Characterization of hemiacetal forms of anthocyanidin 3-O-beta-glycopyranosides

The 3-O-beta-glucopyranosides of delphinidin, petunidin, and malvidin (1-3) and cyanidin 3-O-beta-galactopyranoside (4) dissolved in deuterated methanolic solutions without and with acid (5%, CF3COOD) were identified by homo- and heteronuclear NMR techniques. The hemiacetal forms of all the four anthocyanins were characterized as two epimeric 2-hydroxy-hemiacetals on the basis of assignments of both proton and carbon NMR signals together with chemical shift considerations. This is the first report of 13C NMR assignments of two epimeric anthocyanin hemiacetal forms. No 4-hydroxy-hemiacetal form was detected for any of the pigments. For each anthocyanin dissolved in deuterated methanol, the equilibrium between each of the two epimeric hemiacetals and the corresponding flavylium cation was confirmed by the observed positive exchange cross-peaks in the 2D 1H NOESY spectra. The molar proportions of the flavylium cation and the two hemiacetals of 1-4 in deuterated methanol were very similar for all pigments, even during storage for weeks. The majority of the anthocyanins reported to occur in fruits have the same or similar structures as 1-4. These pigments have been proposed to exist predominantly as hemiacetals in slightly acidic to neutral solvents, which is a relevant pH range in plants and in the human gastrointestinal tract.     

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.     

Accumulation and extractability of grape skin tannins and anthocyanins at different advanced physiological stages

Quantitative and qualitative modifications of tannins and anthocyanins in grape skin were investigated at different dates of harvest, from berries sorted on the basis of their density. Free anthocyanins accumulated until 170 g/L of sugars in pulp before undergoing a slight decrease. Changes in anthocyanin composition were observed with increasing sugar levels in the pulp that reflected structural differences between classes of anthocyanins. The proportion of methoxylated anthocyanins continued to increase in the skin as sugar accumulated while the proportion of coumaroylated anthocyanins initially increased (up to 200 g/L of sugars in the pulp) and then rapidly decreased. In comparison, no major quantitative nor qualitative change was observed for tannins, except for a slight increase of the mean degree of polymerization. Whatever the physiological stage of the pulp, the extraction yield of skin phenolics into hydroalcoholic solution for 5 h was lower than 77% for anthocyanins and 38% for proanthocyanidins. For both classes of compounds, no clear evolution in these extraction yields could be observed as sugars accumulated in pulp (from 162.6 to 275.0 g/L). Nevertheless, some structural features within each family of compounds significantly influenced extractability, for example, a lower extraction yield for coumaroylated anthocyanins and for tannins with a high degree of polymerization. Finally, no direct relationship could be found in extraction media between the amounts of all red pigments (measured in acidic conditions) and the color intensity at 520 nm (measured in wine-like model solutions).     

Pistachio skin phenolics are destroyed by bleaching resulting in reduced antioxidative capacities

Pistachio shells split naturally prior to maturity leading to their unique crack-shell form. Within 24 h of harvest, hull-trapped moisture may cause shell staining. The illegal process of bleaching has been used to restore a desirable white color to pistachio shells. It is not known whether bleaching adversely affects phytochemical levels in pistachios. Therefore, we identified for the first time multiple pistachio skin phenolics as quercetin (14.9 microg/g), luteolin (10.0 microg/g), eriodictyol (10.2 microg/g), rutin (1.6 microg/g), naringenin (1.2 microg/g), apigenin (0.2 microg/g), and the anthocyanins, cyanidin-3-galactoside (696 microg/g) and cyanidin-3-glucoside (209 microg/g). We investigated the effects of bleaching (0.1-50% hydrogen peroxide) on phenolic levels and antioxidative capacities in raw and roasted nuts. Because of their flavylium cation structures, anthocyanins were the most sensitive to bleaching. Bleaching decreased total anthocyanin levels [mug/g of skins (% hydrogen peroxide)]: 905 and 549 (0%); 653 and 145 (0.1%); 111 and 18.4 (5%); 6.1 and 3.2 (25%); 0 and 0 (50%) for raw and roasted nuts, respectively. Bleaching also reduced antioxidative capacity [microM/g of Trolox (% hydrogen peroxide)]: 945 and 725 (0%); 940 and 472 (0.1%); 930 and 455 (5%); 433 and 370 (25%); 189 and 173 (50%), for raw and roasted nuts, respectively. Raw nuts preserved phenolic levels and antioxidant capacity better than roasted nuts, suggesting contributing effects of other substances and/or matrix effects that are destroyed by the roasting process. The destruction of bioactive phenolics in pistachio skins may negatively impact the potential health benefits arising from pistachio consumption.     

