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International audience; The oxygen transfer rate (OTR) of closures is a well-known parameter impacting the quality of Sauvignon blanc wines (SBw) within the first years of storage, but little research has been published on its long-term effects. The chemical changes in oxidation odor intensity in three SBw sealed with natural cork and other closures that had different known OTRs, ranging from

International audience; This work aimed at improving knowledge about sweetness in dry wines. Following on from the empirical observations of winegrowers, we assessed the contribution of grape seeds to wine sensory properties. An inductive fractionation method guided by gustatometry was used to isolate and characterize sweet-tasting compounds from grapes. Fractionation of grape seed macerates was achieved by liquid-liquid extraction, centrifugal partition chromatography (CPC) and preparative HPLC. Then, the structures of the purified compounds were elucidated by use of FTMS and NMR. Five compounds were identified: two new compounds, 2-hydroxy-3-methylpentanoic-2-O-β-glucopyranoside (H3MP-G) and 2-hydroxy-4-methylpentanoic-2-O-β-glucopyranoside acids (H4MP-G), along with gallic-4-O-β-glucopyranoside acid (AG-G), 3-indolyl-(2R)-O-β-d-glycoside lactic acid (ILA-G) and epi-DPA-3′-O-β-glucopyranoside acid (epi-DPA-G). These compounds exhibited various levels of sweetness in a hydro-ethanolic solution and in white and red wines. Additionally, H3MP-G, H4MP-G and epi-DPA-G were identified for the first time in grapes and wines, whereas AG-G has already been reported in white grapes but never in wine.

Chardonnay wines impart a unique complex aroma characterized by its buttery, yellow stone fruit, melon, bready, and woody notes. Among the terms used in the sensory analysis of these wines, this study investigated hazelnut-like attributes. Multidimensional gas chromatography coupled to olfactometry identified five pyrroles reminiscent of hazelnut: 1-ethylpyrrole-2-carboxaldehyde, 1H-pyrrole, 2-acetyl-1H-pyrrole (first identification in wine), 1-methylpyrrole-2-carboxaldehyde, and 1H-pyrrole-2-carboxaldehyde. Quantitative analyses demonstrated their significantly higher abundance in Chardonnay wines. However, they proved irrelevant in sensory terms, given the low amounts measured in wine compared to their olfactory detection threshold. Nevertheless, the presence of methanethiol derivatives from these pyrroles was investigated in wine. 1-Methylpyrrole-2-methanethiol and 1-ethylpyrrole-2-methanethiol were identified and exhibited hazelnut-like aroma. These compounds, which have not been observed in natural products to date, are potent volatile compounds with detection thresholds of 0.7 and 1.4 ng/L, respectively, in model wine. These findings open up promising perspectives concerning the interpretation of the typical aromatic nuances of some Chardonnay wines.

Background and Aims Winemakers observe a sensory effect of oak ageing in wines, but the phenomenon has never been fully described. The aim of this study was to determine the influence of the ageing container on the sweetness of dry wines and to evaluate the contribution of oak volatile compounds. Methods and Results Both white and red dry wines were produced in various containers, such as stainless steel and oak tanks, and new and used oak barrels. Sensory analysis (with or without use of nose clip) by a panel of experts showed an increase in sweetness when wine was in contact with wood. Oak volatile compounds (vanillin, β-methyl-γ-octalactone and eugenol) were quantified by gas chromatography-mass spectrometry and then added to the wines to obtain the same concentration in all samples. To determine the contribution of the volatiles to the increase in sweetness, the treatments were tasted again after such an ‘oak aroma’ homogenisation. The ranking of the wines remained unchanged. Conclusion These results demonstrate that the sweet perception of dry wines depends on the nature of the ageing container, and that these oak volatiles are not involved in this phenomenon. Significance of the Study This work confirms an empirical observation and establishes for the first time the sweetening effect of oak ageing, strongly suggesting the existence of sweet non-volatile compounds in oak wood.

International audience; Two main precursors (S-3-(hexan-1-ol)-l-cysteine and S-3-(hexan-1-ol)-l-glutathione) of 3-sulfanylhexanol (3SH, formerly named 3-mercaptohexanol) have been identified so far in grape juice but a correlation between precursor concentrations in grape juices and 3SH concentrations in wines is not always observed. This suggests that there may be other compounds associated with the aromatic potential. In this work, S-3-(hexanal)-glutathione (Glut-3SH-Al) and its bisulfite (Glut-3SH-SO3) adduct were identified in Sauvignon blanc grape juice by liquid chromatography coupled to Fourier transform mass spectrometry experiments. A partial purification of the compounds was carried out by Medium Pressure Liquid Chromatography (MPLC) on the reverse phase using 5 L of grape juice. The addition of synthetized Glut-3SH-Al and Glut-3SH-SO3 in the synthetic medium induced a significant release of 3SH after fermentation. Moreover, we demonstrate that Glut-3SH-Al and its bisulfite adduct are present in grape juice and could be considered as new direct 3SH precursors with molar conversion yields close to 0.4%. Chemical compound studied in this article : 3-Sulfanylhexan-1-ol (PubChem CID: 521348)

