated to have beneficial effects on the concentration of anthocyanins and total phenolics in berry skins. A similar pattern was observed for the phenolic content of wines elaborated after vinification of grapes harvested on each plot, in both seasons. Limited water availability seemed to increase glycoconjugates of the main aromatic components of grapes as a quantitative increase in levels of bound volatile compounds of the experimental wines was observed under water deficit in both years. Wines produced from grapes of stressed vineyards were also preferred in tasting trials.     

Changes in low molecular weight phenolic compounds in Spanish, French, and American oak woods during natural seasoning and toasting

The evolution of low molecular weight polyphenols in Spanish oak heartwood of Quercus robur,Quercus petraea, Quercus pyrenaica, and Quercus faginea was studied by HPLC, in relation to the processing of wood in barrel cooperage. The polyphenolic composition of Spanish woods subjected to natural seasoning for 3 years and to the toasting process was studied in relation to those of French oak of Q. robur (Limousin) and Q. petraea (Allier) and American oak of Q. alba (Missouri), which are habitually used in cooperage. The concentrations of benzoic and cinnamic acids and aldehydes of Spanish woods increased during seasoning depending on the duration of this process and in the same way as those of French and American woods. The process having the main influence on the phenolic composition of wood was the toasting. It led to high increases in the concentration of phenolic aldehydes and acids, especially cinnamic aldehydes (sinapic and coniferylic aldehydes), followed by benzoic aldehydes (syringaldehyde and vanillin) and benzoic acids (syringic and vanillic acids). This polyphenolic composition in Spanish oak species evolved during toasting as in French and American oak, but quantitative differences were found, which were especially important in American species with respect to the others.