Influence of major polyphenols on antioxidant activity in Mencía and Brancellao red wines

The purpose of this work was to examine the relationship of the total polyphenol index (TPI) as measured spectrophotometrically and individual phenols as determined by HPLC to antioxidant activity in red wines made from two Vitis vinifera grape varieties grown in NW Spain (viz. Mencía and Brancellao) during bottled storage in the dark for 12 months. Antioxidant activity was determined by using various methods based on inhibition of the coupled oxidation of the β-carotene/linoleic acid mixture. Also, free radical scavenging activity was determined with 2,2-diphenyl-1-picrylhydrazyl (DPPH). Antioxidant activity as measured by DPPH after storage for 3 months was higher in Mencía wines than in Brancellao wines (4.5 ± 0.60 vs. 3.7 ± 0.30 mmol/L trolox equivalents). Beyond 3 months of storage, radical scavenging activity increased in both types of wine (from 4.5 ± 0.60 to 6.0 ± 0.80 mmol/L in Mencía wines and from 3.7 ± 0.30 to 4.7 ± 0.71 mmol/L trolox equivalents in Brancellao wines). The significant correlation found between antioxidant activity and TPI in all wines (r > 0.88) is indicative of the significance of condensation and polymerisation products to the total antioxidant activity of the wines. The relatively high correlation of total flavonols (r = 0.89) and acylated anthocyanins (r = 0.70) as measured by HPLC with to the overall antioxidant capacity suggests that these two polyphenol classes can substantially influence the antioxidant properties of these wines. The linoleic acid/β-carotene assay exposed a higher antioxidant capacity in Brancellao wines than in Mencía wines after 3 months of storage (6.0 ± 0.80 vs. 4.7 ± 0.70). Most of the studied wines lost an average 45% antioxidant activity during bottled storage. Antioxidant activity as measured with the linoleic acid/β-carotene assay was closely correlated with both hydroxycinnamic acids (r = 0.90) and flavanols (r = 0.71 and 0.61 for monomeric and polymeric forms, respectively).     

Phenolic compounds and colour stability of Vinhão wines: Influence of wine-making protocol and fining agents

The purpose of this work is to study the evolution, over three selected harvests, of phenolic compounds and colour stability of red wines produced in the north of Portugal by means of two wine-making processes (conventional maceration/fermentation and fermentation after initial carbonic maceration), with and without the use of four different fining agents (polyvinylpolypyrrolidine, gelatine, egg albumin, and casein). In general, it was observed that wines obtained by conventional maceration/fermentation (PO) present the highest colour intensity and polyphenolic content (total and monomeric anthocyanins, flavan-3-ol monomers and polymers), and the lowest orange–red hue, immediately following vinification. Nevertheless, carbonic maceration (CM) afforded wines with most stability in colour density, for 26 months’ storage. Different evolutions of anthocyanins and of flavan-3-ol monomers (catechins) and polymers (procyanidins) in PO and CM protocols during storage were observed. Decrease of anthocyanins and flavan-3-ol dimmers were, in general, more remarkable in PO wines. Monomers and trimers underwent a rise, especially in CM wines. Wines treated with fining agents tended to have somewhat lower anthocyanins levels, and especially in the case of PVPP, less intense colouration than untreated wines. Principal component analysis (PCA) revealed that catechins and some procyanidins are mainly responsible for the separation and evolution of wines during storage according polyphenolic composition. Partial least squares (PLS) regression models confirm that colour density in wines from PO and CM protocols explains a high proportion of the variance in hue, chemical age, IFC and anthocyanins and a prediction model has been built.     