Quercoresinosides A and B (1 and 2), two new lignans, were isolated from a toasted Quercus petraea heartwood extract along with a known compound, 3-methoxy-4-hydroxyphenol 1-O-β-d-(6′-O-galloyl)glucopyranoside (3). The purification protocol was based on a taste-guided approach that sought to reveal new bitter compounds released from oak wood into wines and spirits. HRMS and NMR data were used to establish that compounds 1 and 2 are lignan derivatives bearing a glucosyl unit and a galloyl unit at the same positions. Hydrolysis of these compounds showed that they could be distinguished by the absolute configuration of their respective lyoniresinol genin as determined by chiral LC-HRMS in comparison with (+)- and (−)-lyoniresinol standards. Sensory analyses were performed in a non-oaked wine on the pure compounds 1–3. The three molecules exhibited a bitter taste at 2 mg/L that was particularly intense for compounds 2 and 3. Finally, LC-HRMS demonstrated the occurrence of compounds 1–3 in oaked wine and brandy, which supports the hypothesis of their contributions to the increase in bitterness during oak aging.

International audience; A preparative HPLC method, which preserves wine aromas and isolates fruity characteristics in specific fractions, was applied to red wine aroma extracts. Various odor-active zones were detected in typical fractions by GC-O analysis of their extracts. Through further GC-MS analyses, the aromatic compounds responsible for 15 of these odoriferous zones were identified as various ethyl esters and alkyl acetates. In view of their olfactory thresholds, the concentrations of these compounds had no direct impact on the fruity aroma of red wines. Nevertheless, an overall sensory effect of “red-” or “black-berry” nuances was clearly established. Higher than average levels of ethyl propanoate, ethyl 2-methylpropanoate, and ethyl 2-methylbutanoate were involved in black-berry aromas, whereas ethyl butanoate, ethyl hexanoate, ethyl octanoate, and ethyl 3-hydroxybutanoate conferred red-berry aromas.

International audience; Botrytized wines (BW) are famous for their distinctive, complex aromas. To date, only a few studies have analysed the volatile compounds involved in their typical flavours. In this paper, GC-O was applied to BW and dry white wines (DW) made from the same grape varieties to characterize the main odorants responsible for their sensory differences. Surprisingly, only two odorous zones, with grapefruit or curry nuances, were apparently specific to BW. However, GC-AEDA revealed important differences in the FD values between BW and DW, making it possible to screen potent odorants of BW, such as 3-mercaptohexan-1-ol, homofuraneol®, furaneol®, sotolon, methional, and phenylacetaldehyde. GC-MS quantification of homofuraneol®, furaneol®, norfuraneol®, phenylacetaldehyde, and methional in 14 BW, mostly at levels above their perception thresholds, confirmed their contribution to the aroma of BW. Increased concentrations of some of these odorants in BW were shown to be associated with grape botrytization, partially through the desiccation process.

Glutathione (GSH) was assayed in must and wine using capillary electrophoresis coupled with laser-induced fluorescence (LIF) detection. Sample preparation involved conjugating thiols with monobromobimane (MBB) in a 2-( N -cyclohexylamino)ethanesulfonic acid [CHES] buffer (179 mM). The electrophoretic conditions were 30 kV with a capillary length of 105 cm from the inlet to the detector (120 cm total length) and a 50 μm inner diameter. Under these conditions, the complete separation from the other main non-volatile thiols took less than 20 min. We also described the optimum conditions for derivatizing wine samples with MBB to increase eletrophoretic sensitivity. The detection limit for glutathione assay is 65 nmol/L. This simple, sensitive method provides a specific assay of glutathione in reduced form, as the sample preparation technique does not modify the balance of oxidized and reduced forms. We used this method to monitor changes in the reduced glutathione content of a white wine during alcoholic fermentation and barrel aging.