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.     

Anthocyanin color behavior and stability during storage: effect of intermolecular copigmentation

Intermolecular copigmentation reactions are significantly responsible for the manifold color expression of fruits, berries, and their products. These reactions were investigated with five anthocyanins and five phenolic acids acting as copigments. The stability of the pigment-copigment complexes formed was studied during a storage period of 6 months. The study was conducted using a UV-visible spectrophotometer to monitor the hyperchromic effect and the bathochromic shift of the complexes. The greatest copigmentation reactions took place in malvidin 3-glucoside solutions. The strongest copigments for all anthocyanins were ferulic and rosmarinic acids. The immediate reaction of rosmarinic acid with malvidin 3-glucoside resulted in the biggest bathochromic shift (19 nm) and the strongest hyperchromic effect, increasing the color intensity by 260%. The color induced by rosmarinic acid was not very stable. The color intensity of pelargonidin 3-glucoside increased greatly throughout the storage period with the addition of ferulic and caffeic acids.     

PH-dependent forms of red wine anthocyanins as antioxidants

Anthocyanins are one of the main classes of flavonoids in red wines, and they appear to contribute significantly to the powerful antioxidant properties of the flavonoids. In grapes and wines the anthocyanins are in the flavylium form. However, during digestion they may reach higher pH values, forming the carbinol pseudo-base, quinoidal-base, or the chalcone, and these compounds appear to be absorbed from the gut into the blood system. The antioxidant activity of these compounds, in several metal-catalyzed lipid oxidation model systems, was evaluated in comparison with other antioxidants. The pseudo-base and quinoidal-base malvidin 3-glucoside significantly inhibited the peroxidation of linoleate by myoglobin. Both compounds were found to work better than catechin, a well-known antioxidant. In a membrane lipid peroxidation system, the effectiveness of the antioxidant was dependent on the catalyst: In the presence of H(2)O(2)-activated myoglobin, the inhibition efficiency of the antioxidant was malvidin 3-glucoside > catechin > malvidin > resveratrol. However, in the presence of an iron redox cycle catalyzer, the order of effectiveness was resveratrol > malvidin 3-glucoside = malvidin > catechin. The pH-transformed forms of the anthocyanins remained effective antioxidants in these systems, and their I(50) values were between 0.5 and 6.2 microM.     

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.     

Color stability of commercial anthocyanin-based extracts in relation to the phenolic composition. Protective effects by intra- and intermolecular copigmentation

Anthocyanin extracts are increasingly used as food ingredients. A current challenge is to maintain their color properties. The stability of some colorants has been studied in sugar and non-sugar drink models at three pH values (3, 4, and 5) under thermal and light conditions simulating rapid food aging. At a given pH, color stability mainly depends on the structures of anthocyanins and of colorless phenolic compounds. Colorants rich in acylated anthocyanins (purple carrot, red radish, and red cabbage) display great stability due to intramolecular copigmentation. The protection of red chromophore is higher for diacylated anthocyanins in red radish and red cabbage. For colorants without acylated anthocyanins (grape-marc, elderberry, black currant, and chokeberry), intermolecular copigmentation plays a key role in color protection. Colorants rich in flavonols and with the highest copigment/pigment ratio show a remarkable stability. By contrast, catechins appear to have a negative effect on red colorants, quickly turning yellowish in drink models. This effect is more pronounced when the pH is increased. Finally, color does not seem to be greatly influenced by the addition of sugar.     

