Anthocyanin composition and extractability in berry skin and wine of Vitis vinifera L. cv. Aglianico

BACKGROUND: The present article reports the anthocyanin content in the berry skin and wine of the Italian red grape cultivar Aglianico (clone VCR11 grafted onto 1103 Paulsen), one of the most ancient vines and famous for its deep‐red colour. Anthocyanins were extracted from frozen berry skin in an acidified methanol solution. The extraction mixtures, monitored for 120 h, were analysed by high‐performance liquid chromatography. RESULTS: The extraction from berry skin of delphinidin, petunidin and malvidin appeared to be a time‐independent process, whereas the concentration of peonidin increased linearly with time. Peonidin‐O‐acetyl‐glucoside was transferred from skin more slowly than petunidin‐O‐acetyl‐glucoside and malvidin‐O‐acetyl‐glucoside. The anthocyanin composition of the resulting wine showed that the total anthocyanin content was about one‐tenth of the corresponding berry skin content. The ratio acetyl/coumaroyl anthocyanins in the wine was sharply higher than the value in berry skin (0.85 and 0.10, respectively), indicating an enrichment of acetyl derivatives in the wine. CONCLUSION: Levels of single anthocyanins in wine were not always correlated with those detected in grapes, as they were affected by winemaking. The high values of some anthocyanins in Aglianico wine could ameliorate its quality, increasing the chromatic properties, aging stability and product acceptance. Copyright © 2011 Society of Chemical Industry     

Cell wall anthocyanin adsorption by different Saccharomyces strains during the fermentation of Vitis vinifera L. cv Graciano grapes

This work reports the adsorption of anthocyanins by the cell walls of different strains of Saccharomyces during the production of red wine from Vitis vinifera L. cv Graciano grapes. The anthocyanin derivative contents of the yeast cell walls were substantially different to those of their corresponding wines. Cinnamoyl derivatives (6-p-coumaroyl and 6-caffeoyl) were strongly adsorbed while vitisins (adducts of pyruvic acid and acetaldehyde) were weakly adsorbed. The mean total anthocyanin concentration of the wines was 507.64 mg L^?1 with the following distribution: 3-glucosides (3G), 82.2%; vitisins, 0.97%; 6-acetyl derivatives, 7.44%; 6-caffeoyl derivatives, 1.81%; and 6-p-coumaroyl derivatives, 7.54%. A mean of 18.57 mg of anthocyanins were adsorbed by the lees corresponding to 1 L of wine; this quantity was distributed: 3G, 52.60%; vitisins, 0.15%; 6-acetyl derivatives, 4.06%; 6-caffeoyl derivatives, 6.61%; and 6-p-coumaroyl derivatives, 36.58%. Large differences were seen between the different yeast strains examined with respect to the quantities of anthocyanins adsorbed. The mean adsorption percentage was 3.67%, but this varied between 1.60% (strain 3VA) and 5.85% (strain 9CV). The adsorption percentage of 6-p-coumaroyl derivates for strain 3VA (7.61%) was fourfold less than that of 9CV (28.37%). Strains 2EV and 3VA showed no vitisin adsorption.     

Anthocyanins in Fruits of Vaccinium oxycoccus L. (Small Cranberry)

Peonidin-3-glucoside (41.9%) and cyanidin-3-glucoside (38.3%) were the main anthocyanins isolated from fruits of Vaccinium oxycoccus L. (Small cranberry). Smaller amounts of the 3-monogalactosides and 3-monoarabinosides of peonidin and cyanidin were found in addition to the 3-monoglucosides of delphinidin, petunidin and malvidin. The total anthocyanin content in the fruit averaged 78 mg/100g fresh fruit. This anthocyanin pattern is different from that of the American cranberry (Vaccinium macrocarpon L.).     

Grape phenolics: The anthocyanins of Vitis vinifera,variety shiraz

The pigments of the Shiraz variety of Vitis vinifera grown in the Barossa Valley of South Australia have been identified as the 3-monoglucosides of delphinidin, petunidin, malvidin and peonidin, together with a number of acylated derivatives of these anthocyanins. involving both p-coumaric and caffeic acids. The principal acyl derivatives are two different p-coumaroyl and one caffeoyl derivative of malvidin 3-glucoside, and a p-coumaroyl derivative of peonidin 3-glucoside. Corresponding derivatives of the two other 3-glucosides are present in small amounts. The point of attachment of the acyl substituent in the main group of p-coumaroyl derivatives has been shown to be on the glucose moiety. The major pigment component is malvidin 3-glucoside which in the various forms present is responsible for approximately 70% of the total colour. Crystalline samples of several of the components have been isolated and their extinction values determined.     

