Colour features and pigment composition of Italian carbonic macerated red wines

Thirty commercially available Italian carbonic macerated young red wines, have been analysed by HPLC–DAD–MS with the aim to characterise their pigment composition and find possible correlations with the colour features evaluated by means of spectrophotometric measurements. The composition in anthocyanin monoglucosides, acetates, p-coumarates as well as that in pyranoanthocyanins and direct and ethyl-bridged adducts with flavanols, was studied. Because of the peculiar maceration process, carbonic macerated wines demonstrated to be qualitatively rich in pyranoanthocyanins and pigment adducts. A number of ethyl-bridged anthocyanin isomers was found, together with significant contents of vitisin A and vitisin B (up to 15.5 mg/L as a sum). Malvidin-3-glc-4-vinylphenol was the main pyranoanthocyanin-vinylphenol adduct (up to 1.10 mg/L). The colour features of the wines were broadly distributed as a consequence of the percentage of carbonic macerated wine present in the marketed product. The statistical treatment of the entire data set revealed that pyranoanthocyanins are positively correlated with colour density (while no correlation was found for monoglucosides) and that direct adducts and/or ethyl-bridged compounds can play a role for what concerns the hue of carbonic macerated wines.     

The effect of Saccharomyces cerevisiae and Saccharomyces bayanus yeast on colour properties and pigment profiles of a Cabernet Sauvignon red wine

Red wine was made from the same batch of Cabernet Sauvignon grapes but with two different yeasts, Saccharomyces cerevisiae (SC) or Saccharomyces bayanus (SB). The colour properties and pigment profiles of SC and SB wines were compared at 8 days and 387 days after yeast inoculation. Grape anthocyanin concentration was found to be lower in SB wines than in SC wines at day 8 and 387, but SB wine exhibited greater wine colour density, a* and b*. The anthocyanin concentration did not correlate with wine colour density. The levels of pigmented polymers and SO₂ non-bleachable pigments were found to be higher in SB wine at day 387, demonstrating that the formation of stable pyranoanthocyanins and pigmented polymers was enhanced by SB yeast. Electrospray mass spectrometry was used for the compositional analysis of pyranoanthocyanins, and direct and ethyl-bridged linked condensation dimers of malvidin 3- O -glucoside (MvG) with flavanols (catechin or epicatechin). The data demonstrated that the formation of acetaldehyde-mediated pigments was enhanced by the use of the SB yeast. The compositional analysis suggested that the differences in colour properties and pigment profiles of SC and SB wines were largely due to the greater production of acetaldehyde-mediated pigments by the use of SB yeast.     

Evolution of polyphenols in red wines from Vitis vinifera L. during aging in the bottle

The evolution of anthocyanins and pyranoanthocyanins (as measured by high-performance liquid chromatography) in young red wines from Vitis vinifera L. cv Tempranillo, Graciano and Cabernet Sauvignon (vintage 2000) from Navarra (Spain) was studied during 26 months of aging in the bottle. For the anthocyanin pigments of grape origin, a progressive decrease in their concentration, corresponding to first-order kinetics, was observed during this period. Independently of the anthocyanin structure studied, grape anthocyanins in Tempranillo wine presented twofold slower kinetics than those in Graciano and Cabernet Sauvignon wines, which exhibited a very similar disappearance rate. Acylated anthocyanins presented a slightly higher disappearance rate than the nonacylated ones, indicating the possible hydrolysis of the former into the latter forms. However, no distinction was observed in the kinetics of the different anthocyanidin forms (delphinidins, petunidins, peonidins and malvidins). These results indicate that during aging under nonoxidative conditions (bottle), the chemical reactivity of grape anthocyanins in wine is influenced by the grape variety, a factor that imposes over the stability associated with the chemical structure of each anthocyanin form. In relation to the evolution of pyranoanthocyanins, anthocyanin–pyruvic acid adducts presented a similar or lower disappearance rate than their corresponding anthocyanin precursors during the first months of aging in the bottle, while anthocyanin–vinylphenol and anthocyanin–vinylflavanol adducts did not exhibit significant variations during the whole period studied.     

