Extraction, detection, and quantification of flavano-ellagitannins and ethylvescalagin in a Bordeaux red wine aged in oak barrels

An extraction procedure and an analytical method have been developed to detect and quantify for the first time a series of ellagitannin derivatives formed in wine during aging in oak barrels. The method involves a preliminary purification step on XAD7 HP resin followed by a second purification step on TSK 40 HW gel. The resulting extract is analyzed for compound identification and quantitative determination by high-performance liquid chromatography-electrospray ionization-mass spectrometry in single ion recording mode. Reference compounds, which are accessible through hemisynthesis from the oak C-glycosidic ellagitannin vescalagin, were used to build calibration curves, and chlorogenic acid was selected as an internal standard. This method enabled us to estimate the content of four flavano-ellagitannins and that of another newly identified wine polyphenol, beta-1-O-ethylvescalagin, in a Bordeaux red wine aged for 18 months in oak barrels. All five ellagitannin derivatives are derived from the nucleophilic substitution reaction of vescalagin with the grape flavan-3-ols catechin and epicatechin or ethanol.     

Volatile compounds in a spanish red wine aged in barrels made of Spanish, French, and American oak wood

A red Rioja wine was aged in barrels made of Spanish oak wood (Quercus robur, Quercus petraea,Quercus pyrenaica, and Quercus faginea) during 21 months. The concentrations of some volatile compounds [syringaldehyde, vanillin, eugenol, maltol, guaiacol, 4-ethylphenol, cis and trans isomers of beta-methyl-gamma-octalactone, 2-furfuraldehyde, 5-methyl-2-furfuraldehyde, 5-(hydroxymethyl)-2-furfuraldehyde, and furfuryl alcohol] were studied in these wines and compared with those of the same wine aged in barrels made from French oak of Q. robur (Limousin, France) and Q. petraea (Allier, France) and American oak of Quercus alba (Missouri). Similar concentrations of these compounds were found in wines aged in Spanish and French oak wood barrels, and significantly different concentrations were found with respect to wines aged in barrels made of American oak wood, indicating a different behavior. Thus, wines with different characteristics were obtained, depending on the kind of wood. Also, the kind of wood had an important influence on sensory characteristics of wine during the aging process. Spanish oak wood from Q. robur, Q. petraea, and Q. pyrenaica can be considered to be suitable for barrel production for quality wines, because a wine aged in barrels made of these Spanish oak woods showed similar and intermediate characteristics to those of the same wine aged in French and American oak woods usually used in cooperage.     

Impact of toasting oak barrels on the presence of polycyclic aromatic hydrocarbons in wine

Toasting Quercus sp. oak wood is one of the key stages in manufacturing barrels intended for aging wines and spirits. During this operation, the increase in temperature causes variable modifications in the physical structure and, more importantly, the chemical composition of the wood. Polycyclic aromatic hydrocarbons (PAH) are high-risk molecules likely to be formed during toasting of the wood and later extracted by wine or spirits in direct contact with the barrel. In the context of an analysis of all potential sources of risk associated with the manufacture of barrels for winery use [prevention policy defined using a Hazard Analysis Critical Control Point (HACCP) approach], we carried out a preliminary study to provide a more accurate assessment of potential risks related to the presence of PAH in cooperage and winemaking. Wood toasted to different levels under different conditions, as well as wines aged in barrels made using different methods, was analyzed by gas chromatography and mass spectrometry (GC-MS) for the identification of the main PAH present, quantification of each of the molecules extracted, and estimation of any possible toxicological risks, via a comparison of values with those measured in other types of food. The results clearly showed that the heating processes associated with barrel production actually resulted in the formation of various molecules in the PAH family. However, only a minority of the target PAH presented high toxicity, particularly carcinogenic potential. Because of the specific toasting process used, benzo[a]pyrene, the best-known, and one of the most dangerous, contaminants, was not significantly present in toasted barrel wood. In view of the PAH concentrations in wood and the low solubility of these compounds, their extraction in wine is apparently relatively slow and limited. Finally, comparing the overall PAH concentrations, and particularly those of the most toxic compounds, with estimated absorption from food or the environment, we found it was obvious that the contribution of toasted barrels to the total amount was extremely low and should not, therefore, be considered a major health concern.     

