Identification and quantification of phenolic composition from different species of Jabuticaba (Plinia spp.) by HPLC-DAD-ESI/MSn.

The aim of this study was to investigate phenolic compounds in peel, pulp and seeds of five different jabuticabas - Plinia trunciflora, "cabinho", P. cauliflora, cultivars "paulista" and "canaã-açu", P. jaboticaba, "sabará" and P. phitrantha, "branca-vinho". In addition to the commonly reported cyanidin-3-glucoside and delphinidin3-glucoside, it was also found the unreported cyanidin-3-coumaroylglucoside in the peels. Flavonols derived from quercetin and myricetin were also detected in jaboticaba peels, along with a wide variety of derivatives of ellagic acid and methyl ellagic acid. The latter derivatives occurred in acylated forms, which were not usually found in jabuticabas. The pulps and seeds of jabuticabas contained large amounts of ellagitannins vescalagin and castalagin, as well as gallic and ellagic acids. The jabuticabas showed small amounts of catechin and gallocatechin. P. jaboticaba showed the highest levels of anthocyanins and flavonols derived from myricetin, and P. phitrantha presented the highest concentration of ellagitannins and flavan-3-ols.

Effects of the pre-fermentative addition of chitosan on the nitrogenous fraction and the secondary fermentation products of SO2 -free red wines.

BACKGROUND: Different red winemaking were carried out to evaluate the effects of the prefermentative addition of chitosan, as an alternative to the use of SO2 , on the secondary products of alcoholic fermentation, yeast available nitrogen (YAN), biogenic amines and ethyl carbamate. RESULTS: The wines made with chitosan presented higher total acidity and higher content of tartaric and succinic acids than those made only with SO2 . The use of chitosan in winemaking resulted in wines with higher glycerol and diacetyl content without increasing the concentration of ethanol, acetic acid, acetaldehyde or butanediol. YAN was lower in wines made with chitosan, which may mean an advantage for the microbial stability of the wines. Furthermore, the use of chitosan at the beginning of alcoholic fermentation did not increase the concentration of biogenic amines or the formation of ethyl carbamate in SO2 -free red wines. CONCLUSION: The total or partial substitution of SO2 for chitosan at the beginning of the alcoholic fermentation gives rise to quality red wines without negatively affecting their nitrogen fraction or their very important secondary fermentation products such as acetic acid or acetaldehyde. © 2020 Society of Chemical Industry.

Comprehensive Chemical and Sensory Assessment of Wines Made from White Grapes of Vitis vinifera Cultivars Albillo Dorado and Montonera del Casar: A Comparative Study with Airén.

The ability to obtain different wines with a singular organoleptic profile is one of the main factors for the wine industry's growth, in order to appeal to a broad cross section of consumers. Due to this, white wines made from the novel grape genotypes Albillo Dorado and Montonera del Casar (Vitis vinifera L.) were studied and compared to the well-known Airén at two consecutive years. Wines were evaluated by physicochemical, spectrophotometric, high-performance liquid chromatography-diode array detection-mass spectrometry, gas chromatography-mass spectrometry and sensory analyses. The chromatic characteristics of the new wines were defined by more color purity than Airén, with greenish highlights. In general, the phenolic profile of the Albillo Dorado wines showed a higher flavonol and hydroxycinnamic acid derivative content. Several volatile compounds were determined, and their odor activity values were calculated to determine their impact on wine aroma. A fruity series dominated the wine aromatic composition, but spicier and greener notes characterized the aroma profile of Airén wines. Albillo Dorado and Montonera del Casar were sensory evaluated as wines with a less fresh taste compared to Airén. Unique chemical and sensory profiles were determined for wines made from these novel grape genotypes, providing alternative monovarietal wines to encourage the wine market growth and extend the offer to consumers.

Influence of grape seeds on wine composition and astringency of Tempranillo, Garnacha, Merlot and Cabernet Sauvignon wines.

BACKGROUND: The aim of this work was to study the influence of grape berry morphology, especially the seed weight percentage, on the tannin concentration and astringency of red wine. Clusters of Tempranillo, Garnacha, Merlot, and Cabernet Sauvignon were characterized and their seeds were extracted and macerated in a model wine solution. In parallel, we elaborated three types of wines of each cultivar. One wine was made with only grape juice, one wine was made adding the appropriate proportion of seeds to the grape juice, and the last wine was elaborated with the complete destemmed and crushed berries. RESULTS: Merlot and Cabernet Sauvignon grapes, which have higher percentage of seed weight with respect to the berry weight than Tempranillo and Garnacha grapes originated wines with higher tannin concentration and astringency than Tempranillo and Garnacha wines. CONCLUSION: The main conclusion of this study is that the seed weight percentage with respect to the berry weight is one of the main determinants of the final tannin concentration and astringency of red wines.