Phenolic composition of Tempranillo wines following early defoliation of the vines

BACKGROUND: Early defoliation is a viticultural practice aimed at crop control. So far, the impact of early leaf removal on the monomeric phenolic composition of wines has not been explored. This study examines the effects of early defoliation on the phenolic profile and content in Tempranillo wines. The influence of the defoliation method (manual vs mechanical) and the timing of leaf removal (pre‐bloom vs fruit set) was investigated. RESULTS: Over two consecutive seasons, 2007 and 2008, the monomeric phenolic composition in Tempranillo wines was studied by high‐performance liquid chromatography with photodiode array detection, and 22 compounds were identified and quantified. Overall, early defoliation led to wines more intensely coloured, of higher alcohol content and with larger concentrations of hydroxycinnamic acids, flavonols and anthocyanins (in 2008 only for mechanical treatments). In the absence of fungal infection, resveratrol was found to increase in wines corresponding to early defoliation treatments. The method of leaf removal seemed to be more critical than the timing of intervention, and larger effects on wine phenolic composition were observed for mechanical treatments. CONCLUSION: Early defoliation proved to be an effective technique for improving the phenolic composition of Tempranillo wines, by favouring the accumulation of hydroxycinnamics, flavonols and anthocyanins. This is an important achievement, as wine quality is often described by its colour and phenolic attributes. Copyright © 2011 Society of Chemical Industry     

Comparing the effects of exogenous abscisic acid on the phenolic composition of Yan 73 and Cabernet Sauvignon (Vitis vinifera L.) wines

Phenolic compounds from red wines exert a strong influence on wine quality. Abscisic acid (ABA) is essential for the physiological and biochemical function of plants, but few investigators have thoroughly researched its effects on phenolic compounds in dyer grape varieties. The effects of exogenous ABA treatment on the phenolic composition and individual anthocyanin and non-anthocyanin phenolic contents of Yan 73 and Cabernet Sauvignon wines from the ABA-treated grapes, including anthocyanins, flavan-3-ols, flavonols, phenolic acids, and stilbenes were compared. The phenolic compounds in the Yan 73 wine were different from those in the Cabernet Sauvignon wine. The phenolic content (anthocyanins and non-anthocyanins) of the Yan 73 wine was significantly higher than that of the Cabernet Sauvignon wine. The concentrations of the individual phenolic compounds were enhanced by the ABA treatment for the two different wine varieties. The effects on the compositions varied, a similar trend was observed for the ratios of Cy-derivative and Dp-derivative pigments from the two wine varieties, and all non-acylated pigments were enhanced. The stilbene content was enhanced, the ratios of flavan-3-ol dimers and dimer-glucosides were reduced, and the effects on the composition of other compounds varied between the two grape varieties.     

A survey of phenolic compounds in Spanish wines of different geographical origin

 The phenolic composition of red and white wines from four Spanish Appellations of Origin (official classification of Spanish wines) was investigated. Different hydroxybenzoic and hydroxycinnamic acids, catechins, procyanidins, alcohols, stilbenes and flavonols were identified. Additionally, the ketone 2,3-dihydroxy-1-guaiacylpropan-1-one was identified for the first time in red wines aged in oak barrels. The concentration of most of the phenolic compounds quantified was higher in red wines than in white wines, as would be expected from the different methods of vinification and the grape varieties used. These differences could also contribute to differences in the antioxidant ability of these wines. The multivariate analysis applied to the phenolic compounds quantified allowed the relationships among these compounds to be examined and the origin of the wines to be distinguished. Received: 31 May 1999 / Revised version: 16 August 1999     

Phenolic characterisation of red wines from different grape varieties cultivated in Mendoza province (Argentina)

BACKGROUND: Knowledge of the chemical composition of wine and its association with the grape variety/cultivar is of paramount importance in oenology and a necessary tool for marketing. Phenolic compounds are very important quality parameters of wines because of their impact on colour, taste and health properties. The aim of the present work was to study and describe the non‐flavonoid and flavonoid composition of wines from the principal red grape varieties cultivated in Mendoza (Argentina). RESULTS: Sixty phenolic compounds, including phenolic acids/derivatives, stilbenes, anthocyanins, flavanols, flavonols and dihydroflavonols, were identified and quantified using high‐performance liquid chromatography with diode array detection coupled with electrospray ionisation mass spectrometry (HPLC‐DAD/ESI‐MS). Marked quantitative differences could be seen in the phenolic profile among varieties, especially in stilbenes, acylated anthocyanins and other flavonoids. CONCLUSION: The polyphenolic content of Malbec wines was higher compared with the other red varieties. Dihydroflavonols represent a significant finding from the chemotaxonomic point of view, especially for Malbec variety. This is the first report on the individual phenolic composition of red wines from Mendoza (Argentina) and suggests that anthocyanins, flavanols and phenolic acids exert a great influence on cultivar‐based differentiation. Copyright © 2011 Society of Chemical Industry     

