The effect of prefermentative addition of gallic acid and ellagic acid on the red wine color, copigmentation and phenolic profiles during wine aging.

Though non-anthocyanin phenolics normally do not have red color, they affect the red color expression in the copigmentation of red wines. In this study, the influence of prefermentative addition of 300mg/L gallic acid and ellagic acid, as cofactors, on aging dry red wines had been systematically evaluated at the industrial scales from the perspectives of color, phenolic profiles and copigmentation effects of anthocyanins. Red wines made with these two compounds exhibited better color properties than the control, having better CIELAB chromatic parameters. Additionally, significantly higher levels of detectable anthocyanins and copigmented anthocyanin ratio had been observed. Wines with ellagic acid showed better chromatic properties and phenolic profiles than wines with gallic acid, as shown in previous theoretical results. Anti-copigmentation phenomenon was noticed and elucidated. These practical results confirmed that ellagic acid was the better cofactor, and would give more additional guidance for the production of high quality wine. CHEMICAL COMPOUNDS: Malvidin-3-O-glucoside (PubChem CID: 443,652); Petunidin-3-O-glucoside (PubChem CID: 443,651); Delphinidin-3-O-glucoside (PubChem CID: 443,650); Peonidin-3-O-glucoside (PubChem CID: 443,654); Ellagic acid (PubChem CID: 5,281,855); Gallic acid (PubChem CID: 370); Quercetin (PubChem CID: 443,654); Caffeic acid (PubChem CID: 689,043); (+)-catechin (PubChem CID: 9064); Vanillic acid (PubChem CID: 8468).

Phenolic Analysis and Theoretic Design for Chinese Commercial Wines' Authentication.

To develop a robust tool for Chinese commercial wines' varietal, regional, and vintage authentication, phenolic compounds in 121 Chinese commercial dry red wines were detected and quantified by using high-performance liquid chromatography triple-quadrupole mass spectrometry (HPLC-QqQ-MS/MS), and differentiation abilities of principal component analysis (PCA), partial least squares discriminant analysis (PLS-DA), and orthogonal partial least squares discriminant analysis (OPLS-DA) were compared. Better than PCA and PLS-DA, OPLS-DA models used to differentiate wines according to their varieties (Cabernet Sauvignon or other varieties), regions (east or west Cabernet Sauvignon wines), and vintages (young or old Cabernet Sauvignon wines) were ideally established. The S-plot provided in OPLS-DA models showed the key phenolic compounds which were both statistically and biochemically significant in sample differentiation. Besides, the potential of the OPLS-DA models in deeper sample differentiating of more detailed regional and vintage information of wines was proved optimistic. On the basis of our results, a promising theoretic design for wine authentication was further proposed for the first time, which might be helpful in practical authentication of more commercial wines. PRACTICAL APPLICATION: The phenolic data of 121 Chinese commercial dry red wines was processed with different statistical tools for varietal, regional, and vintage differentiation. A promising theoretical design was summarized, which might be helpful for wine authentication in practical situation.

A systematic analysis strategy for accurate detection of anthocyanin pigments in red wines.

RATIONALE: To develop a reliable and accurate method for the identification of anthocyanins and their subsequent derivatives formed during red grape fermentation and wine maturation. METHODS: By using a Poroshell 120 EC-C18 column in a high-performance liquid chromatography/triple-quadrupole tandem mass spectrometry (HPLC/QqQ-MS/MS) system, combined with multiple reaction monitoring (MRM), it was possible to establish and validate a method for the determination of anthocyanin and a range of complex reaction products. A selected range of six 3-O-glucosidic anthocyanins were used as standards. A database was established from these results. Then various red wines were examined and quantified by this method. RESULTS: With the range of accuracy and precision being 86.97-111.39% and 0.09-4.32%, respectively, the HPLC/QqQ-MS/MS method was found to be a reliable method for anthocyanin detection. By using this HPLC/QqQ-MS/MS method combined with the inclusive database, accurate identification of 95 anthocyanin compounds of different families from various wine samples was systematically achieved in 29 min. CONCLUSIONS: By combining this analytical system with an inclusive database, it was possible to determine a wide range of anthocyanins and related complex derivatives for the first time. We consider that it should be possible to extend this method further to include more complex anthocyanins, and to other complex compounds. Copyright © 2016 John Wiley & Sons, Ltd.

Phenolic and Chromatic Properties of Beibinghong Red Ice Wine during and after Vinification.