Impact of oenological antioxidant substances on the formation of 1-hydroxyethyl radical and phenolic composition in SO2 free red wines.

BACKGROUND: Different natural substances, chitosan, inactive dry yeasts and freeze-dried aqueous extracts from two wine industry by-products (stems and shoots) were used in red winemaking as possible alternatives to SO2 . The resistance to oxidation of wines was evaluated by electron paramagnetic resonance. The phenolic composition of wines was analyzed by high-performance liquid chromatography-diode array detection/electrospray ionization mass spectrometry, antioxidant activity was determined by DPPH (1,1-diphenyl-2-picrylhydrazyl radical) and ABTS [2,2'-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid) radical cation] assays and spectrophotometric measurements of color were compared. RESULTS: The wines elaborated with chitosan and inactive dry yeast presented greater capacity to inhibit the formation of the 1-hydroxyethyl radical compared to the wines elaborated with stem or shoot extracts. The total content of anthocyanins was higher in the wines elaborated with SO2 ; however, the concentration of flavan-3-ols was higher in the wines with chitosan. In addition, the wines with chitosan and inactive dry yeast presented the highest % polymerization. Wines elaborated with stem extract had a lower concentration of flavonols and stilbenes. CONCLUSION: Chitosan and inactive dry yeast, which are used as an alternative to SO2 in winemaking, allow the control of the formation of 1-HER in red wines. Wines with stem and shoot extracts showed a lower resistance to oxidation. © 2020 Society of Chemical Industry.

Analysis of the phenolic composition and yield of 'BRS Vitoria' seedless table grape under different bunch densities using HPLC-DAD-ESI-MS/MS.

Grapes are considered to be a major source of phenolic compounds as compared with other fruits. To improve the quality of table grapes, some techniques like thinning can be used. In addition, grape cultivars with distinct characteristics are directly linked to its phenolic profile. This study aimed to identify and quantify the phenolic compound profile and yield of the hybrid 'BRS Vitoria' seedless table grape under different bunch densities, using a combination of solid-phase extraction (SPE) methodologies and analytical high-performance liquid chromatography-diode array detector with tandem mass spectrometry (HPLC-DAD-ESI-MS/MS). A trial was carried out in 2016, in a commercial vineyard at Marialva, state of Parana (South Brazil). Three weeks after anthesis, the following bunch densities were evaluated: 4.0, 4.5, 5.0, 5.5, and 6 bunches per m2 (corresponding to an estimation of 16, 18, 20, 22, and 24 tons ha-1). The randomized block design was used as a statistical model with each treatment was replicated four times, with one vine per plot. Different characteristics were evaluated at harvest, e.g., soluble solids content (SS), total acidity (TA), maturation index (MI = SS/TA), bunch and berry masses, yield, as well hydroxycinnamic acid derivative (HCAD), anthocyanin, flavonol, and flavan-3-ol contents by HPLC-DAD-ESI-MS/MS analysis. The evaluated bunch densities did not interfere with the physicochemical characteristics of the berries, such as SS and MI. Under the density of 6.0 bunches per m2, the highest yield of 25 tons ha-1 was reached. Under all bunch densities, the phenolic profile presented the same compounds, but at different concentrations. Under a density of 5.0 bunches per m2, the compounds belonging to the anthocyanin and flavonol families were present in high concentrations. In contrast, at the densities of 4.0 and 4.5 bunches per m2, there was a reduction in the flavan-3-ol content. With respect to stilbenes, only the trans-piceid and its cis- isomer were detected. However, their concentrations had no significant influence on the evaluated bunch densities.

Potential of Different Natural Antioxidant Substances to Inhibit the 1-Hydroxyethyl Radical in SO2-Free Wines.

The potential of different natural antioxidants to inhibit the 1-hydroxyethyl radical formation in SO2-free wines was analyzed by electron paramagnetic resonance (EPR). Chitosan, glutathione, inactive dry yeast, oak and grape seed extracts, and ascorbic acid were tested in white and red wines. The ability of these substances to prevent the formation of acetaldehyde after the Fenton reaction and the oxygen consumption capacity were measured. Ascorbic acid was the antioxidant substance that offered higher percentages of 1-hydroxyethyl radical inhibition at 30 min of reaction. However, wines with ascorbic acid showed higher concentrations of acetaldehyde after the Fenton reaction. Grape seed extract and chitosan provided higher percentages of radical inhibition in red wine than those in white wine, in contrast to the inactive dry yeast that only produced radical inhibition in white wine. Although oak extract did not produce changes in the 1-hydroxyethyl radical, wines with that extract had lower concentrations of acetaldehyde.