Influence of micro-oxygenation treatment before oak aging on phenolic compounds composition, astringency, and color of red wine

Micro-oxygenation is usually applied to red wines as a cheaper alternative to oak aging. It has been suggested, however, that micro-oxygenation can also be used to complement oak aging in order to improve the quality of very astringent and herbaceous red wines. In this paper we study how applying the micro-oxygenation technique before oak aging affects the composition and quality of astringent red wines. When this technique is applied prior to oak aging, the wines have a slightly less intense red color and significantly higher levels of combined and free anthocyanins and ethyl-bridged anthocyanin-flavanol pigments. On the other hand, no differences in other newly formed pigments are found. Applying micro-oxygenation before oak aging does not affect the total proanthocyanidin concentration, but it produces wines with a slightly (though significantly) higher mean degree of proanthocyanidin polymerization and a drastically lower astringency. These wines also present a clearer impact of wood aromas.     

Determination of ellagitannins in extracts of oak wood and in distilled beverages matured in oak barrels

A method is described for determination of ellagitannins in ethanol-water extracts of oak wood and in distilled alcoholic beverages matured in oak barrels. It is based on the combined ellagic acid content according to ellagitannin structure. Hydrolysis was carried out in the presence of hydrochloric acid under reflux in a 100 degrees C oil bath for 3 h. Total ellagic acid was thus determined by liquid chromatography (LC), and the free ellagic acid content present in the ethanol-water media was subtracted, the difference being the combined ellagic acid content corresponding to ellagitannins. A 5 micron C18 column was used with detection at 254 nm. The method is specific for ellagitannins, which is an advantage over other analytical techniques for overall evaluation of these substances extracted from wood. Results for spirits distilled from wine, grain, and sugarcane were highly variable.     

Concurrent phenomena contributing to the formation of the aroma of wine during aging in oak wood: an analytical study

Red wine was stored in different oak barrels or in stainless steel, and samples were taken for two years to determine 79 aroma compounds. Aging in oak affects 41 compounds. The type of wood affects 11 compounds. At least seven different processes seem to take place concurrently in aroma evolution, and five such processes, affecting 37 compounds, are linked to the oak cask. These are extraction from the wood, oxidation of wine alcohols and amino acids, microbiological formation of ethyl phenols, sorption processes, and condensation of acetaldehyde with polyphenols. The wood can release linear gamma- and delta-lactones, beta-damascenone, and ionones. Some compounds are released very fast from wood, which suggests they lie in the external part of the wood. Some extraction profiles are too complex to be explained by physical processes. Finally, the levels of 2,5-dimethyl-4-hydroxy-3(2H)-furanone and 2-ethyl-5-methyl-4-hydroxy-3(2H)-furanone increase even in the reference wine, which suggests the presence of a precursor.     

Monitoring acetaldehyde concentrations during micro-oxygenation of red wine by headspace solid-phase microextraction with on-fiber derivatization

An analytical method was developed to quantify levels of acetaldehyde in wine samples. The method utilizes headspace solid-phase microextraction with on-fiber derivatization using O-(pentafluorobenzyl)hydroxylamine and quantification by gas chromatography with flame ionization detection. The technique showed good sensitivity and reproducibility in samples of Chardonnay, Petite Sirah, and Merlot wines containing acetaldehyde at levels below the sensory threshold (40-100 ppm). The method was used to monitor acetaldehyde concentrations during the micro-oxygenation of Merlot wine in a 141 L pilot-plant experiment and a 2400 L full-scale study. In both experiments, levels of acetaldehyde remained constant for several weeks before increasing at rates of the order of 1 ppm/day. Variations in the levels of acetaldehyde present are discussed within the context of the underlying chemical reactions.     