Phytochemical composition and pigment stability of Açai (Euterpe oleracea Mart.)

Anthocyanin and polyphenolic compounds present in a?ai (Euterpe oleracea Mart.) were determined and their respective contribution to the overall antioxidant capacity established. Color stability of a?ai anthocyanins against hydrogen peroxide (0 and 30 mmol/L) over a range of temperatures (10-30 degrees C) was also determined and compared to common anthocyanin sources. Additionally, stability in a model beverage system was evaluated in the presence of ascorbic acid and naturally occurring polyphenolic cofactors. Cyanidin 3-glucoside (1040 mg/L) was the predominant anthocyanin in a?ai and correlated to antioxidant content, while 16 other polyphenolics were detected from 4 to 212 mg/L. Red grape anthocyanins were most stable in the presence of hydrogen peroxide, while a?ai and pigments rich in acylated anthocyanins displayed lower color stability in a temperature-dependent manner. In the presence of ascorbic acid, acylated anthocyanin sources generally had increased color stability. A?ai was recognized for its functional properties for use in food and nutraceutical products.     

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.     

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.     

UV-visible spectroscopic investigation of the 8,8-methylmethine catechin-malvidin 3-glucoside pigments in aqueous solution: structural transformations and molecular complexation with chlorogenic acid

The physicochemical properties of 8,8-methylmethine catechin-malvidin 3-O-glucoside isomers, commonly referred to as catechin-ethyl-malvidin 3-O-glucoside, have been studied in aqueous solutions and compared with those of the parent anthocyanin (malvidin 3-O-glucoside). The hydration and acidity constants (pKh and pKa) of the catechin-ethyl-malvidin 3-O-glucoside pigments and malvidin 3-O-glucoside were determined by UV-visible spectroscopic measurements. The ethyl-linked catechin-malvidin 3-O-glucoside pigments present higher stability toward hydration than the parent anthocyanin. The high resistance of these ethyl-linked pigments toward the hydration is related to the self-association that offers optimal protection from the nucleophilic attack of water. Moreover, the ethyl link may confer to the molecule enough flexibility to undergo intramolecular interaction, further protecting it from hydration and bisulfite discoloration. In the wine pH range (3.2-4.0), due to the low pKa and high pKh values, the ethyl-linked pigments are present as colored forms (flavylium cation and quinonoid bases).     

Interactions between grape anthocyanins and pyruvic acid, with effect of pH and acid concentration on anthocyanin composition and color in model solutions.

The formation of vitisin A, an anthocyanin formed naturally in small quantities in maturing port wines, was studied in model wine solutions at a range of pH values (2.0-4.5) and pyruvate concentrations [molar ratios of pyruvic acid to total anthocyanins (PA/TA) ranging from 12.20 to 172.40]. Additionally, the effect of vitisin A formation on the color changes of these model wines was evaluated. Vitisin A was formed through the interaction between malvidin 3-glucoside and pyruvic acid, and vitisin A in acylated forms, having the 6-position of the sugar acylated with acetic acid (3-acetylvitisin A) and p-coumaric acid (3-p-coumarylvitisin A), formed through the interaction between pyruvic acid and malvidin 3-acetylglucoside and malvidin 3-p-coumarylglucoside, respectively; their identities were confirmed by spectral analysis and FABMS. The maximum formation of these new anthocyanin derivatives was at pH 2. 7-3.0, at the higher pyruvic acid concentration (PA/TA of 172.40 units). The vitisins A caused changes in the color of the solution and expressed about 11 times (pH 3) to 14 times (pH 2) more color than the normal anthocyanins. On aging, the model solutions changed from a bluish red, attributable to the main anthocyanins present, to a slightly more orange red, attributable to the vitisin compounds. The aged models containing vitisins A were all much redder than the more red-brown color of the models aged without pyruvic acid.     