Oak barrel maturation vs. micro-oxygenation: Effect on the formation of anthocyanin-derived pigments and wine colour

The objective of this study was to check whether micro-oxygenation (MO) could mimic oak barrel ageing as regard the effect on wine colour. A red wine was submitted to micro-oxygenation for three months while another lot from the same wine was matured in oak barrels for three or six months. After these times, oak-matured and micro-oxygenated wines were bottled and analyzed six months later. The chromatic characteristics of these wines were also compared with those of a control wine that remained in a stainless steel tank all the time. Anthocyanins and anthocyanin-derived compounds were studied by LC–ESI-MS. Monomeric anthocyanins and other compounds including direct anthocyanin–flavanol adducts, ethyl-linked anthocyanin–flavanol compounds, and pyranoanthocyanins were detected. The application of MO for three months produced wines with a lower concentration of monomeric anthocyanins and a higher concentration of vitisin-related pigments than the control wine, the oak mature wines showing similar results than MO wines when aged for the same period of time. Differences were also observed in the chromatic characteristics, the micro-oxygenated and the oak matured wines showing a higher colour intensity than control wine. However, after six months in bottle differences were found between the micro-oxygenated wines and oak matured wines, the latter showing a more stable colour, probably due to the beneficial effects of compounds extracted from the wood (e.g. ellagitannins or wood aldehydes).     

Statistical interpretation of the color parameters of red wines in function of their phenolic composition during aging in bottle

The relationships between the color parameters (colorimetric indexes and CIELAB variables) and the phenolic components (anthocyanins, pyranoanthocyanins, hydroxybenzoic and hydroxycinnamic acids, flavanols and flavonols) of young red wines from Vitis vinifera L. cv. Tempranillo, Graciano and Cabernet Sauvignon (vintage 2000, Navarra, Spain), have been investigated during 26 months of wine aging in bottle (a period embracing their commercial life), through the application of different statistical analysis (principal component, correlation and polynomial regression). The results of the principal component analysis first indicated that for each variety a high degree of interrelation existed between the color parameters and the anthocyanin pigments. Moreover, it was found that for each variety the color parameters were correlated with the anthocyanins during aging in bottle. Finally, by the application of polynomial regression analysis, both anthocyanins (simple glucosides and acetyl-glucosides) and pyranoanthocyanins (anthocyanin-pyruvic acid adducts) were selected as the variables that best described the different color parameters during aging in bottle. However, differences were found between varieties in relation to the type of anthocyanin pigment selected for describing each color parameter, finally indicating the importance of the grape variety factor in the definition of the wine chromatic characteristics.     

Do white grapes really exist?

Anthocyanins are natural coloured pigments representing part of the protective mechanism of many plants, including Vitis vinifera L., and they have a considerable influence on wine quality. Moreover, the presence of anthocyanins in ripe berries is used as the accepted qualitative parameter for distinguishing red from white grapes, since these pigments are known to be present only in red berries. On the other hand, pyranoanthocyanins are important pigments for the colour stability of red wines and are known to be formed after berry crushing, during vinification and wine ageing.In this work, for the first time we provide clear evidence that the skin of international white grape cultivars (Chardonnay, Sauvignon Blanc and Riesling) contains measurable traces of anthocyanins. In addition, for the first time we report clear proofs about the presence of pyranomalvidin 3-O-glucoside (B-type vitisin) and carboxypyranomalvidin 3-O-glucoside (A-type vitisin) in fresh grapes and we quantify them.     

Effect of the modifier (Graciano vs. Cabernet Sauvignon) on blends of Tempranillo wine during ageing in the bottle. I. Anthocyanins, pyranoanthocyanins and non-anthocyanin phenolics

The effect of Graciano (GRA) (Spanish valuable variety of limited production) vs. Cabernet Sauvignon (CS) (world wide known French variety) wines on the anthocyanin, pyranoanthocyanin and non-anthocyanin phenolic composition of wines from Tempranillo (TEM-base wine) (largely cultivated Spanish variety) was studied in wine blends prepared with 25% and 10% (v/v) of each modifier after 4, 6, 9, 16.5 and 23 months of ageing in the bottle. Blending mainly resulted in a higher concentration of peonidin anthocyanins for the TEM-GRA blends, of acetyl-glucoside anthocyanins and anthocyanin-pyruvic acid adducts for the TEM-CS blends, and of flavanols for the blends with both GRA and CS varieties, giving rise to wines with a more balanced anthocyanin/flavanol ratio. Blending also enhanced the changes expected to occur in the phenolic compounds during ageing in the bottle. Particularly, anthocyanins and flavanols in the blends disappeared faster than in the base wine, and this was more pronounced for the 75:25 than for the 90:10 blends. These effects were similar for both modifier wines, independent of the specific changes produced in the anthocyanin profile of the base wine, but coincided with the similar optimization of the anthocyanin/flavanol ratio provided by both Graciano and Cabernet Sauvignon wines.     