Anthocyanin transformation in Cabernet Sauvignon wine during aging

Anthocyanins in Cabernet Sauvignon grapes and wines were elucidated by HPLC-MS/MS. Major anthocyanins in Cabernet Sauvignon grape extract are malvidin 3-O-glucoside and malvidin 3-O-acetylglucoside. In matured wine, anthocyanins are transformed to anthocyanin-vinyl derivatives, ethyl bridged anthocyanin-flavanol adducts, and anthocyanin-flavanol adducts. The major anthocyanin pigments are malvidin 3-O-glucoside-pyruvate, malvidin 3-O-acetylglucoside-pyruvate, malvidin 3-O-coumaroylglucoside-pyruvate, malvidin 3-O-glucoside-4-vinylphenol, malvidin 3-O-acetylglucoside-4-vinylphenol, and malvidin 3-O-coumaroylglucoside-4-vinylphenol. The presence of syringetin 3-O-glucoside and syringetin 3-O-acetylglucoside has been established for the first time in grape and wine.     

Maturing wines in oak barrels. Effects of origin,volume, and age of the barrel on the wine volatile composition

The influence of the oak origin, volume, and age of the barrel on the volatile composition of a red wine after six months of maturation have been studied. Major volatile compounds in wine were determined using liquid-liquid extraction with dichloromethane, and those volatiles being due to the oak were determined by extraction with pentane-ether using deuterated analogues as internal standards. The results show that there is little difference between the volatile composition of wines matured in French oak barrels and those matured in American oak barrels. The concentration of cis-oak lactone was the most significant difference. The greatest instrumental and sensory differences were found between new and used barrels, with important decreases in lactones and vanillin concentration in used barrels. When studying the effect of the volume of the barrel, the characteristics of the wine matured in 220-L new barrels versus those matured in 1000-L new barrels were very different. In new barrels, the larger the volume of the barrel, the lower the concentrations of those compounds responsible for the oaky aroma. These differences were less evident when comparing wines matured in used barrels with different capacities.     

Influence of aging conditions on the quality of red Sangiovese wine

A red Sangiovese wine was stored in barrels of different woods (oak and chestnut) and types (225-L "barriques" and 1000-L barrels) at 12 and 22 degrees C for 320 days to evaluate the effects of different aging conditions on wine quality. Chestnut barrels led to wines richer in phenolics, and which were more tannic, colored, and fruity. Oak barrels gave wines with more monomeric phenolics, but less astringent, with higher vanilla smell, and more harmonious. The type of barrel could be used as a parameter to regulate the extraction of wood components and the polymerization of monomeric phenolics. Storage at 22 degrees C favored the formation of polymerized phenolics and the increase of color density and color hue. The temperature produced less pronounced effects on aroma and taste, even if wines stored at 12 degrees C showed more harmony.     

Behavior of monosaccharides, phenolic compounds, and color of red wines aged in used oak barrels and in the bottle

A red wine with appropriate basic quality characteristics for aging was stored in oak barrels for 12 months and then bottled and aged for a further 6 months. The same ambient conditions of temperature and humidity were maintained throughout the entire aging process. The barrels used were made from three different species of oak by four different cooperages and had been used for at least two years. Analysis of variance and principal component analysis were run on the values for hexoses, pentoses, total anthocyanins, ortho-diphenols, low- and high-polymer polyphenols, and color parameters to study the behavior of the monosaccharides and polyphenols in response to the factors of aging time, the oak variety employed, and the source cooperage where the barrels had been made. Time trends for all the phenolic components were directly related to aging time, with low-polymeric polyphenols (LPPs) being the most affected by wood type and source cooperage. Wine color was defined by a basic red color which decreased with aging time in the barrel and was altered by yellowish pigment components differing for each of the barrels in which oxidative aging took place and by increased stability of the blue copigments. Principal component analysis showed that samples of the same source wine aged in different barrels tended to be grouped together according to each of the aging intervals considered.     

