Polyphenolic composition and content in the ripe berries of wild Vitis species

To explore wild genetic resources for improving fruit and processing quality of cultivated grape cultivars, the polyphenolic composition and content in the ripe berries of 147 grape accessions from 16 Vitis species for two consecutive years were characterised. A total of 48 polyphenolic compounds, including 28 anthocyanins, 6 flavonols, 6 flavanols, 6 hydroxycinnamic derivatives, and 2 hydroxybenzoic acids, were identified via HPLC-MS and quantified by HPLC-DAD. These wild grape species had unique presence of abundant di-glucoside derivatives of anthocyanins. In addition, anthocyanins in most wild species were predominantly nonacylated. The mean contents for anthocyanins, flavanols, flavonols, hydroxycinnamic derivatives, and hydroxybenzoic acids were 9.610, 0.769, 0.093, 0.441 and 0.027 mg g⁻¹ FW, respectively. They were about 2 to 10 folds higher than their respective counterparts in the most widely cultivated grape species Vitis vinifera. As expected, most of these groups of compounds were correlated negatively with berry weight, but positively with the content of total soluble solids.     

Phenolic profile of Sercial and Tinta Negra Vitis vinifera L. grape skins by HPLC–DAD–ESI-MS: Novel phenolic compounds in Vitis vinifera L. grape

This study represents the first phytochemical research of phenolic components of Sercial and Tinta Negra Vitis vinifera L. The phenolic profiles of Sercial and Tinta Negra V. vinifera L. grape skins (white and red varieties, respectively) were established using high performance liquid chromatography–diode array detection–electrospray ionisation tandem mass spectrometry (HPLC–DAD–ESI-MSⁿ), at different ripening stages (véraison and maturity). A total of 40 phenolic compounds were identified, which included 3 hydroxybenzoic acids, 8 hydroxycinnamic acids, 4 flavanols, 5 flavanones, 8 flavonols, 4 stilbenes, and 8 anthocyanins. For the white variety, in both ripening stages, hydroxycinnamic acids and flavonols were the main phenolic classes, representing about 80% of the phenolic composition. For red variety, at véraison, hydroxycinnamic acids and flavonols were also the predominant classes (71%), but at maturity, anthocyanins represented 84% of the phenolic composition. As far as we know, 10 compounds were reported for the first time in V. vinifera L. grapes, namely protocatechuic acid-glucoside, p-hydroxybenzoyl glucoside, caftaric acid vanilloyl pentoside, p-coumaric acid-erythroside, naringenin hexose derivate, eriodictyol-glucoside, taxifolin-pentoside, quercetin-glucuronide-glucoside, malylated kaempferol-glucoside, and resveratrol dimer. These novel V. vinifera L. grape components were identified based on their MSⁿ fragmentation profile. This data represents valuable information that may be useful to oenological management and to valorise these varieties as sources of bioactive compounds.     

Nutraceutical properties and polyphenolic profile of berry skin and wine of Vitis vinifera L. (cv. Aglianico)

Red grapes are rich in phenolics, flavonoids, anthocyanins and resveratrol, all substances which have been suggested as having nutraceutical and health benefits. The berry skin and wine of grape cultivar Vitis vinifera L. (cv. Aglianico), grown in Basilicata (Southern Italy) were examined to determinate the presence of the above mentioned compounds as well as to establish the inorganic cation profile. HPLC analysis coupled with LC–ESI/MS/MS detected high contents of total flavonols and anthocyanins in berry skin and wine. The wine made with the same grape used for berry skin assays showed a notable presence of quercetin-3-O-glucoside (39.4% of total flavonols), and malvidin and petunidin derivatives (63.9% and 10.8% of total anthocyanins, respectively). The strong antioxidant ROS-scavenging activity, determined by both DPPH and FRAP assays, and the high resveratrol content confer high sensory characteristics resulted to be associated with positive nutraceutical properties of these grapes and wine. The level of cis-resveratrol was lower than trans-resveratrol in both berry skin and wine reaching 44.1 mg/kg and 0.3 mg/l, respectively. The cation profile presents low levels of Ca, Cu, K, Fe, Zn and Cd compared to numerous, important red wines, such as Monastrell and Tempranillo.     