Effect of Storage Conditions on Various Parameters of Colour and the Anthocyanin Profile of Rosé Wines

Colour compounds of rosé wines can be very sensitive to storage conditions because of the low levels of naturally-occurring protective compounds. This article deals with the effects of storing rosé wines under different temperature and light conditions, with regard to their colour characteristics and anthocyanin profile. Samples were taken seven times altogether over a period of 582 days. At the end of the storage period, the resulting differences in the wines were studied by μLC/MS. It was found that storing rosé wine at room temperature caused a reduction of 50% in the levels of anthocyanins compared to storing them at 3°C. Increasing the storage temperature to 45°C caused the total decomposition of all anthocyanins. Furthermore, during the maturation of the wine, a loss of sugar moiety, hydration of aglycone, and the formation of the corresponding chalcone or diketone were observed. Levels of pyranoanthocyanins in the wines were studied as well. Vitisins A and B, hydroxyphenyl-pyranomalvidin-3-glucoside, dihydroxyphenyl-pyranomalvidin-3-glucoside, and methoxyhydroxyphenyl-pyranomalvidin-3-glucoside were identified. The highest levels of both chalcones and pyranoanthocyanins were found in samples stored at room temperature. The effect of irradiation on the pigments also appeared to be significant but less important than the effect of high temperature.     

First confirmation in red wine of products resulting from direct anthocyanin–tannin reactions

Analysis of wine fractions before and after thiolysis confirmed the occurrence in red wine of direct reactions between anthocyanins and tannins established earlier in model solutions. Results showed the presence of two types of structures differing in the linkage position of the anthocyanin moiety. On one hand, detection of malvidin‐3‐glucoside (Mv3g) among thiolysis products revealed the presence of anthocyanin‐derived pigments in which Mv3g is linked by its C‐6 or C‐8 top. On the other hand, LC/MS analysis allowed the detection of two derivatives tentatively identified as flavenes or a bicyclic condensation products yielded by the reaction of a flavanol monomer (C‐6 or C‐8 top) with malvidin‐3‐glucoside (C‐4 position). The presence of the corresponding benzylthioethers after thiolysis of the polymeric fractions confirmed that procyanidins are similarly involved in the latter reaction. Besides, MS also allowed the detection of new benzylthioethers of catechin derivatives released after thiolysis of the wine fractions, indicating that in addition to the postulated processes other types of reactions take place in wines. © 2000 Society of Chemical Industry     

Anthocyanin pigments in strawberry

The anthocyanin composition was analysed in strawberry fruits from five different cultivars (cv. Eris, Oso Grande, Carisma, Tudnew and Camarosa). Twenty-five defined anthocyanin pigments were detected, most of them containing Pelargonidin (Pg) as aglycone; some cyanidin (Cy) derivatives were also found. Glucose and rutinose were the usual substituting sugars, although arabinose and rhamnose were also tentatively identified; some minor anthocyanins showed acylation with aliphatic acids. A relevant aspect was the detection of anthocyanin-derived pigments, namely 5-carboxypyranopelargonidin-3-glucoside and four condensed pigments containing C-C linked anthocyanin (Pg) and flavanol (catechin and afzelechin) residues. Total anthocyanin content ranged between 200 and 600 mg kg⁻¹, with Pg 3-gluc constituting 77-90% of the anthocyanins in the strawberry extracts followed by Pg 3-rut (6-11%) and Cy 3-gluc (3-10%). A notable variability was found among the anthocyanin concentrations in samples of a same variety and harvest, indicating a strongly influence of the degree of maturity, edaphic-climatic factors and post-harvest storage.     

Chromatic characteristics and anthocyanin profile of a micro-oxygenated red wine after oak or bottle maturation

Micro-oxygenation (MOX) was applied to a red wine for 5 months following the end of alcoholic fermentation and then both a non-oxygenated control wine and the micro-oxygenated wine were matured in oak barrels or bottles. The concentration of anthocyanin and anthocyanin-derived compounds and the chromatic characteristics of the control and micro-oxygenated wines after the maturation period were studied. Anthocyanin and anthocyanin-derived compounds composition were determined by liquid chromatography-mass spectrometry; and, together with monomeric anthocyanins, compounds including direct anthocyanin-flavanol adducts, ethyl-linked anthocyanin-flavanol compounds, and pyranoanthocyanins were identified. The results showed that the improvements in the chromatic characteristics obtained by applying the MOX technique to Monastrell wines were maintained after an aging period in bottle or barrel. The color intensity of wines increased during maturation in oak barrels, whereas the color of the bottled wines decreased, although MOX wines always showed higher color intensity than the respective control wines. Bottled wines also showed a higher increase in tint and a lower quantity of compounds resistant to SO₂ discoloration than oak matured wines, indicating that the formation of these compounds is favored by the oxidative conditions in oak barrels.     