Wine phenolics—analysis of low molecular weight components by high performance liquid chromatography

Low molecular weight phenolic compounds were separated by high performance liquid chromatography on hydrocarbon-bonded reverse phase packings, with a water-methanol elution gradient. Phenolic compounds were extracted from wine with ethyl acetate. A first extraction at pH 7 enabled isolation of neutral molecules (catechins, procyanidins, flavonols, aromatic alcohols); a second extraction at pH 2 was performed to extract phenolic acids. Successive injections of these two extracts in the chromatograph gave the distribution of the different phenolic compounds in the wine under analysis. Analytical data are given for low molecular weight phenolic compounds present in young red Bordeaux wines from different vine cultivars.     

Anthocyanins and flavonols berries from Vitis vinifera L. cv. Brancellao separately collected from two different positions within the cluster

Galicia (N.W. Iberian Peninsula) is a Spanish region with several old-traditional winegrowing areas. Vitis vinifera L. cv. Mencía is one of the most often used to produce quality red wines in the five Galicia Denomination of Origin. However, there are traditional cultivars such as Brancellao, which were not exploited for their potential to produce quality red wines. Dynamics of anthocyanin and flavonol accumulation were studied separately in two different positions within the cluster (tips and shoulders), during 30 days before harvest. The objective of separating berries is to assess the existence of different polyphenol quality in both positions; as a consequence, the selection and harvest of those berries with a higher content of anthocyanins and flavonols could produce red wines with different qualities. Derivatives of five anthocyanins (malvidin, peonidin, petunidin, delphinidin and cyanidin) were detected in skins at both positions within the cluster. Anthocyanin contents stabilized in the 30 days prior to harvest in the berries from the shoulders whereas they continue to increase in those from the tips. Derivatives of six flavonols (quercetin, myricetin, kaempherol, laricitrin, isorhamnetin and syringetin) were detected in skin and flesh at both positions within the cluster. Dynamics of anthocyanins (from 400 to 515 mg/kg in tips; and from 598 to 574 mg/kg in shoulders) and flavonols (from 19 to 29.3 mg/kg in tips; and from 22.7 to 29.4 mg/kg in shoulders) over ripening confirmed that these polyphenols presented upward trends. Therefore, it is not necessary to harvest Brancellao berries separately and a high quality red wine will be obtained with berries from entire clusters regarding these compounds.     

The impact of oxygen exposure before and after bottling on the polyphenolic composition of red wines

The impact of moderate oxygen exposure after bottling on wine phenolic composition and colour properties has been investigated on four Grenache red wines showing high and low phenolic contents, obtained by flash release (FR) and traditional soaking (Trad), respectively, and processed with (Mox, 4.6 mg l⁻¹ O₂) or without (noMox) micro-oxygenation. Four oxygen transfer rate (OTR) conditions (0.8, 1.9, 8.0, and 11.9 μl oxygen/bottle/day) were ensured by using synthetic closures with controlled oxygen permeability and storage under controlled atmosphere. Wine phenolic composition and colour were monitored by triplicate analysis of bottles sampled at bottling (T0) and after 5 and 10 months of ageing. Phenolic composition was determined by reverse-phase HPLC-DAD–MS analysis, performed directly on the wines and after phloroglucinolysis for proanthocyanidins. Colour was evaluated by UV–visible spectrophotometry and tristimulus colorimetry. At T0, FR wines contained larger amounts of catechins, proanthocyanidins and hydroxycinnamic acids and slightly lower amounts of anthocyanins than the Trad wines while the Mox wines showed higher levels of some derived pigments, especially carboxypyranoanthocyanins, resulting from reactions of anthocyanins with pyruvate. During ageing, a progressive decrease of proanthocyanidins and hydroxycinnamic acid concentrations was observed, independently of OTR. In contrast, the loss of free SO₂, flavan-3-ol monomers and the conversion rate of anthocyanins to new pigments, especially into sulphite bleaching resistant pigments, increased with OTR levels. Among derived pigments, carboxypyranoanthocyanins levels increased both with micro-oxygenation and with OTR and can be considered as oxidation markers while flavan-3-ol–anthocyanin adducts were formed in larger amounts with lower oxygen exposure.     