Polyphenolic content of Vranec wines produced by different vinification conditions

Macedonian Vranec wines were analysed by HPLC coupled with DAD and MS detections and by spectrophotometric methods. ESI-IT MS and MS–MS methods with alternating ionisation polarity were used for identification of the phenolic compounds. Both, nonflavonoids (stilbens, hydroxybenzoic and hydroxycinnamic acids and derivatives) and flavonoids (flavonols, flavan-3-ols and anthocyanins) were detected in the samples. Vranec wines were produced under different fermentation conditions: maceration time of 3, 6 and 10 days, two doses of SO₂ (30 and 70 mg l⁻¹) and two yeasts for fermentation, in order to examine their effects on the extraction of phenolic compounds from grapes into the wine.     

延迟采收对酿酒葡萄类黄酮物质的影响

以梅鹿辄和赤霞珠葡萄为实验材料,研究延迟采收对葡萄类黄酮物质的影响。结果表明：延迟采收后酿酒葡萄果粒质量和果粒纵径均降低,可溶性固形物的含量增加,可滴定酸含量降低。梅鹿辄果皮中共检测出19 种花色苷、6 种黄烷醇和15 种黄酮醇,延迟1 周后,黄烷醇和黄酮醇含量增加,相较于对照分别增加了69%和1.67%,延迟2～3 周后黄烷醇和黄酮醇含量降低;而延迟采收后,花色苷含量下降。赤霞珠果皮中共检测出15 种花色苷、4 种黄烷醇和15 种黄酮醇,花色苷、黄烷醇和黄酮醇的含量在延迟3 周后显著增加,相较于对照分别增加了22%、102%、80%。     

HPLC-DAD detection of changes in phenol content of red berry skins during grape ripening

With increasing concern for a demand from consumers for natural products, there is a wide interest in bioactive substances. The new frontier of dietary quality is the study and promotion of functional foods. Phenols are among the most important functional molecules. Red grape and red wine contain bioactive products as phenols. Changes occurring in the concentrations of phenols, such as hydroxycinnamic tartaric acids (hctas), flavonols, and anthocyanins in berry skins, were measured during growth and ripening of four red grape cultivars, Alicante, Black Malvasia, Nerello, and Prunesta (Vitis vinifera L.), cultivated in a coastal location of the Reggio Calabria Province (Southern Italy). These cultivars are the most popular and are considered to be the most suitable grape cultivars for cultivation in the Tyrrhenian side of the Reggio Calabria Province. Fractioning of three phenolic classes was conducted through the adsorbing resin Serdolit XAD-2. Each single phenolic fraction was analyzed by liquid chromatography with diode array detector (HPLC-DAD). Each cultivar presented a different chromatographic profile particularly for anthocyanins. The cultivar Nerello was distinguished from other for its high content of anthocyanins. The rate, at which the concentration of hctas, flavonols and anthocyanins increased, varied greatly among the cultivars. The hydroxycinnamic tartaric acid profile varied in the studied cultivars, in fact in Alicante, Black Malvasia and Prunesta cultivars, the predominant was trans-coumaroyl tartaric acid, while in Nerello cultivar, trans-caffeoyl tartaric acid was the most abundant. In addition, the results showed that amounts of phenolic compounds contained in grape skin changed throughout the grape ripening process.     

Polyphenol and glycoalkaloid contents in potato cultivars grown in Luxembourg

The polyphenol (phenolic acids, flavanols and flavonols) and glycoalkaloid (α-chaconine and α-solanine) contents of potato tubers grown in Luxembourg were analyzed by UPLC–DAD and HPLC–MS/MS separately in peel (approx. 2 mm), outer (approx. 1 cm) and inner flesh. Polyphenol contents decreased from the peel via the outer to the inner flesh and differed among the cultivars. The cultivars Vitelotte and Luminella had the highest polyphenol contents (5202 and 572 μg/g dry weight (DW) in the outer flesh), whereas Charlotte and Bintje had the lowest contents (19.5 and 48.0 μg/g DW). Chlorogenic acid and its isomers (neo- and cryptochlorogenic acid) were the major polyphenols. Glycoalkaloid contents were highest in the peel and lowest in the inner flesh, values in the flesh were below guideline limits in all cultivars. In conclusion, potatoes contribute to the daily intake of polyphenols and their consumption, thereby, may have positive effects on health.     