The phenolic and chromatic characteristics of a special red ice wine made from a Vitis amurensis × V. vinifera hybrid cultivar Beibinghong were studied. Results from two different vintages (2013 and 2014) showed that during vinification, the phenolic acid content increased, while the level of flavonoids (flavonols, flavan-3-ols, and anthocyanins) reduced by a variable extent. The color intensity and red % decreased together with a decrease in anthocyanin content. This was accompanied by an increase in hue as well as yellow %. The final phenolic content was found to be between 119.54 and 180.93 mg/L, with anthocyanins as the predominant phenolic group (92.06%-93.03%), of which 3,5-O-diglucosidic anthocyanins made up 53.55%-79.04%. Phenolic acids were the primary non-anthocyanin phenolics at about 6.64%-7.5%. The phenolic contents and color parameters of Beibinghong dry red wine and several V. vinifera dry red wines of superior color quality were also used in an attempt to clarify the relationship between phenolics and color in the Beibinghong red ice wine. By using Pearson correlation analysis and principal component analysis (PCA), it was found that 3,5-O-diglucosidic anthocyanins and protocatechuic acid were the only characteristic phenolics that differentiated Beibinghong wines from the other selected red wines from more traditional varieties. They were also the main phenolics to be positively correlated with the hue and yellow % of the wine at the early stages leading into maturation. Their presence might, therefore, explain the relatively high hue and yellow % of Beibinghong ice wine.

Molecular and biochemical characterization of the UDP-glucose: Anthocyanin 5-O-glucosyltransferase from Vitis amurensis.

Generally, red Vitis vinifera grapes only contain monoglucosidic anthocyanins, whereas most non-vinifera red grapes of the Vitis genus have both monoglucosidic and bis-glucosidic anthocyanins, the latter of which are believed to be more hydrophilic and more stable. Although previous studies have established the biosynthetic mechanism for formation of monoglucosidic anthocyanins, less attention has been paid to that of bis-glucosidic anthocyanins. In the present research, the full-length cDNA of UDP-glucose: anthocyanin 5-O-glucosyltransferase from Vitis amurensis Rupr. cv. 'Zuoshanyi' grape (Va5GT) was cloned. After acquisition and purification of recombinant Va5GT, its enzymatic parameters were systematically analyzed in vitro. Recombinant Va5GT used malvidin-3-O-glucoside as its optimum glycosidic acceptor when UDP-glucose was used as the glycosidic donor. Va5GT-GFP was found to be located in the cytoplasm by analyzing its subcellular localization with a laser-scanning confocal fluorescence microscope, and this result was coincident with its metabolic function of modifying anthocyanins in grape cells. Furthermore, the relationship between the transcriptional expression of Va5GT and the accumulation of anthocyanidin bis-glucosides during berry development suggested that Va5GT is a key enzyme in the biosynthesis of bis-glucosidic anthocyanins in V. amurensis grape berries.

A review of polyphenolics in oak woods.

Polyphenolics, which are ubiquitous in plants, currently are among the most studied phytochemicals because of their perceptible chemical properties and antioxidant activity. Oak barrels and their alternatives, which are widely used in winemaking nowadays, contribute polyphenolics to wines and are thought to play crucial roles in the development of wines during aging. This study summarizes the detailed information of polyphenolics in oak woods and their products by examining their structures and discussing their chemical reactions during wine aging. This paper evaluates the most recent developments in polyphenolic chemistry by summarizing their extraction, separation, and their identification by the use of chromatographic and spectral techniques. In addition, this paper also introduces polyphenol bioactive ingredients in other plant foods.

Differences in volatile profiles of Cabernet Sauvignon grapes grown in two distinct regions of China and their responses to weather conditions.

Volatile compounds are considered important for plants to communicate with each other and interact with their environments. Most wine-producing regions in China feature a continental monsoon climate with hot-wet summers and dry-cold winters, giving grapes markedly different growing environments compared to the Mediterranean or oceanic climates described in previous reports. This study focused on comparing the volatile profiles of Vitis vinifera L. cv. Cabernet Sauvignon berries from two regions with distinct climate characteristics: Changli has a warm and semi-humid summer, and Gaotai has a cool-arid summer and a cold winter. The relationship between meteorological metrics and the concentrations of grape volatiles were also examined. In harvested grapes, benzyl alcohol, phenylethyl alcohol, 1-hexanol and 1-octen-3-ol were more abundant in the Changli berries, while hexanal, heptanal, 2-methoxy-3-isobutylpyrazine, and (E)-ß-damascenone presented higher levels in the Gaotai berries. The fluctuation in the accumulation of volatile compounds observed during berry development was closely correlated with variations in short-term weather (weather in a week), especially rainfall. The concentration of some volatiles, notably aliphatic aldehydes, was significantly related to diurnal temperature differences. The variability during berry development of concentrations for compounds such as C6 volatile compounds, 2-methoxy-3-isobutylpyrazine and (E)-ß-damascenone strongly depended upon weather conditions. This work expands our knowledge about the influence of continental monsoon climates on volatile compounds in developing grape berries. It will also improve the comprehension of the plant response to their surrounding environments through the accumulation of volatiles. The results will help growers to alter viticultural practices according to local conditions to improve the aromatic quality of grapes.