Electron spin resonance spectroscopy studies on the free radical scavenging activity of wine anthocyanins and pyranoanthocyanins

Anthocyanins are a group of natural occurring pigments responsible for the red-blue color of grapes and many fruits and vegetables. Anthocyanins and derived pigments are of double interest, one technological, as they can be used as natural colorants, and another one due to their implication on human health through their antioxidant activity. Although there are numerous studies regarding the antioxidant activity of grape extracts as well as red wine, the free radical scavenging activity of purified anthocyanins and pyranoanthocyanins is largely unknown. In the present study, the hydroxyl and superoxide anion scavenging activities of anthocyanins and their pyruvic acid adducts were systematically investigated by electron spin resonance spectroscopy and spin trapping. The 3-glucosides of delphinidin, cyanidin, petunidin, pelargonidin and malvidin, and the pyruvic adduct of the 3-glucoside of delphinidin exhibited a potent superoxide anion radical scavenging and, to a lesser extent hydroxyl anion radical scavenging activity. The pyranoanthocyanins of cyanidin, petunidin, malvidin and pelargonidin showed a high capacity to scavenge superoxide anion radicals but did not scavenge hydroxyl radicals. Current data indicate that formation of anthocyanin adducts with pyruvic acid, which may occur during wine ageing or fruit juice processing, decreases the hydroxyl and superoxide anion scavenging and thus could decrease the antioxidant potential of these compounds.     

中国东亚种红葡萄酒的颜色特征及酚类组成研究

为探究东亚种红葡萄酒的颜色特征以及酚类物质轮廓,采用分光光度法、酶标仪和高效液相色谱-串联质谱（HPLC-MS/MS）技术分别对3款东亚种、3款欧亚种及2款杂交种（山葡萄×欧亚种）红葡萄酒的颜色和酚类物质组成进行分析,并对其花色苷衍生物进行鉴定。结果表明,与欧亚种红葡萄酒相比,东亚种红葡萄酒的辅色花色苷含量较高（55.63%～55.66%）,而聚合花色苷含量较低（19.63%～27.01%）,并且花色苷含量较为丰富（399.30～829.95 mg/L）,以花色素-3,5-O-双葡萄糖苷为主（＞97.50%）,酰化花色苷较低（＜21.78%）。花色苷衍生物检测结果表明,东亚种红葡萄酒中的花色苷与（表）儿茶素聚合产物和吡喃花色苷的含量极低（痕量水平）。东亚种红葡萄酒在非花色苷酚组成上的突出特点为单体和二聚体黄烷醇的含量极低,因此其对酒体颜色的潜在影响可能较小。     

Copigmentation,colour and antioxidant activity of single-cultivar red wines

A hundred and thirty-six single-cultivar red wines of different vintages were collected from several wineries in the Canary Islands in order to study the magnitude of the copigmentation phenomenon and the antioxidant activity. The contribution of free anthocyanins, copigmented anthocyanins and polymeric pigments to the colour of wine, as well as the total phenols, the antioxidant activity (2,2-diphenyl-1-picrylhydrazyl, DPPH method) and the chromatic characteristics of the wines were determined. The influence of ageing time and the climatic conditions on these parameters was also studied. The wines made with Merlot, Ruby Cabernet and Syrah cultivars showed the highest parameters of colour, and the largest contribution to the copigmented anthocyanins was from the Ruby Cabernet, Listán negro and Syrah cultivars. The copigmented anthocyanins and the free anthocyanins decrease with the age of the wine, and the antioxidant activity of the samples appears to be related to the total phenol content. An influence of the climatic conditions on colour parameters has been found. The correlation study between parameters suggests that the parameters b* and L* could be used as suitable indicators of evolution or oxidation stage of red wines.     

Reaction Between Malvidin 3-Glucoside and (+)-Catechin in Model Solutions Containing Different Aldehydes

ABSTRACT: The contribution of the aldehyde composition of wine spirit to the color changes in Port red wine was studied in model solutions. Malvidin 3-glucoside was shown to be very reactive towards catechin in the presence of different aldehydes: acetaldehyde, isovaleraldehyde, benzaldehyde, propionaldehyde, isobutyraldehyde, formaldehyde, and 2-methylbutyraldehyde. LC/MS data confirmed the formation of oligomeric pigments resulting from the reaction between the anthocyanin and the flavanol (colored products) and between 2 flavanol units (colorless products) mediated by each aldehyde assayed. The UV-visible spectra of the colored pigments showed a λ_max bathochromically shifted relatively to the λ_max of original anthocyanins. All samples revealed a "blueing" and "darkening" color effects using the CIELAB system.     