Anthocyanin composition and content in grape berry skin in Vitis germplasm

The composition and content of anthocyanins were surveyed by HPLC–MS for assessing genotypic variation in berry skin of 110 grape cultivars, including 3 species and 5 interspecific hybrids. Twenty-nine anthocyanins were identified. For total anthocyanin content, Vitis vinifera and hybrids of Vitis labrusca and V. vinifera were low, and in general, wild species and rootstock were higher than interspecific hybrids, and wine grapes were higher than table grapes in the same species. As regards the composition of anthocyanins, malvidin-derivatives were the most abundant anthocyanins in the majority of germplasms. All anthocyanins were monoglucoside derivatives in V. vinifera, but all the other Vitis germplasms had both mono- and di-glucoside derivatives. Moreover, peonidin-derivatives and malvidin 3-O-glucoside were, respectively, main anthocyanins in table and wine grapes of V. vinifera. Via principal component analysis, the distribution of the cultivars in a scatter plot depended upon their total anthocyanins content, mono- and di-glucoside derivatives.     

Study of phenolic composition and sensory properties of red grape varieties in danger of extinction from the Spanish region of Castilla-La Mancha

This paper reports on a study of the profiles of different phenolic compounds (anthocyanins, flavonols, hydroxycinnamic acids and stilbenes) of five minor red grape varieties from the Spanish region of Castilla-La Mancha (Bobal, Moravia Agria, Moravia Dulce, Rojal and Tortosí) and a traditional variety from this growing region (Cencibel) as reference. Grape skin extracts of each variety were analysed by High Performance Liquid Chromatography coupled to Diode Array Detector (HPLC–DAD). The content of grape skins in anthocyanins (21.1–453 mg kg⁻¹), flavonols (26.9–288 mg kg⁻¹) and hydroxycinnamic acids (6.80–18.2 mg kg⁻¹) showed differences according to mainly varietal origin, although other important factors have to be taken into account such as the degree of ripeness, berry size or vintage year. In all the studied varieties, the major anthocyanin was malvidin 3-glucoside (>40%) with the exception of Rojal variety, which major one was peonidin 3-glucoside together with cyanidin 3-glucoside. Moravia Dulce and Rojal varieties contained more than 46% of quercetin 3-glucuronide; the rest of them contained less than 27%. No relation was found between profiles of hydroxycinnamic acids in the studied samples and their variety or year of vintage. All the studied grapes presented high concentrations of stilbenes that could be interesting due to the health benefits.     

Regional characteristics of anthocyanin and flavonol compounds from grapes of four Vitis vinifera varieties in five wine regions of China

Anthocyanins and flavonols are important flavonoid metabolites in grapes, making a dominant contribution to the color, the mouth feel and even the flavor of grapes and wines. The accumulation of these flavonoids in grapes is greatly influenced by a many, diverse but interacting factors, of which variety and climate are among the most important ones. In the present study, the anthocyanin and flavonol profiles of four grape varieties (Vitis vinifera L.), Cabernet Sauvignon, Carmenere, Syrah and Merlot, from five major wine regions in China were examined for two consecutive years (2006 and 2007). The results showed that the total anthocyanin content of the berry skins in these cultivars tended to increase from east to west in China, yet the proportion of the acylated anthocyanins displayed the opposite trend. It seemed possible that the western grape regions, with their high altitude and low annual rainfall, had an advantage in producing high level of anthocyanins. In addition, a high proportion of trihydroxylated flavonols were always found in the western region grapes, whereas dihydroxylated flavonols were more prominent in the lower altitude eastern regions. This suggested that the relative amounts of these flavonoid compounds may depend on their corresponding cultivar characteristics, while the amounts are more affected by the environmental factors where they were growing.     