Evolution of polyphenolic compounds in red wine from Cabernet Sauvignon grapes processed by pulsed electric fields during aging in bottle

The evolution of the Folin–Ciocalteu index, colour intensity and the principal individual polyphenols throughout 12 months of aging in bottles of red wine from Cabernet Sauvignon grapes treated and untreated by pulsed electric fields (PEF) have been compared. PEF technology allowed bottling of wines with higher Folin–Ciocalteu index, colour intensity and individual polyphenols concentrations using a shorter maceration time. For both wines, aging did not affect the colour intensity, whereas the Folin–Ciocalteu index decreased. The evolution of the principal individual polyphenols during the 12 months of storage followed a similar pattern in both wines. At the end of aging, there were no significant differences observed in the content of monomeric anthocyanins between both wines, however, the content of flavan-3-ols, flavonols and hydroxycinnamic acids and derivatives was higher in PEF treated wine. These results indicate that PEF could be a suitable technology for obtaining wines with higher phenolic content or reducing the maceration time during vinification.     

Evaluation of the potential of high pressure technology as an enological practice for red wines

The impact of high hydrostatic pressure (HHP) treatments on the phenolic compounds composition of a red wine was studied after storage in order to evaluate the potential of this technology as an enological practice. Red wines pressurized at 500 and 600 MPa at 20 °C for 5 and 20 min, respectively, showed a lower content of monomeric anthocyanins (13 to 14%), phenolic acids (8 to 11%), and flavonols (14 to 19%) after 5 months of storage, when compared to the unpressurized wine. These results, together with the different degree of tannin polymerization and flavan-3-ol content in the pressurized wines led to propose an effect of HHP in the increase of polymerization and cleavage reactions of proanthocyanidins. The sensorial analysis of pressurized wines showed lower astringency, a higher intensity of cooked fruit aroma and lower intensity of fruity notes, when compared with the unpressurized wine. These effects are associated to those observed during wine aging.Industrial relevanceDuring the last decade, the use of high hydrostatic pressure (HHP) as a non-thermal technology for food preservation and modification has increased substantially. Recently, pressure treatments have shown to influence long term red wine physicochemical and sensorial characteristics, leading to aged wine-like characteristics. Therefore, the use of HHP technology to modify wine composition could benefit the wine industry, especially to improve wines with low aging potential. This work shows that HHP can be potentially used as enological practice, modulating the organoleptic properties of wine by decreasing astringency and increasing pleasant aromas. It seems possible to exploit commercially the production of young red wines with distinct characteristics using this technology, addressing the market and consumer demand.     

Practical interventions that influence the sensory attributes of red wines related to the phenolic composition of grapes: a review

The phenolic composition of red wines is complex and intimately involved in colour, taste, mouth‐feel and aroma. There have been significant advances in knowledge of compounds with relatively simple structures, but understanding of those with more complex and probably diverse structures is challenging. A number of phenolic compounds may form temporary complexes with anthocyanins and/or be involved in reactions that lead to relatively stable coloured compounds. A wide range of phenolic compounds is implicated in the oral sensory attributes of red wines. Of particular importance are flavan‐3‐ols, including proanthocyanidins (PAs). The generally observed decline in the extractability of PAs during berry ripening is due to binding with cell wall material, which may occur within the developing berry and also from tissues brought into contact during processing. Studies have shown that exposure/reduced vigour results in an increasing proportion of skin PAs being extractable during wine making. Temperature and light influence anthocyanin with temperature probably being more important and the most sensitive stage being 1–3 weeks after véraison. Skin PAs are extracted earlier than those from seeds during wine‐making. Recent results suggest some rearrangement of skin and/or seed PAs occurs during vinification which involves the cleavage of large polymers or the aggregation of small ones. The polymeric material is particularly influential in wine astringency and is transformed by incorporation of anthocyanins into tannin‐like compounds during wine‐making and storage. Although some grape‐derived phenolic compounds contribute to the aroma of red wines, likely of greater importance are the effects of nonvolatile phenolics on the volatility of a diverse range of aroma compounds. Advances in analytical techniques are likely to provide greater insights into the structures and conformations of phenolic polymers and the role of cell wall material in relation to phenolic extraction and reaction during vinification. In relation to aroma, much more research is required to reveal the details of the interactions involving phenolics with volatile compounds. It seems likely that the ability to influence the relative extraction and subsequent reaction of skin and seed phenolics is important in the production of full colour, aromatic and long‐lived wines.     