Preparation of novel distinct highly aromatic liquors using fruit distillates

This work describes the preparation of aromatised liquors using deodorised and concentrated fruit distillates. The raw spirits were improved by making a partial deodorisation, using activated charcoal, followed by concentration, using a distiller. The liquors were prepared by a maceration process. The procedure is exemplified using fig distillates to prepare myrtle berry liquors. The acidity, copper, polyphenol and anthocyanin indexes and volatile and anthocyanin profiles were monitored in each preparation step. The concentration process increased the ethanol proof to 75% v/v and decreased the acidity and the copper content. The partial deodorisation decreased the levels of high molecular weight volatiles, while the content of lower molecular weight compounds that contribute to flavour was maintained. Delphinidin‐3‐O‐glucoside, cyanidin‐3‐O‐glucoside, petunidin‐3‐O‐glucoside and malvidin‐3‐O‐glucoside were the major anthocyanins.     

The distribution of anthocyanins in grape skin extracts of port wine cultivars as determined by high performance liquid chromatography

The distribution of anthocyanins in methanolic skin extracts of 16 grape cultivars used for port wine production and grown at five sites in the Douro Valley in Northern Portugal has been assessed by high performance liquid chromatography. Results are confined to the seven most readily separated and identified anthocyanins and are expressed as percentages of their total (88–99% of the total integrated area). Anthocyanins based on malvidin (Mv) predominated. Of these, Mv 3-glucoside was the major pigment (33–60%), being exceeded by Mv 3-p-coumarylglucoside (2–51%) in only two cultivars; Mv 3-acetylglucoside (1–15%) was consistently the lowest. Peonidin 3-glucoside (1–27%) was prominent in four cultivars, but delphinidin 3-glucoside (1–11%), petunidin 3-glucoside (2–11%) and cyanidin 3-glucoside (trace-6%) were of low proportions throughout. The ratio Mv 3-acetylglucoside/total Mv glucosides appeared characteristic of cultivar, independent of site, and a useful aid to identification of grape cultivars. The coloured pulp of some cultivars contained peonidin 3-glucoside as a major component, present in greater proportions than in the skin; the percentage of Mv 3-p-coumarylglucoside was lower in pulp than in skin. The identities of six of the seven anthocyanins were confirmed by fast atom bombardment mass spectrometry and the structures of the Mv derivatives were determined by nuclear magnetic resonance. The formation of formyl and acetyl anthocyanin artefacts is described.     

Pigmented flower extracts of plant species from the Geraniaceae and Lamiaceae families as natural food colourants: anthocyanin composition,thermal and oxidative stability

This study determined the anthocyanin profile of pigmented flower extracts from some Geraniaceae and Lamiaceae plant species found in South Africa, and their thermal and oxidative stability to assess their potential food application. Anthocyanins in the Geraniaceae (Pelargonium grandiflorum Willd. and Pelargonium × hortorum L.H. Bailey, Pelargonium zonale hybrid) were 3,5-diglucosides of delphinidin, petunidin, pelargonidin, peonidin and malvidin and acetyl-acylated malvidin, delphinidin and petunidin. The Lamiaceae species (Salvia aurea × dolomitica Bae’s blue, Salvia dolomitica Codd and Plectranthus zuluensis T. Cooke) mainly contained rutinosides of pelargonidin, glucosides of petunidin, pelargonidin and p-coumaric acid- and malonyl-acylated delphinidin and malvidin. Lamiaceae pigments had higher thermal and oxidative stability. This could be due to aromatic malonyl-acylated anthocyanin self-association and strong intermolecular interactions with phenolic acids and derivatives. Flowers from Lamiaceae and Geraniaceae have potential application as natural food colourants, but temperature and oxidising conditions must be considered depending on the particular species being used.     

Effect of allyl isothiocyanate on antioxidant enzyme activities,flavonoids and post-harvest fruit quality of blueberries (Vaccinium corymbosum L., cv. Duke)