Phenolic compound profiles in selected Queensland red wines at all stages of the wine-making process

The phenolic profiles of Queensland red wines (two Cabernet Sauvignons and one Shiraz) from different stages of wine-making were studied. Samples were taken at crush, after the primary and malolactic fermentations, post-oaking, and post-bottling, and then extracted and separated into aqueous and organic fractions using liquid–liquid extraction and solid-phase extraction, and analysed by HPLC-DAD-MS. About 75% of the phenolic compounds were extracted into the aqueous fraction, with malvidin-3-glucoside and derivatives as the main components. The major non-anthocyanin phenolic compounds (∼25%) included gallic acid, syringic acid, ethyl gallate, caftaric acid, coutaric acid, caffeic acid, coumaric acid, catechin, and quercetin. The polymerisation of anthocyanins was shown to occur progressively throughout the wine-making process. Most of the 25 identified phenolic compounds had highest concentrations during the fermentation stage, and stabilised or slowly decreased thereafter. There were weak and insignificant correlations (P > 0.05) between individual phenolic compounds and the total antioxidant activities (ORAC). Four groups of phenolic compounds (anthocyanins, hydroxybenzoic acids, flavanols and hydroxycinnamic acids) each showed some correlation with the total antioxidant activity, as did the total polyphenol content, suggesting that the antioxidant properties of red wine are due to a complex mixture of phenolic compounds that vary in composition throughout the wine-making process.     

Changes of polyphenols, sugars, and organic acid in 5 Vitis genotypes during berry ripening

The concentrations of sugars, organic acids, and polyphenols during berry ripening in 5 grape genotypes were analyzed using HPLC and HPLC-MS to determine which were correlated. Veraison is critical stage during grape berry development, and marks the beginning of ripening. Glucose and fructose accumulated sharply in a 1 : 1 ratio, though the concentration of fructose was slightly higher than that of glucose at maturation. Malic acid and tartaric acid were the dominant organic acids, and they decreased rapidly during berry ripening. The 5 cultivars contained 28 anthocyanins and 8 other polyphenols. All anthocyanins accumulated and were positively correlated with the sugars and negatively correlated with the organic acids. Hydroxycinnamic acids declined and were positively correlated with anthocyanin contents. Changes in flavanols and flavonols different among the 5 genotypes, with flavonols positively correlated with anthocyanin content, but the flavanols procyanidin B1 and epicatechin negatively correlated with anthocyanins content. There were obvious differences in patterns of change of polyphenols among 5 grape genotypes. PRACTICAL APPLICATION: The results could be used for improving grape berry quality during ripening and developing a comprehensive database of primary and secondary metabolites in the Vitis for grape breeding.     

Determination of phenolic composition and antioxidant capacity of blood orange juices obtained from cvs. Moro and Sanguinello (Citrus sinensis (L.) Osbeck) grown in Turkey

The phenolic compounds and antioxidant capacities of orange juices obtained from cvs. Moro and Sanguinello (Citrus sinensis (L.) Osbeck) were determined. A high-performance liquid chromatographic method coupled with diode-array detection was used to identify and quantify phenolic compounds of the orange juices. A total of 18 phenolic compounds were identified and quantified in Moro and Sanguinello orange juices, including hydroxybenzoic acids (2), hydroxycinnamic acids (5), flavanones (5), and anthocyanins (6). It was observed that total phenolic content of Moro juice was higher than that of Sanguinello juice. Ferulic acid was the most dominant hydroxycinnamic acid and cyanidin 3-(6″-malonyl glucoside) and cyanidin 3-glucoside were the most dominant anthocyanins in both cultivars. Antioxidant activities of orange juices were measured using the DPPH^· (2,2-diphenyl-1-picrylhydrazyl) method. According to DPPH^· assays, the antioxidant capacity of Moro juice was found to be higher than that of Sanguinello juice.     

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.     