Sensory descriptive and comprehensive GC-MS as suitable tools to characterize the effects of alternative winemaking procedures on wine aroma. Part II: BRS Rúbea and BRS Cora.

The present manuscript assessed the volatile and sensory profiles of BRS Rúbea and BRS Cora wines elaborated from traditional, grape pre-drying and submerged cap winemaking. The wines contained a higher concentration of acetates (257 mg L-1 to 547 mg L-1) and ethyl and methyl esters (183 mg L-1 to 456 mg L-1) in comparison with Vitis vinifera wines. PCA was applied (explaining 68.43% of the total variance), and the higher concentration of ethyl decanoate and ethyl octanoate, diethyl succinate, hydroxylinalool, and 2-phenyl ethanol was responsible for describing the BRS Rúbea wines as fruity/foxy. They also presented an intense jam note, probably due to their higher concentration of syringol and guaiacol. BRS Cora wines exhibited a vegetal note, possibly due to their higher concentration of 1-hexanol and cis-3-hexenol. Wines from pre-dried grapes presented higher concentration of furfural, assuming a bitter/burned almond aroma. Alternative winemaking accounted for suitable changes in wine aroma, enhancing wine quality.

Natural extracts from grape seed and stem by-products in combination with colloidal silver as alternative preservatives to SO2 for white wines: Effects on chemical composition and sensorial properties.

The search for alternative additives to sulfur dioxide, with antioxidant and antimicrobial activity, in the production of wines is one of the current objectives of the enological industry. In the present study, aqueous extracts obtained from winery byproducts (grape seeds and stems), alone or in combination with colloidal silver complex, have been used in white vinification. The antimicrobial effect of the extracts was similar to that of sulfur dioxide, being more effective on lactic and acetic bacteria in those wines to which colloidal silver was added. The effect on the color, the phenolic compounds and the volatile fraction of the wines was evaluated, as well as their sensory profile. The use of both extracts modified the color of the wines, increasing the chromatic parameters a* and b*, indicating a browning tendency, although no other signs of oxidation were found. Wines with seed extracts contained higher amounts of flavan-3-ols, and a significant increase in some volatile compounds such as fatty acid ethyl esters and benzene compounds, which were identified in the extracts. From a sensorial point of view, the wines with stem extracts were the most similar to those elaborated with SO2, detecting a certain bitterness in wines with seed extracts.

Phenolic compounds profile of different berry parts from novel Vitis vinifera L. red grape genotypes and Tempranillo using HPLC-DAD-ESI-MS/MS: A varietal differentiation tool.

The detailed phenolic composition of different berry parts from two novel V. vinifera L. red grape genotypes (Moribel and Tinto Fragoso), together the well-known Tempranillo, was established using high performance liquid chromatography-diode array detection-electrospray ionization tandem mass spectrometry (HPLC-DAD-ESI-MS/MS) over two consecutive vintages (2016 and 2017). More than 50 phenolic compounds were identified and quantified: 25 anthocyanins, 17 flavonols, 7 hydroxycinnamic acid derivatives, 2 stilbenes, and several flavan-3-ols. As far as we know, some anthocyanin and flavonol dihexosides were reported for the first time in V. vinifera L. grapes. Application of Principal Component Analysis (PCA) to experimental data showed a good separation of the novel grape genotypes and Tempranillo according to the phenolic profile of skins and seeds, mainly based on the proportion of trisubstituted anthocyanin derivatives, flavonols and flavan-3-ols, being a useful tool to differentiate these grape varieties.

Systematic study of hydroxyl radical production in white wines as a function of chemical composition.

The chemical oxidation of white wines through the Fenton reaction has been widely studied, wherein the primary species is the hydroxyl radical (OH). This radical possesses high oxidising power and may oxidise the primary components in wines. The Fenton reaction in wines is complex and includes the participation of phenolic compounds, organic acids, and metals. However, there has been no systematic study to date that relates wine composition to OH production in real white wines. In this paper, a multivariate model was generated using the partial least squares (PLS) algorithm, and linear correlations were established between wine composition and OH production. Based on the results, the variables were classified as either pro-oxidants (malic acid, p-coumaric acid, and caffeic acid, % prodelphinidins, procyanidins B1, Mn, Cu, and Zn) or antioxidants (cis-piceid, ellagic acid, gallic acid, proanthocyanins, glucose, and proton concentration). Finally, the pathways by which wine compounds participate in OH production are discussed.