Comparison of distinct transcriptional expression patterns of flavonoid biosynthesis in Cabernet Sauvignon grapes from east and west China.

Flavonoids make a very important contribution to the organoleptic qualities of grapes and wines. In this work these were analyzed in Cabernet Sauvignon grown in Changli, Hebei Province in east China and Gaotai, Gansu Province in west China. These regions have distinctly different climates contributing to their different 'terroir'. RNA sequencing was performed to trace transcriptome changes in Cabernet Sauvignon berries at pea size, veraison and ripening, corresponding to E-L 31, 35 and 38. The accumulation of flavonols, flavan-3-ols and anthocyanins together with the expression of relevant genes were analyzed and compared between the two regions. The biosynthesis patterns were similar between two regions, but more flavonols, anthocyanins, and tri-hydroxylated flavonoids accumulated in grapes from Gaotai before berry harvest, possibly due to the higher transcript levels of the genes that encode biosynthetic enzymes and their potential candidate transcription factors. The lower levels of flavan-3-ols, mainly (-)-epigallocatechin, in the pre-veraison grapes from Changli, might be due to limited flow of carbon to the F3'5'H branch pathway, as the ratio of F3'5'H to F3'H was lower in these berries from Changli. It is suggested that the combination of climatic factors profoundly affect the flavonoid pathway in grapes from China, providing regionally specific metabolism patterns.

Influence of pre-fermentation cold maceration treatment on aroma compounds of Cabernet Sauvignon wines fermented in different industrial scale fermenters.

The influence of pre-fermentation cold maceration (CM) on Cabernet Sauvignon wines fermented in two different industrial-scale fermenters was studied. CM treatment had different effects on wine aroma depending on the types of fermenter, being more effective for automatic pumping-over tank (PO-tank) than automatic punching-down tank (PD-tank). When PO-tank was used, CM-treated wine showed a decrease in some fusel alcohols (isobutanol and isopentanol) and an increase in some esters (especially acetate esters). However, no significant changes were detected in these compounds when PD-tank was used. Ethyl 2-hexenoate and diethyl succinate were decreased, while geranylacetone was increased by the CM treatment in both fermenters. ß-Damascenone was increased by the CM treatment in PO-tank fermented wines but decreased in PD-tank fermented wines. The fruity, caramel and floral aroma series were enhanced while chemical series were decreased by the CM treatment in PO-tank fermented wines. The content of (Z)-6-nonen-1-ol in the final wines was positively correlated to CM treatment.

Free and glycosidically bound aroma compounds in cherry (Prunus avium L.).

This paper reports the occurrence of both free and glycosidically bound aroma compounds in three sweet cherry cultivars ('Hongdeng', 'Hongyan' and 'Rainier'), with 97 compounds being identified in the three cultivars. The major free volatile compounds found were hexanal, (E)-2-hexenal, (E)-2-hexen-1-ol, benzyl alcohol and benzaldehyde. The major bound volatile compounds found were benzyl alcohol, geraniol, 2-phenylethanol. Also 4-vinylphenol was found in cherry fruit for the first time, and has a relatively high concentration of the glycosidically-bound form in 'Rainier'. Odour activity values (OAVs) were determined for both free and bound volatiles, with 18 compounds having an OAV above 1. The highest OAVs for three cultivars were (E)-ß-ionone, hexanal, decanal and (E)-2-hexenal with the highest being over 800 for (E)-ß-ionone in 'Honyang'. From these results, it was concluded that the aroma compounds present were similar in all three cultivars, but there was significant variation found in their levels and hence contribution to the aroma of these cultivars.

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.

Comparative study of phenolic compounds in Cabernet Sauvignon wines made in traditional and Ganimede fermenters.