Changes in nitrogen compounds in must and wine during fermentation and biological aging by flor yeasts.

Urea, ammonium, and free amino acid contents were quantified in a must from Vitis vinifera cv. Pedro Ximenez grapes and in fermented wine and after a short aging of this wine by Saccharomyces cerevisiae race capensis yeast under variable oxygen availability conditions. The previous compounds were also determined in a wine in which the nitrogen source was depleted by the same race of flor yeast (old wine) and also following the addition of ammonium ion, L-glutamic acid, and L-proline. Under specific conditions such as low oxygen level and the absence of some nutrients, the yeasts release some amino acids including L-threonine, L-tryptophan, L-cysteine, and L-methionine to the medium. These amino acids must originate primarily in a de novo synthesis from ethanol that regenerates NAD(P)+. On the basis of these results, the yeasts may be able to use amino acids not only as nitrogen sources but also as redox agents to balance the oxidation-reduction potential under conditions of restricted oxygen, when electron transport along the respiratory chain may be hindered or limited.     

Impact of concentration of ellagitannins in oak wood on their levels and organoleptic influence in red wine

Some wood substances such as ellagitannins can be extracted during wine aging in oak barrels. The level of these hydrolyzable tannins in wine depends of some parameters of oak wood. Their impact on the organoleptic perception of red wine is poorly known. In our research, oak staves were classified in three different groups according to their level of ellagitannins estimated by NIRS (near infrared spectroscopy) online procedure (Oakscan). First, the ellagitannin level and composition were determine for each classified stave and an excellent correlation between the NIRS classification (low, medium and high potential level of ellagitannin) and the ellagitannin content estimated by HPLC-UV was found. Each different group of NIRS classified staves was then added to red wine during its aging in a stainless tank, and the extraction and evolution of the ellagitannins were monitored. A good correlation between the NIRS classification and the concentration of ellagitannins in red wine aging in contact with the classified staves was observed. The influence of levels of ellagitannins on the resulting wine perception was estimated by a trained judge's panel, and it reveals that the level of ellagitannins in wine has an impact on the roundness and amplitude of the red wine.     

Changes in red wine soluble polysaccharide composition induced by malolactic fermentation

The polysaccharide content of wine is generally assumed to originate from grapes and yeasts, independent of bacterial metabolism, except for the action of certain spoilage species. This study shows that malolactic fermentation (MLF) significantly modifies the soluble polysaccharide (SP) concentration of various red Bordeaux wines. Wines with the highest initial SP concentration go on to present decreased SP concentration, whereas those with the lowest initial SP concentration rather go on to have a higher SP concentration after MLF. These tendencies were observed whatever the Oenococcus oeni strain (indigenous or starter) used for MLF. Neutral and charged SPs were affected, but to a degree that depended on the microorganisms driving the MLF. The SP modifications were directly linked to bacterial development, because non MLF controls did not present any significant change of SP concentration.     

Evolution of sugars in cider brandy aged in oak barrels: a contribution to its characterization

A chemometric study was carried out to typify cider brandies according to the type of wood employed in the maturation process and their aging time. Monosaccharides, previously derivatized with p-aminobenzoic ethyl ester, were analyzed using a reversed-phase high-performance liquid chromatographic method. Univariate data treatment was not sufficient to enable differentiation of the classes of cider brandies on the basis of wood type and maturation time. Two linear combinations of original variables, ascertained by principal components analysis, provided an adequate data structurization. A mathematical decision rule was established to classify cider brandies with prediction capacities of 92 and 97% using an LDA method and Bayesian analysis, respectively. The use of the PLS algorithm allowed the authors to differentiate cider brandies according to the age and type of oak used in the aging process.     

Evolution and stability of anthocyanin-derived pigments during Port wine aging.