First chemical and sensory characterization of Moribel and Tinto Fragoso wines using HPLC-DAD-ESI-MS/MS, GC-MS, and Napping® techniques: comparison with Tempranillo.

BACKGROUND: Due to the current dominance of a few grape varieties in the wine market, the aim of this work was to study the detailed phenolic and volatile composition, chromatic characteristics, and sensorial properties of red wines elaborated with new Vitis vinifera grapes (Moribel and Tinto Fragoso) identified using the High Perfomance Liquid Chromatography-Diode Array Detector-Electrospray Ionization-Tandem Mass Spectrometry (HPLC-DAD-ESI-MS/MS), Gas Chromatography- Mass Spectrometry (GC-MS), CIELab color space, and Napping ® techniques. RESULTS: Tinto Fragoso wine showed higher phenolic content than Moribel, with more anthocyanins, flavonols, and stilbenes. These wines also contained anthocyanin diglucosides not reported for Vitis vinifera wines. The odor activity values of free volatile compounds were calculated to indicate their influence on wine aroma, the fruity aromas of Moribel standing out particularly. The wines studied were positively evaluated by the tasters. Moribel's sensory profile was characterized by red fruit aromas and Tinto Fragoso showed more aromatic intensity and persistence in the mouth. CONCLUSION: The results obtained from the first characterization of red wines made from novel Vitis vinifera grapes suggest that Moribel and Tinto Fragoso could be appropriate raw materials for the elaboration of quality young red wines. Tinto Fragoso provided wines with sensorial properties different from those of Tempranillo, and could be an alternative to the well known red wines on the market. © 2018 Society of Chemical Industry.

Sensory descriptive and comprehensive GC-MS as suitable tools to characterize the effects of alternative winemaking procedures on wine aroma. Part I: BRS Carmem and BRS Violeta.

This study analyzed the volatile composition and aroma profile of BRS Carmem and BRS Violeta red wines elaborated from traditional and two alternative winemaking procedures: grape pre-drying and submerged cap. The wines contained higher concentration of acetates (ranging from 303 mg L-1 to 905 mg L-1) and ethyl and methyl esters (ranging from 138 mg L-1 to 415 mg L-1). The BRS Carmem wines were described as fruity due to the higher concentration of esters and BRS Violeta wines were described as vegetal mainly due to the higher concentration of terpenes and methoxyphenols. C6 alcohols also influenced the vegetal notes of BRS Violeta wines from traditional and submerged cap procedures and the pre-dried wines also presented a relevant jam note possibly due to the presence of 2-phenylethyl acetate. The changes in winemaking procedures can possibly lead to changes in the aromatic profile of red wines in a positive way, improving the wine aroma quality.

Oenological potential of extracts from winery and cooperage by-products in combination with colloidal silver as natural substitutes to sulphur dioxide.

The aim of this study was to evaluate the oenological potential of natural extracts from winery and cooperage by-products, either alone or with a colloidal silver complex (CSC), on the quality of red wines, as possible substitutes to SO2. Natural extracts were obtained from grape seeds and American oak wood by accelerated extraction with subcritical water. The prefermentative addition of grape seed or oak wood extracts was an useful tool to control acetic acid bacteria development, without affecting the alcoholic and malolactic fermentations. Both extracts protected the wines against oxidation, without negatively modifying their phenolic and volatile composition. They did not cause organoleptic defects in wines, which presented greater aromatic complexity and were positively evaluated by the tasters. Therefore, the use of grape seed or oak wood extracts in red vinification could be a good alternative to replace or reduce the doses of SO2.

Vine-Shoot Tannins: Effect of Post-pruning Storage and Toasting Treatment.

For the first time vine-shoot tannin composition was carried out by means of HPLC-DAD-ESI-MS/MS. Two vine-shoot cultivars (Airén and Cencibel) with different post-pruning storage times were submitted to a toasting process and assayed. There were no traces of gallotannins nor ellagitannins, but a high proanthocyanidin content and a mean degree of polymerization (mDP) close to 3 were characterized. The higher concentration of proanthocyanidins corresponded to Airén after 6 months post-pruning storage and at 3 months for Cencibel. Procyanidins were the most abundant fraction (70-95%), which decreased with storage, and especially significant was the contribution of B1, B2, and B4 dimers. Prodelphinidins were also found (8-24%), increasing their % with storage time. Toasting produced a considerable reduction of proanthocyanidin content and a loss of a monomer mDP unit, suggesting that if used as oenological tannins, then they may be more bitter and less astringent when compared with the nontoasted vine-shoot samples.