Free radical scavenging and antibacterial activities of southern Serbian red wines

Free radical scavenging and antibacterial activities were determined for several red wines from different grape varieties from the southern Serbia wine region. The amount of polyphenols and anthocyanins in selected wines was investigated and the potential antibacterial activity of the wines against pathogenic strains of Staphylococcus aureus and Escherichia coli was also determined. The free radical scavenging and antibacterial activity of the wines was correlated with polyphenolic and anthocyanin content. The significant differences in the antioxidant and antibacterial activities between the wines from grape cultivars (Cabernet Sauvingon and Pinot Noir) and the indigenous varieties (Vranac and Prokupac) were not confirmed. The hypothesis of a protective effect of red wine is supported by our results that show that the red wines with higher amounts of polyphenols and anthocyanins had higher antioxidant and antibacterial properties.     

‘桂葡6号’葡萄酒花色苷组分HPLC-MS分析

利用高效液相色谱-质谱联用技术测定野生资源‘桂葡6号’乙醇发酵结束和瓶储3?个月的葡萄酒中花色苷类物质的组成及含量,并与欧亚种‘赤霞珠’进行对比。结果发现,‘桂葡6号’乙醇发酵结束和瓶储3?个月酒样中花色苷总量为548.94?g/L和427.89?g/L,分别是同期‘赤霞珠’的1.2?倍和2.7?倍左右。‘桂葡6号’乙醇发酵结束和瓶储3?个月酒样中分别检测到25?种和19?种花色苷,双糖苷是其中最主要的花色苷类型,含量最高的是甲基花青素-3,5-O-双葡萄糖苷。与欧亚种‘赤霞珠’相比,瓶储3?个月‘桂葡6号’酒样中3’,5’-羟基取代花色苷比例较高,而酰基化、甲基化和吡喃型花色苷比例较低。‘桂葡6号’花色苷组成及含量与欧亚种‘赤霞珠’差异明显,这由其品种特性决定。?     

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.     

Effect of sulphur dioxide and must extraction on colour,phenolic composition and sensory quality of red table wine

Red wines were made during 1992 from Vitis vinifera var Roriz grapes using a high and a low level of extraction and three levels of total sulphur dioxide (0, 75 and 150 mg SO₂ kg⁻¹). From this single experiment, the effects of total SO₂ and extraction on anthocyanin composition and colour were observed by HPLC, spectrophotometry and tristimulus colorimetry. High extraction produced a wine with more total pigments and total phenols than low extraction and increased the amount of organic acids extracted during fermentation. More anthocyanins were extracted with increasing SO₂ levels. On maturation, all wines lost colour and increased in brownness. Wines made without SO₂ browned more than the wines made with SO₂. The anthocyanins normally present in wines were all rapidly lost to trace levels at 24 months. Vitisin A, a more stable and highly coloured anthocyanin than malvidin 3-glucoside, showed a slower decrease in concentration than malvidin 3-glucoside and contributed significantly to the wine colour during aging. At the first analysis, the wines made without SO₂ had a higher percentage colour due to polymers than the wines made with SO₂. Polymerisation progressed during maturation, although the initial differences were maintained. Sensory analysis after 6 and 18 months storage by expert tasters revealed differences mainly related to the colour attributes, indicating that when wines are made using modern hygienic techniques, total SO₂ has a negligible effect on aroma and flavour attributes. © 1998 Society of Chemical Industry.     

The magnitude of copigmentation in the colour of aged red wines made in the Canary Islands

In order to study the magnitude of the copigmentation phenomenon in aged red wines, 84 samples of Listán negro wines were collected from several wineries in the Canary Islands. They were analysed at 1 and 2 years of age. The contribution of free anthocyanins, copigmented anthocyanins and polymeric pigments to the colour of wine, and the total phenols were determined. Moreover, coloured anthocyanins, total anthocyanins, percentage of total anthocyanins in coloured form and chemical age factor, and the chromatic characteristics of the wines were determined. The contribution to colour due to copigmented anthocyanins in these aged red wines remained at 22.3 and 18.5% (mean values) after 1 and 2 years of age, respectively, and the free anthocyanins at 37.0 and 32.5%. A comparison between the results obtained by Somers and Boulton methods has been established.