The effect of allyl isothiocyanate (AITC) on antioxidant enzyme activities, flavonoid content, and fruit quality of blueberries var. Duke (Vaccinium corymbosum L.) was evaluated. Results from this study showed that AITC was effective in maintaining higher amounts of sugars and lower organic acids compared to untreated fruit during storage at 10 °C. However, AITC reduced antioxidant enzyme activities [superoxide dismutase (SOD), guaiacol peroxidase (G-POD), glutathione-peroxidase (GSH-POD), ascorbate peroxidase (AsA-POD), dehydroascorbate reductase (DHAR), monodehydroascorbate reductase (MDAR) and glutathione reductase (GR)] and non-enzyme components, ascorbate (AsA) and glutathione (GSH). AITC treatments also reduced the amount of phenolic acids (chlorogenic acid, myricetin 3-arabinoside, quercetin 3-galactoside, quercetin 3-arabinoside, and kaempferol 3-glucoside) and anthocyanins (delphinidin 3-galactoside, delphinidon 3-glucoside, delphinidin 3-arabinoside, petunidin 3-galactoside, petunidin 3-glucoside, petunidin 3-arabinoside, malvidin 3-galactoside, and malvidin 3-arabinoside) during storage at 10 °C. The results from this study indicate that AITC does not promote antioxidant property or scavenge constitutive reactive oxygen species (ROS), but maintain blueberry fruit quality through other mechanisms.     

Pattern recognition of three Vitis vinifera L. red grapes varieties based on anthocyanin and flavonol profiles,with correlations between their biosynthesis pathways

The presence of anthocyanins and flavonols in three selected red grape varieties was investigated, in order to use their polyphenolic characterisation as a fingerprint. Berry skins of Gran Negro grapes were characterised by the presence of high content of malvidin- and peonidin-3-O-glucoside; Mouratón grapes, by the presence of high content of petunidin- and delphinidin-3-O-glucoside; and Brancellao grapes, by the presence of high content of cyanidin-3-O-glucoside. The main flavonols found included the 3-O-glucosides of quercetin, myricetin, kaempferol, laricitrin, isorhamnetin and syringetin. Using cluster analysis and principal components analysis, Gran Negro could be characterised by their content of isorhamnetin-3-O-glucoside and syringetin-3-O-glucoside and, along with Mouratón, by their myricetin conjugates. Flavonol profile could not provide a fingerprint of Brancellao variety. Stepwise discriminant analysis was performed in order to find the polyphenolic compounds, which characterised the selected grape varieties. Finally, anthocyanin and flavonol profiles in red grapes were compared and results confirmed that biosynthesis of flavonols is closely related to that of anthocyanins.     

The polyphenolic profiles of common bean (Phaseolus vulgaris L.)

Based on the phenolic profiles obtained by high performance liquid chromatography-electrospray ionization mass spectrometry (HPLC-DAD-ESI/MS), 24 common bean samples, representing 17 varieties and 7 generic off-the-shelf items, belonging to ten US commercial market classes can be organized into six different groups. All of them contained the same hydroxycinnaminic acids, but the flavonoid components showed distinct differences. Black beans contained primarily the 3-O-glucosides of delphinidin, petunidin and malvidin, while pinto beans contained kaempferol and its 3-O-glycosides. Light red kidney bean contained traces of quercetin 3-O-glucoside and its malonates, but pink and dark red kidney beans contained the diglycosides of quercetin and kaempferol. Small red beans contained kaempferol 3-O-glucoside and pelargonidin 3-O-glucoside, while no flavonoids were detected in alubia, cranberry, great northern, and navy beans. This is the first report of the tentative identification of quercetin 3-O-pentosylhexoside and flavonoid glucoside malonates, and the first detailed detection of hydroxycinnamates, in common beans.     

Original article: Anthocyanin profile in Monastrell grapes in six different areas from Denomination of Origen Jumilla during ripening stage

The aim of our research has been to investigate the pattern of accumulation of anthocyanins in the skin of Monastrell variety and to establish if the fingerprint of this cultivar changed in six different areas from Denomination of Origen Jumilla during ripening stage in two consecutive seasons (2007 and 2008). The results show that the anthocyanin profile for Monastrell variety is maintained: it could be observed a higher proportion of non‐acylated anthocyanins, a higher proportion of coumarylated than acetyl derivatives and a higher proportion of trihydroxylated than dihydroxylated anthocyanins. During ripening period, in all zones studied, we observed the same trends: increasing of cyanidin, peonidin and malvidin‐3‐glucoside and decreasing of the other two monoglucosides (delphinidin and petunidin). Slightly quantitative differences were observed for the different zones in the 2 years studied, leading to the conclusion that edaphoclimatic factors also influence the accumulation of anthocyanin compounds.     