Oxygen consumption rates by different oenological tannins in a model wine solution.

The kinetics of oxygen consumption by different oenological tannins were measured in a model wine solution using the non-invasive method based on luminiscence. The results indicate that the oxygen consumption rate follows second-order kinetics depending on tannin and oxygen concentrations. They also confirm that the oxygen consumption rate is influenced by temperature in accordance with Arrhenius law. The indications are that ellagitannins are the fastest oxygen consumers of the different oenological tannins, followed in decreasing order by quebracho tannins, skin tannins, seed tannins and finally gallotannins. This methodology can therefore be proposed as an index for determining the effectiveness of different commercial tannins in protecting wines against oxidation.

Improved method for the extraction and chromatographic analysis on a fused-core column of ellagitannins found in oak-aged wine.

A new method for the analysis of ellagitannins observed in oak-aged wine is proposed, exhibiting interesting advantages with regard to previously reported analytical methods. The necessary extraction of ellagitannins from wine was simplified to a single step of solid phase extraction (SPE) using size exclusion chromatography with Sephadex LH-20 without the need for any previous SPE of phenolic compounds using reversed-phase materials. The quantitative recovery of wine ellagitannins requires a combined elution with methanol and ethyl acetate, especially for increasing the recovery of the less polar acutissimins. The chromatographic method was performed using a fused-core C18 column, thereby avoiding the coelution of main ellagitannins, such as vescalagin and roburin E. However, the very polar ellagitannins, namely, the roburins A, B and C, still partially coeluted, and their quantification was assisted by the MS detector. This methodology also enabled the analysis of free gallic and ellagic acids in the same chromatographic run.

Storage stability of phenolic compounds in powdered BRS Violeta grape juice microencapsulated with protein and maltodextrin blends.

The stabilities of the phenolic compounds, antioxidant activity and colour parameters of microencapsulated powdered BRS Violeta red grape juice were evaluated throughout storage at 5, 25 and 35°C for up to 150days. Different soy protein (S) or whey protein (W) blends with maltodextrin (M) were used as carrier agents, added at diverse concentrations and proportions. The treatment combining S and M with the highest carrier agent concentration (1SM) preserved almost all the anthocyanins. Except for 1SM, the proportion of p-coumaroylated anthocyanins increased during storage, and the flavonol content of the 1SM powder decreased after 150days. The hydroxycinnamate content decreased for all treatments, independent of storage temperature, and flavan-3-ols were lost at 35°C. The time and temperature did not influence the antioxidant activity of the powder or the colour of the reconstituted grape juice after 150days.

Influence of Grape Seeds and Stems on Wine Composition and Astringency.

The aim of this paper is to study the real influence of seeds and stems on wine composition, astringency, and bitterness. A decolored grape juice and a grape juice macerated for 4 days from the same Cabernet Sauvignon grapes were fermented with or without supplementation with 100% seeds, 300% seeds, or 100% stems. Once alcoholic fermentation had finished, the wines were analyzed and tasted. The presence of seeds and stems increased the concentration of flavan-3-ol monomers with respect to the controls. However, the seeds mainly released (+)-catechin and (-)-epicatechin, whereas the stems mainly released (+)-catechin and (+)-gallocatechin. The seeds and stems also released proanthocyanidins; those from seeds have a lower mDP and a high percentage of galloylation, whereas those from stems have a higher mDP and a relatively high percentage of prodelphinidins. The presence of seeds and stems brought about a slight but significant increase in pH and lowered titratable acidity and ethanol content. The presence of seeds boosted color intensity, whereas stems had the opposite effect. Finally, both seeds and stems increased wine astringency and bitterness.

Oxygen consumption by oak chips in a model wine solution; Influence of the botanical origin, toast level and ellagitannin content.

The botanical origin, toast level and ellagitannin content of oak chips in a model wine solution have been studied in terms of their influence on oxygen consumption. French oak chips released significantly higher amounts of ellagitannins than American oak chips at any toast level. The release of ellagitannins by oak chips decreased as the toast level increased in the French oak but this trend was not so clear in American oak. Oxygen consumption rate was clearly related to the level of released ellagitannins. Therefore, oak chips should be chosen for their potential to release ellagitannins release should be considered, not only because they can have a direct impact on the flavor and body of the wine, but also because they can protect against oxidation.