Colour and phenolic compounds in sweet red wines from Merlot and Tempranillo grapes chamber-dried under controlled conditions

Chamber drying under controlled temperature and humidity conditions of the red grape varieties Merlot and Tempranillo grown in Andalusia (Spain), and the fortification and maceration of the musts in the presence of skin from both types of grapes, to obtain sweet red wines, has been studied. Changes in colour and in monomeric and polymeric phenols during the vinification process were examined. Chamber drying increased the sugar content to about 31.4 °Brix within 48 h in Merlot grapes and 72 h in Tempranillo grapes. This drying process also causes skin rupture, facilitating the access of phenolic compounds to the pulp. The resulting musts exhibited slight browning and increased red hues, due to a high concentration of anthocyanins; maceration in the presence of grape skins for 24 h provided the best results. The end-product contained highly acceptable tannin, colour and phenolic compounds for marketing as a high quality sweet red wine, in comparison with other commercial sweet red wines.     

Impact of Processing Parameters on the Phenolic Profile of Wines Produced from Hybrid Red Grapes Maréchal Foch,Corot noir,and Marquette

Phenolic extraction in hybrid and interspecific wine grape cultivars is poorly understood, especially in terms of the impact of fermentation and enological conditions on condensed tannins and anthocyanins. Following fractionation via solid‐phase extraction and high‐performance liquid chromatography, phenolic profiles of must and wine from red hybrid grape cultivars Maréchal Foch, Corot noir, and Marquette were examined to assess the impact of enzyme and tannin addition, cold soak, and hot press during vinification. Across cultivars, hot press treatments resulted in the greatest extraction of condensed tannin, anthocyanin, and other monomeric phenolic compounds in musts, and treatments that increased skin contact time or cellular degradation during fermentation produced higher concentrations of tannins, anthocyanins, and flavonols. However, these increases were transient, evincing incomplete carryover into finished wines. Depending on initial must extraction, diglucoside forms of anthocyanins were either selectively extracted or selectively retained throughout fermentation when compared to their monoglucoside counterparts. Typical of hybrid grapes, tannin concentrations across cultivars were low, even under hot press conditions. For condensed tannins and anthocyanins, a cultivar‐specific, stable‐state concentration and phenolic profile emerged regardless of fermentation conditions. Due to the high levels of diglucoside anthocyanins and low levels of condensed tannins, it is expected that the color development and profile in these wines produced from hybrid grape cultivars will be dictated by the monomeric anthocyanins and their potential role in copigmentation processes involving other monomeric phenolic species, as opposed to the formation of polymeric color pigments.     

Changes in phenolic composition of Tinta Miúda red wines after 2 years of ageing in bottle: effect of winemaking technologies

The major phenolic compounds (catechins, oligomeric and polymeric proanthocyanidins, and anthocyanins) in Tinta Miúda red wines made by various winemaking technologies (i.e., fermentation with carbonic maceration, fermentation with stem contact and fermentation without stem contact) were analyzed after 2 years of ageing in bottle, and compared with the data on their younger state (i.e., at the time of bottling). The concentrations of all individual phenolic compounds analyzed were significantly changed and their degradation rates (percent of decrease) were highly dependent on the winemaking technology used. The degradation of anthocyanins was, in general, more remarkable than that of catechins and proanthocyanidins. Catechins and proanthocyanidins in carbonic maceration wine appeared more stable than in skin fermentation wines, during ageing in bottle.     