Quantitative analysis of phenolic compounds in Chinese hawthorn (Crataegus spp.) fruits by high performance liquid chromatography–electrospray ionisation mass spectrometry

Eleven major phenolic compounds (hyperoside, isoquercitrin, chlorogenic acid, ideain, epicatechin, two procyanidin (PA) dimers, three PA trimers and a PA dimer-hexoside) were quantified in the fruits of 22 cultivars/origins of three species of the Chinese hawthorn (Crataegus spp.) by HPLC–ESI-MS-SIR. Hyperoside (0.1–0.8 mg/g dry mass [DM]), isoquercitrin (0.1–0.3 mg/g DM), chlorogenic acid (0.2–1.6 mg/g DM), epicatechin (0.9–11.7 mg/g DM), PA B2 (0.7–12.4 mg/g DM), PA dimer II (0.1–1.5 mg/g DM), PA trimer I (0.1–2.7 mg/g DM), PA trimer II (0.7–6.9 mg/g DM), PA trimer III (0.01–1.2 mg/g DM) and a PA dimer-hexoside (trace–1.1 mg/g DM) were detected in all the samples. Ideain (0.0–0.7 mg/g DM) was found in all the samples except Crataegus scabrifolia. Significant correlations between the contents of individual PA aglycons were observed (r > 0.9, P < 0.01). A strong correlation between flavonols was also shown (r = 0.71, P < 0.01). Fruits of Crataegus pinnatifida var. major had higher contents of PAs but lower contents of flavonols compared with Crataegus brettschneideri. The fruits of C. scabrifolia contained the highest level of PA dimer-hexoside, which was present in trace amounts in the fruits of C. pinnatifida.     

Phytochemical profiles and inhibitory effect on free radical-induced human erythrocyte damage of Dracaena draco leaf: A potential novel antioxidant agent

The present study reports for the first time the metabolite profile and antioxidant activity of aqueous extract obtained from Dracaena draco L. leaf. Volatiles profile was determined by HS-SPME/GC-IT-MS, with 34 compounds being identified, distributed by distinct chemical classes: 2 alcohols, 5 aldehydes, 16 carotenoid derivatives and 8 terpenic compounds. Carotenoid derivative compounds constituted the most abundant class in leaf (representing 45% of total identified compounds). Phenolics profile was determined by HPLC/DAD and 9 constituents were identified: 2 hydroxycinnamic acid derivatives – 5-O-caffeoylquinic and 3,5-O-dicaffeoylquinic acids; 4 hydroxycinnamic acids – caffeic, p-coumaric, ferulic and sinapic acids and 3 flavonol glycosides – quercetin-3-O-rutinoside, kaempferol-3-O-glucoside and kaempferol-3-O-rutinoside. The most abundant phenolic compound is quercetin-3-O-rutinoside (representing 50.2% of total polyphenols). Organic acids composition was also characterised, by HPLC–UV and oxalic, citric, malic and fumaric acids were determined. Oxalic and citric acids were present in higher amounts (representing 47%, each). The antioxidant potential of this material was assessed by the ability to protect against free radical-induced biomembrane damage, using human erythrocyte as in vitro model. Leaf extract strongly protected the erythrocyte membrane from haemolysis (IC₅₀ of 39 ± 11 μg/ml), in a time- and concentration-dependent manner. This is the first report showing that D. draco leaf is a promising antioxidant agent.     

Identification and quantification of phenolic compounds from pomegranate (Punica granatum L.) peel,mesocarp, aril and differently produced juices by HPLC-DAD–ESI/MS