For three years, the evolution of the three major anthocyanidin monoglucosides (malvidin 3-glucoside, malvidin 3-acetylglucoside, and malvidin 3-coumaroylglucoside) and their anthocyanin-pyruvic acid adducts was monitored in Port wines stored in oak barrels. The degradation reactions of all pigments followed first-order kinetics in all the wines studied. The degradation rate constants of the anthocyanin-pyruvic acid adducts were much lower than those of the anthocyanidin monoglucosides. The results of both anthocyanins and pyruvic acid adducts show that acylation on the sugar moiety of all the pigments decreased their stability in wine. The levels of malvidin 3-glucoside-pyruvic acid adduct and its acylated forms increased right after wine fortification with wine spirit before starting to decrease around 100 days. The initial formation of anthocyanin-pyruvic acid adducts was concurrent with the degradation of anthocyanidin monoglucosides.     

Changes in the aroma compounds of sake during aging

Changes in the aroma of sake during aging were investigated by aroma extract dilution analysis (AEDA) and quantitative analysis using the stir bar sorptive extraction method. In AEDA, more odor zones were detected in aged sake than in fresh sake. The dilution factors of aldehydes, polysulfides, and some esters were greater in the aged sake, and their increase during aging was confirmed through a quantitative analysis of sake stored for 0-35 years. Among these compounds, 3-methylbutanal, methional, and dimethyltrisulfide (DMTS) were present in aged sake at concentrations exceeding their odor thresholds, and the highest odor active value was observed for DMTS. Sensory tests showed that supplementation with DMTS contributed to both the total odor intensity and the sulfury odor of aged sake aroma.     

干红葡萄酒中白黎芦醇的研究

该文系统研究了葡萄果实中白黎芦醇的分布、工艺条件、产地和年份等因素对葡萄酒中白藜芦醇含量影,结果表明葡萄浆果中的白黎芦醇主要分布在果皮,果肉中的含量最低;发酵温度、酵母菌、乳酸菌种类对葡萄酒中白黎芦醇含量有影响;品种及产地、年份所引起的生态条件的差异是引起葡萄酒中白黎芦醇含量差异的主要原因.     

Aroma compound sorption by oak wood in a model wine

Oak wood used for wine barrels was immersed into a model wine containing eight aroma compounds (e.g., aromatic and terpene alcohols, ethyl esters, and aldehyde), for which activity coefficients in water and model wine were determined using the mutual solubility measurement. A mass balance of these volatiles considering their reactivity in model wine was established. For most of the studied aroma compounds, and mainly for linalool and ethyl octanoate, a sorption behavior into wood was reported for the first time. This phenomenon was selective and could not be related to the solubilities in model wine and hydrophobicities of the studied aroma compounds, suggesting that acid-base and polar characteristics of wood were more involved in this sorption mechanism. This study has also shown that the level of sorption is a function of the ratio of wood surface area/solution volume.     

Changes in the concentration of yeast-derived volatile compounds of red wine during malolactic fermentation with four commercial starter cultures of Oenococcus oeni

The effects of malolactic fermentation (MLF) on the concentration of volatile compounds released by yeasts during the production of red wine were investigated by inoculation with four commercial starters of Oenococcus oeni. Volatile compounds in wine at the end of MLF were extracted, analyzed by GC-MS and GC, and compared with those extracted form a noninoculated reference sample. Several esters known to play a role in the aroma profile of red wine, such as C4-C8 ethyl fatty acid esters and 3-methylbutyl acetate, were found to increase with MLF, and their final concentration was dependent on the bacterial starter employed for the induction of MLF. The overall increase of ethyl fatty acid esters was generally larger than the one observed for acetate esters. Ethyl lactate, 3-hydroxybutanoate, 2-phenylethanol, methionol, and gamma-butyrolactone were also increased by bacterial metabolism. The impact of MLF on other volatiles or red wine, including several higher alcohols, fatty acids, and nitrogen compounds, was generally negligible.