Reactivity of anthocyanins and pyranoanthocyanins. Studies on aromatic hydrogen-deuterium exchange reactions in methanol

Reactivity studies involving anthocyanin structures and their equilibrium forms will lead to better understanding of the properties of these antioxidants. Hydrogen-deuterium (H --> D) exchange reactions at various sites of the 3-glucosides of delphinidin (1), petunidin (2), malvidin (3), and the corresponding 3-glucosides of carboxypyranodelphinidin (4), carboxypyranopetunidin (5), carboxypyranomalvidin (6), and the flavonol quercetin 3-O-(6-alpha-rhamnopyranosyl-beta-glucopyranoside)(7) have been examined at room temperature in pure CD 3OD and in CD 3OD acidified with CF 3CO 2D. The H --> D exchange rate constants of H-6 and H-8 of 2 determined from (1)H NMR integration data were found to be independent upon pigment concentration (up to 4 x 10 (-2) M) and trifluoroactic acid concentration (0-15%, v/v), respectively. This suggest that these reactions follow first-order kinetics and unexpectedly to be independent of the acid concentration. H-6 and H-8 of the flavylium cation A-rings of 1- 3, and in the corresponding hydrogens of the hemiketal forms, exchanged with half-lives of approximately 100 h ( 1) and approximately 50 h ( 2 and 3), respectively. The pyranoanthocyanins (4-6) experienced no H --> D exchange for the analogous hydrogens, but H --> D exchange of H-beta (H-4)(t 1/2 approximately 25 h) for these compounds was observed. Only H-8 underwent significant H --> D exchange in 7. It is concluded that a stabilization of the sigma-complexes, assumed to be the intermediates in the reactions, takes place for the common anthocyanins (1-3) contrary to the pyranoanthocyanins (4-6).     

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.     

Effects of salinity stress on carotenoids, anthocyanins, and color of diverse tomato genotypes

One nonanthocyanin-accumulating (Ailsa Craig) and three anthocyanin-accumulating tomato genotypes (Anthocyanin fruit type, Atroviolaceum, and Sun Black) were analyzed to assess differences in their carotenoid and anthocyanin levels and color and to evaluate the effects of nutrient solutions with different salt concentrations on these parameters. The carotenoid content of control Atroviolaceum tomatoes was ca. 2-2.5-fold higher relative to the other two types, and the color of its puree could be visually distinguished from those of other genotypes. Salinity stress led in some cases to a 2-3-fold increase in the lycopene content. Saline treatment increased the accumulation of total anthocyanins in fruits of Sun Black (2-fold increase), while it reduced it in fruits of Anthocyanin (10-fold decrease). In general, the treatment increased the differences in color of different purees. These results indicate that salinity stress can lead to similar or higher increases in tomato carotenoids than those achieved by genetic engineering. In addition, these changes were accompanied by visually discernible color differences in tomato products. Our findings show the considerable potential of exploiting saline soils to obtain tomatoes with higher levels of secondary metabolites like carotenoids and anthocyanins.     

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.     

Heat stability of strawberry anthocyanins in model solutions containing natural copigments extracted from rose (Rosa damascena Mill.) petals

Thermal degradation and color changes of purified strawberry anthocyanins in model solutions were studied upon heating at 85 degrees C by HPLC-DAD analyses and CIELCh measurements, respectively. The anthocyanin half-life values increased significantly due to the addition of rose (Rosa damascena Mill.) petal extracts enriched in natural copigments. Correspondingly, the color stability increased as the total color difference values were smaller for anthocyanins upon copigment addition, especially after extended heating. Furthermore, the stabilizing effect of rose petal polyphenols was compared with that of well-known copigments such as isolated kaempferol, quercetin, and sinapic acid. The purified rose petal extract was found to be a most effective anthocyanin-stabilizing agent at a molar pigment/copigment ratio of 1:2. The results obtained demonstrate that the addition of rose petal polyphenols slows the thermal degradation of strawberry anthocyanins, thus resulting in improved color retention without affecting the gustatory quality of the product.     

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.