The distribution and content of anthocyanins in young port wines as determined by high performance liquid chromatography

The distribution and content of anthocyanins in young port wines made in three successive years (1981–1983) from up to sixteen grape cultivars grown at five different sites in the Douro Valley in Northern Portugal has been assessed by high performance liquid chromatography. Distributions are confined to the seven most readily separated and identified anthocyanins and expressed as percentages of their sum (78–97% of the total integrated area). Anthocyanins based on malvidin (Mv) predominated (57–94%). Of these Mv 3-glucoside was the major pigment (43-76%), followed usually by Mv 3-p-coumarylglucoside (1–38%) and then Mv 3-acetylglucoside (2–18%). Peonidin 3-glucoside (2–39%) was prominent in a few cultivars but delphinidin 3-glucoside (1–13%), petunidin 3-glucoside (2–12%) and cyanidin 3-glucoside (trac-4%) were of low proportions throughout. The ratio Mv 3-acetylglucoside/total Mv glucosides appeared characteristic of cultivar, independent of site and a useful aid to identification. The percentages of Mv 3-p-coumarylglucoside were usually lower in ports than in grape skin extracts of the same cultivars. The contents of total anthocyanins in the ports ranged from 143–1080 mg 1^?1 (expressed as malvidin 3-glucoside chloride) and varied according to site and season.     

Anthocyanin Pigments of Royal Okanogan Huckleberry Juice

Juice processed from Royal Okanogan Huckleberries had an intense purple color, (CIE L*a*b*= L*, 22.66, a*, ?0.06, b*, ?0.46) and high anthocyanin pigment content, (>5 g/L). The anthocyanins were separated by HPLC and characterized from retention times and UV-visible spectra of purified pigments and their hydrolysis products. The major pigment (>70%) was petunidin 3-(p-coumaroyl-rutinoside)-5-glucoside. Eleven additional anthocyanins were identified as petunidin, delphinidin, and malvidin with the same glycosidic substitution pattern as the major pigment, and varying degrees of acylation with p-coumaric, ferulic, and caffeic acids. It was concluded from comparative pigment analyses and berry morphology that Royal Okanogan Huckleberries had identical characteristics to the Garden Huckleberry, Solanaceae melanocerasum (renamed S. scabrum).     

Anthocyanin profiles of major red grape (Vitis vinifera L.) varieties cultivated in Greece and their relationship with in vitro antioxidant characteristics

A range of fourty‐six red grape (Vitis vinifera spp.) samples, originating from six widely cultivated varieties and covering major parts of the Hellenic vineyard, were assayed for their content in six principal anthocyanin pigments. Representative in vitro antioxidant parameters were also determined, including antiradical activity (A_AR), reducing power (P_R) and hydroxyl free radical scavenging activity (SA_HFR). Quantitative determination using high performance liquid chromatography showed that the prevalent pigment was malvidin 3‐O‐glucoside (average content 82.53 mg per 100 g fresh berry weight), followed by its coumarate derivative (29.26 mg per 100 g), paeonidin 3‐O‐glucoside (10.84 mg per 100 g), petunidin 3‐O‐glucoside (7.80 mg per 100 g) cyanidin 3‐O‐glucoside (5.67 mg per 100 g) and delphinidin 3‐O‐glucoside (1.28 mg per 100 g). The richest variety was Syrah, with total average anthocyanin content of 186.02 mg per 100 g, whereas the Hellenic native variety Xinomavro had the lowest average anthocyanin level (38.70 mg per 100 g). The establishment of correlations of individual and total anthocyanin contents with the values from the antioxidant test was accomplished with linear regression. The links of total anthocyanins were significant with all antioxidant parameters (P < 0.001), but more importantly with SA_HFR (R² = 0.740). Malvidin 3‐O‐glucoside content had the higher correlation with SA_HFR compared with all other anthocyanins (R² = 0.698, P < 0.001).     

Anthocyanins from Tibouchina grandiflora

From the flowers of Tibouchina grandiflora, four pigments were extracted and two of them were identified as peonidin-3-sophoroside and malvidin-3,5-diglucoside. Another two pigments were tentatively identified as malvidin-3-(p-coumaroyl)-sambubioside-5-glucoside and peonidin-3-sambubioside. Three pigments were also present in T. grandiflora but in amounts insufficient to permit identification.     

Assessing the anthocyanic composition of Port wines and musts and their free radical scavenging capacity

The anthocyanic composition of must and different types of Port wine (Ruby, LBV and Tawny from nine producers) was evaluated by HPLC. In addition, the radical scavenging activity of these Port wines was evaluated by using DPPH radical microassay. Musts, Ruby and LBV Port wines presented similar qualitative profiles of anthocyanins and quantitative differences, ranging from 382-601, 92-156 and 32-78 mg of malvidin-3-O-glucoside equivalent/l, respectively. Anthocyanins in Tawny Port wines ranged between not detected and 51 mg of malvidin-3-O-glucoside equivalent/l. Principal component analysis was applied to the percentage (in weight) of each compound in relation with the total content of anthocyanins. PCA yielded two components explaining 90.9% of the total variance. The first PC correlates positively with the glucoside derivatives of delphinidin, cyanidin, petunidin and malvidin. The second PC correlates positively with pyruvic acid adducts of anthocyanins that resulted from vinification process. Ruby and LBV presented low amounts of glucoside derivatives and variable amounts of pyruvic acid adducts of anthocyanins. Acid hydrolysis allowed the identification of five anthocyanidins. Malvidin was the most abundant one. LBV Port wine showed the strongest antiradical activity, while Tawny Port wines revealed the lowest ones, with these wines presenting lower amounts of anthocyanic compounds owing to their “oxidative” aging in wooden barrels. These results suggest that aging process is an important factor influencing the antioxidant activity of Port wines.     