Chemical profiles of anthocyanin and non-anthocyanin phenolics of Cabernet Sauvignon wine made by two different winemaking techniques (traditional vinification and Ganimede method) were determined by high performance liquid chromatography-mass spectrometry (HPLC-MS). Particularly, effect of extraction on and subsequent stability of the phenolic compounds from the end of fermentation to bottling were investigated. The results showed that the total anthocyanin content was higher in the young wines produced in the Ganimede fermenter. The anthocyanin contents in these wines subsequently decreased significantly after two years of ageing. By contrast, the traditional vinification was slightly better than the Ganimede to yield the non-anthocyanin phenolics. This indicates that the Ganimede fermenter might be suitable for the production of brightly coloured red wines for early consumption, which could save time and labour cost for industrial production of highquality wines.

Phenolic profiles of Vitis davidii and Vitis quinquangularis species native to China.

The accumulation of phenolics in the skins of two Vitis davidii cultivars ('Ziqiu' and 'Xiangzhenzhu') and one Vitis quinquangularis cultivar ('Xiangshan No. 4') native to China was followed during ripening. It was found that the anthocyanin composition of all three grapes was dominated by anthocyanidin 3,5-O-diglucosides. The cultivar 'Xiangshan No. 4' (V. quinquangularis) contained a high level of 3',4'-substituted anthocyanins and low levels of flavonols and 3',4'-substituted flavan-3-ols, indicating that the F3'H branch pathway was the principal carbon pathway synthesizing mainly 3',4'-substituted anthocyanins. No myricetin-type flavonols were found in this cultivar, but in both 'Ziqiu' and 'Xiangzhenzhu' (V. davidii) cultivars the F3'5'H branch pathway was dominant, resulting in malvidin-based diglucoside anthocyanins. Cyanidin-based and petunidin-based anthocyanins were not detected in the 'Ziqiu' cultivar. Principal component analysis revealed that V. davidii grapes had abundant flavonols by the early middle developmental stages and a high level of malvidin-type anthocyanins by the late developmental stage. In contrast, the V. quinquangularis cultivar contained other anthocyanins instead of malvidin-type anthocyanins.

Anthocyanins and their variation in red wines I. Monomeric anthocyanins and their color expression.

Originating in the grapes, monomeric anthocyanins in young red wines contribute the majority of color and the supposed beneficial health effects related to their consumption, and as such they are recognized as one of the most important groups of phenolic metabolites in red wines. In recent years, our increasing knowledge of the chemical complexity of the monomeric anthocyanins, their stability, together with the phenomena such as self-association and copigmentation that can stabilize and enhance their color has helped to explain their color representation in red wine making and aging. A series of new enological practices were developed to improve the anthocyanin extraction, as well as their color expression and maintenance. This paper summarizes the most recent advances in the studies of the monomeric anthocyanins in red wines, emphasizing their origin, occurrence, color enhancing effects, their degradation and the effect of various enological practices on them.

Anthocyanins and their variation in red wines. II. Anthocyanin derived pigments and their color evolution.

Originating in the grapes, anthocyanins and their derivatives are the crucial pigments responsible for the red wine color. During wine maturation and aging, the concentration of monomeric anthocyanins declines constantly, while numerous more complex and stable anthocyanin derived pigments are formed, mainly including pyranoanthocyanins, polymeric anthocyanins produced from condensation between anthocyanin and/or flavan-3-ols directly or mediated by aldehydes. Correspondingly, their structural modifications result in a characteristic variation of color, from purple-red color in young red wines to brick-red hue of the aged. Because of the extreme complexity of chemical compounds involved, many investigations have been made using model solutions of know composition rather than wine. Thus, there is a large amount of research still required to obtain an overall perspective of the anthocyanin composition and its change with time in red wines. Future findings may well greatly revise our current interpretation of the color in red wines. This paper summarizes the most recent advances in the studies of the anthocyanins derived pigments in red wines, as well as their color evolution.

Biosynthesis of anthocyanins and their regulation in colored grapes.

Anthocyanins, synthesized via the flavonoid pathway, are a class of crucial phenolic compounds which are fundamentally responsible for the red color of grapes and wines. As the most important natural colorants in grapes and their products, anthocyanins are also widely studied for their numerous beneficial effects on human health. In recent years, the biosynthetic pathway of anthocyanins in grapes has been thoroughly investigated. Their intracellular transportation and accumulation have also been further clarified. Additionally, the genetic mechanism regulating their biosynthesis and the phytohormone influences on them are better understood. Furthermore, due to their importance in the quality of wine grapes, the effects of the environmental factors and viticulture practices on anthocyanin accumulation are being investigated increasingly. The present paper summarizes both the basic information and the most recent advances in the study of the anthocyanin biosynthesis in red grapes, emphasizing their gene structure, the transcriptional factors and the diverse exterior regulation factors.