Phenolic compounds were extracted from pomegranate (Punica granatum L.) peel, mesocarp and arils. Extracts and juices were characterised by HPLC-DAD–ESI/MSⁿ. In total, 48 compounds were detected, among which 9 anthocyanins, 2 gallotannins, 22 ellagitannins, 2 gallagyl esters, 4 hydroxybenzoic acids, 7 hydroxycinnamic acids and 1 dihydroflavonol were identified based on their UV spectra and fragmentation patterns in collision-induced dissociation experiments. To the best of our knowledge, cyanidin–pentoside–hexoside, valoneic acid bilactone, brevifolin carboxylic acid, vanillic acid 4-glucoside and dihydrokaempferol-hexoside are reported for the first time in pomegranate fruits. Furthermore, punicalagin and pedunculagin I were isolated by preparative HPLC and used for quantification purposes. The ellagitannins were found to be the predominant phenolics in all samples investigated, among them punicalagin ranging from 11 to 20 g per kilogram dry matter of mesocarp and peel as well as 4–565 mg/L in the juices. The isolated compounds, extracts and juices were also assessed by the TEAC, FRAP and Folin–Ciocalteu assays revealing high correlation (R² = 0.9995) of the TEAC and FRAP values, but also with total phenolic contents as determined by the Folin–Ciocalteu assay and by HPLC. Selection of raw materials, i.e. co-extraction of arils and peel, and pressure, respectively, markedly affected the profiles and contents of phenolics in the pomegranate juices, underlining the necessity to optimise these parameters for obtaining products with well-defined functional properties.     

HPLC–MS identification and quantification of flavonol glycosides in 28 wild and cultivated berry species

Berries and red fruits are rich dietary sources of polyphenols with reported health benefits. More than 50 different flavonols (glycosides of quercetin, myricetin, kaempferol, isorhamnetin, syringetin and laricitrin) have been detected and quantified with HPLC–MSⁿ in fruits of blueberry, bilberry, cranberry, lingonberry, eastern shadbush, Japanese wineberry, black mulberry, chokeberry, red, black and white currants, jostaberry, red and white gooseberry, hardy kiwifruit, goji berry, rowan, dog rose, Chinese and midland hawthorn, wild and cultivated species of blackberry, raspberry, strawberry and elderberry. The phenolic constituents and contents varied considerably among the analyzed berry species. Elderberry contained the highest amount of total flavonols (450–568 mg kg⁻¹ FW), followed by berry species, containing more than 200 mg kg⁻¹ FW of total: chokeberry (267 mg kg⁻¹), eastern shadbush (261 mg kg⁻¹), wild grown blackberry (260 mg kg⁻¹), rowanberry (232 mg kg⁻¹), american cranberry (213 mg kg⁻¹) and blackcurrants (204 mg kg⁻¹). Strawberry (10.5 mg kg⁻¹) and white currants (4.5 mg kg⁻¹) contained the lowest amount of total flavonols. Quercetins represent the highest percentage (46–100%) among flavonols in most analyzed berries. In wild strawberry and gooseberry the prevailing flavonols belong to the group of isorhamnetins (50–62%) and kaempferols, which represent the major part of flavonols in currants (49–66%). Myricetin glycosides could only be detected in chokeberry, rowanberry and species from the Grossulariaceae, and Adoxaceae family and Vaccinium genus. Wild strawberry and blackberry contained from 3- to 5-fold higher total flavonols than the cultivated one.     

Anthocyanins and hydroxycinnamic acids of Lambert Compact cherries (Prunus avium L.) after cold storage and 1-methylcyclopropene treatment

Sweet cherries cv. Lambert Compact were treated with 1-methylcyclopropene (1-MCP) at 0, 180 and 360 nL/L for 2 h at 25 °C and then stored at 2–4 °C in refrigerator. Their quality was measured after 12 days of storage in terms of the contents of total and individual anthocyanins and hydroxycinnamic acids, occurrence of rot, and colour change. Colour change was monitored at three day intervals during storage in the CIE L*, a*, b* colour space. 1-MCP did not retard colour change. The contents of total and individual anthocyanins and hydroxycinnamic acids showed no correlation with the colour behaviour of the cherries. All cherries lost their initial shiny red colour on storage, regardless of the treatment. 1-MCP reduced sweet cherry rot at the highest concentration used (360 nL/L) – only 6% were rotten after 12 days in the refrigerator. This differed significantly (P < 0.05) from untreated fruits and those treated with 180 nL/L 1-MCP which resulted on average in 14 and 20% rot (not statistically different P < 0.05), respectively. The occurrence of rot was shown to be correlated with anthocyanin accumulation, (R = 0.62, P < 0.10). The profile of individual anthocyanins and hydroxycinnamic acids in sweet cherry was not affected neither by cold storage nor 1-MCP treatment.