Multivariate statistical analysis for the classification of oak-aged wines based on their chromatic characteristics

The objective of this study was to characterise oak-aged wines according to the ageing conditions by measuring colour and phenolic compounds, and to study the correlations between the studied variables to understand the relationship among them, and help to clarify some of the mechanisms involved in the modification of colour during wine ageing. The results show that the colour of aged wines can be mainly attributed to polymeric compounds and not to monomeric anthocyanins; the cluster analysis showed that the samples could be mainly separated as regards the age of the barrel. The discriminant analysis achieved a good sample separation regarding oak origin and barrel age.     

Comparison between the phenolic composition of Petit Verdot wines elaborated at different maceration/fermentation temperatures

The objective of this work was to contribute to the knowledge of the relationship between phenolic composition and the temperature of maceration/fermentation on Petit Verdot red wines, which were made with three treatments (17°C, 21°C, and 25°C). The phenolic compounds of Vitis vinifera cv. Petit Verdot wines elaborated at different maceration/fermentation temperatures were determined and compared by high-performance liquid chromatography coupled with diode array detector and electrospray ionization mass spectrometry. A total of 45 phenolic compounds were detected in all wines. The phenolic composition was affected by the temperature of maceration. The increment of maceration/fermentation temperature had a positive effect on the total concentration of the phenolic compounds and chromatic characteristics of these wines. The colour of Petit Verdot young red wines showed more colour intensity and their luminosity descended due to the increase in temperature. The highest total content of anthocyanins was determined in wines macerated at 21°C. However, other groups of phenolic compounds (flavonols, proanthocyanidins, and stilbenes) increased their total content by raising the maceration/fermentation temperature, reaching maximum values at 25°C.     

Evolution of the phenolic content of red wines from Vitis vinifera L. during ageing in bottle

The evolution of the phenolic content, as measured by spectrophotometric methodologies [total polyphenols (TP), low-polymerized polyphenols (LPP), total anthocyanins (TA), catechins (CAT), proanthocyanidins (PRO) and o-diphenols (OD)], was studied in young red wines from Vitis vinifera L. cv Tempranillo, Graciano and Cabernet Sauvignon during 26 months of ageing in bottle. Although the wines showed differences in their initial phenolic profiles, the evolution trend of the different families of phenolic compounds was similar in the wines from the three grape varieties. TA markedly decreased during ageing in bottle (43% for Tempranillo, 65% for Graciano and 66% for Cabernet Sauvignon), following a first-order kinetic. Calculation of the kinetic parameters revealed that the disappearance rate of TA was 2-fold lower for Tempranillo wine than for Graciano and Cabernet Sauvignon wines, which exhibited similar kinetics. This decrease in TA (due to the disappearance of monomeric anthocyanins), together with a increase registered in CAT and PRO (due to the cleavage of proanthocyanidins and their structural tranformations), was consistent with a decrease in LPP, suggesting the occurrence of condensation reactions during ageing in bottle. The evolution trends observed for TP and OD during ageing in bottle were the results of changes in the different groups of phenolic compounds involved in both determinations. Global phenolic determinations, usually performed in wineries, provided useful information in relation to the evolution of wine polyphenols during ageing in bottle.     

Micro-oxygenation and oak chip treatments of red wines: Effects on colour-related phenolics,volatile composition and sensory characteristics. Part II: Merlot wines

The character of Merlot wines after the treatments of micro-oxygenation and subsequent chips addition, as regards the colour-related phenolics, volatile composition and sensory characteristics, was studied. An increase in the degree of polymerisation of red pigments and a decrease in the value of the red component of the colour (a^*) and the degree of co-pigmentation were observed. The concentrations of monomeric anthocyanins and anthocyanin-derived pigments, such as hydroxyphenyl-pyranoanthocyanins and anthocyanin-ethyl-flavan-3-ol adducts, significantly decreased. With regard to the wine aroma, the micro-oxygenation produced a decrease of some esters, alcohols and benzenic compounds and increased some terpenes and C₁₃-norisoprenoids. With regard to sensorial analysis, micro-oxygenation treatment resulted in higher scores for the red fruit and spicy attributes and caused the presence of new attributes (nutty and sweet fruit). This technique produces a lower level of the typical oak chip aromas (vanilla and woody) in Merlot wines.