Berry anthocyanins: isolation,identification and antioxidant activities

Anthocyanins from bilberry, blackcurrant and cowberry were isolated for antioxidant evaluation. Individual compounds were identified and quantified using HPLC and HPLC/ESI–MS techniques. Antioxidant and radical‐scavenging capacities of the isolates were studied in emulsified methyl linoleate and human low‐density lipoprotein (LDL) in vitro and in the 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH) test. The total anthocyanin contents in the phenolic extracts of bilberry, blackcurrant and cowberry were 6000, 2360 and 680 mg kg^?1 fresh weight respectively. There were four dominant compounds in blackcurrant (glucosides and rutinosides of cyanidin and delphinidin), three in cowberry (monoglycosides of cyanidin) and 15 in bilberry (monoglycosides of cyanidin, delphinidin, malvidin, peonidin and petunidin). Quantification as cyanidin‐3‐glucoside equivalents gave markedly lower results regarding the total anthocyanin concentration and the content of individual delphinidin and malvidin compounds compared with quantification based on corresponding standard compounds. Berry anthocyanins were highly active radical scavengers in the DPPH test and effective antioxidants in emulsion and human LDL. Copyright © 2003 Society of Chemical Industry     

Characterization of phenolics in Lacrima di Morro d’Alba wine and role on its sensory attributes

Lacrima di Morro d’Alba is a red DOC (controlled designation of origin) wine, which is produced in the region of Marche (Italy) using the homonymous grape cultivar of Vitis vinifera. Lacrima di Morro contains the diglucosides of malvidin, petunidin, peonidin, whereas cyanidin and its derivatives were not detected with high performance liquid chromatography coupled with an ion trap mass spectrometer. Among anthocyanins, only the coumaroyl derivatives of peonidin and petunidin were positively related to copigmentation and color intensity, unlike malvidin-3-coumarylglucoside. Tannins (ranging only from less than 50–224 mg/L) and large polymeric pigments were indifferent with regard to copigmentation, whereas gallic acid and quercetin were the non-pigmented phenolics positively related to copigmentation and color intensity. (+)-catechin was related with a brown, oxidized hue and with non-copigmented anthocyanins. Copigmentation was positively related to the sour taste of the wine, but was negatively related to the astringent taste.     

Study of hydroxycinnamic acids and malvidin 3-monoglucoside derivatives using capillary zone electrophoresis and ultra-performance liquid chromatography

Model solutions (pH = 3.5, 12% ethanol) of malvidin 3-O-glucoside (Mv3glc), the most common free anthocyanin in grapes and red wines from Vitis vinifera, and three free hydroxycinnamic acids present in wines (caffeic, ferulic and p-coumaric acids) were studied.     

Phenolics and antioxidant properties of bayberry (Myrica rubra Sieb. et Zucc.) pomace

Five cultivars of Myrica rubra, Biqi, Wandao, Dongkui, Dingao, and Zaodamei, were collected to analyze the phenolic compounds and evaluate the antioxidant properties of bayberry pomaces. The main anthocyanin was cyanidin-3-o-glucoside (3073.3–6219.2 mg/kg dry weight (DW)) and the main flavonol was quercetin-3-o-glucoside (296.2–907.9 mg/kg dry weight). Quercetin and myricetin were also found in the bayberry pomaces, and quercetin deoxyhexoside and myricetin deoxyhexoside were tentatively identified. The dominant phenolic acids were gallic acid (102.9–241.7 mg/kg dry weight) and protocatechuic acid (29.5–57.2 mg/kg dry weight). Other phenolic acids such as p-hydroxybenzoic, vanillic, caffeic, p-coumaric, and ferulic acids were also present in the bayberry pomaces, whereas, chlorogenic acid was only detected in Dongkui (1.58 mg/kg dry weight). The antioxidant activity of Wandao was the strongest of the five cultivars, whereas the activity of Dongkui was the weakest, and a significant positive relationship was observed between antioxidant activity and total phenolic content or total anthocyanins.