International audience; Volatile and non-volatile molecules are directly responsible for the thrill and excitement provided by wine-tasting. Their elucidation requires powerful analytical techniques and innovative methodologies. In a recent work, two novel sweet compounds called quercotriterpenosides (QTT) were identified in oak wood used for wine-ageing. The aim of the present study is to discover structural analogs of such natural sweeteners in oak wood. For this purpose, an analytical approach was developed as an alternative to chemical synthesis. Orbitrap mass spectrometry proved to be a crucial technique both to demonstrate the presence of QTT analogs in oak wood by targeted screening and to guide the purification pathway of these molecules using complementary chromatographic tools. Four compounds were isolated and identified for the first time: two isomers, one glucosyl derivative and one galloyl derivative of QTT. Their tasting showed that only the two new isomers were sweet, thus demonstrating both the pertinence of the strategy and the influence of functional groups on gustatory properties. Finally, this paper presents some developments involving multistage Fourier transform mass spectrometry (FTMS) to provide solid structural information on these functional groups prior to any purification of compounds. Such analytical developments could be particularly useful for research on taste-active or bio-active products.

International audience; Glutathione (GSH) is a natural tripeptide present in grapes and wines. Its antioxidant properties are particularly useful during winemaking with white varieties like Sauvignon blanc. We examined two winemaking techniques, skin contact and pressing under nitrogen, for their effect on the GSH concentration in the must and wine. GSH was originally reported in the skin (64%), but later investigations on berries showed that juice (51%) and skin (40%) were far greater reduced GSH reservoirs than pulp and seeds. Therefore, we studied the impact of skin contact and pressing on GSH concentrations in must. Climate effects greatly influenced GSH concentrations in mature grapes. Depending on grape quality, GSH increased during skin contact from 2 to 55% and its release occurred in the first hours of maceration. During pressing under nitrogen, must GSH concentrations increased, reaching 80 to 90 mg/L when low pressure was applied (

We analyzed the variability of volatile acidity and glycerol production by Saccharomyces cerevisiae on a large sample of high sugar musts. The production of volatile acidity was inversely correlated with the maximum cell population and the assimilable nitrogen concentration. The higher the nitrogen concentration, the less volatile acidity was produced. An approach to minimize volatile acidity production during high sugar fermentations by adjustment of assimilable nitrogen in musts was investigated in terms of both quantity and addition time. It was found that the optimal nitrogen concentration in the must is 190 mgN· l −1 . The best moment for nitrogen addition was at the beginning of fermentation. Addition at the end of the growth phase had less effect on volatile acidity reduction. We suggest that by stimulating cell growth, nitrogen addition provides NADH in the redox-equilibrating process, which in turn reduces volatile acidity formation.

When Sauvignon blanc or Gros Manseng grape must was percolated through an immobilized γ-glutamyltranspeptidase column, there was a significant increase in the concentration of S-3-(hexan-1-ol)-l-cysteine, the precursor of 3-mercaptohexan-1-ol, a compound that contributes to the varietal aroma of wines made from these grapes. Low- and high-resolution liquid secondary ion mass sepectrometry (LSIMS) analyses established the presence of S-3-(hexan-1-ol)-glutathione in Sauvignon blanc must. The identification of this compound suggests that the S-3-(hexan-1-ol)-l-cysteine in grapes is produced by the catabolism of S-3-(hexan-1-ol)-glutathione. As is the case in other plant or animal organisms, S-glutathione conjugates may be involved in certain detoxification systems in vines. Keywords: Vitis vinifera; Sauvignon blanc; varietal aroma precursors; S-cysteine conjugate; S-glutathione conjugate; aroma potential; tryptophanase; γ-glutamyltranspeptidase; LSIMS

International audience; The modification of wine taste during oak ageing is due to the felease of non-volatile compounds from wood. Among these molecules, some lignans have been previously described as exhibiting bitterness. However, the lack of knowledge concerning this class of compounds in oak wood led us to explore both their structural diversity and their sensory properties. Nine lignans were isolated from extracts of Quercus petraea oak heartwood. Among them, one new compound called quercoresinol was identified and four other molecules were described for the first time in Quercus genus. The presence of these lignans in oaked wine was then established and their gustatory properties were evaluated. Lyoniresinol was the bitterest compound with a detection threshold of 1.5 mg/l. An LC HRMS quantitative method was performed to study the influence of oenological practices on lyoniresinol concentration in wine.

Musty, earthy odors are highly detrimental to the aromatic quality of wines. A characteristic aroma of freshly tilled earth, damp cellar was studied in some red and white wines of different origins. The extraction and purification of the wines marked by this odor have shown after analysis by gas chromatography-olfactometry a unique strong odorous zone having the same odor as the one perceived at tasting. The compound responsible for this odorous zone was identified by gas chromatography-mass spectrometry as geosmin (trans-1,10-dimethyl-trans-9-decalol), which possesses a distinctive earthy odor. Geosmin may be present in wines at levels higher than the racemic geosmin olfactory perception threshold, thus suggesting its contribution to their off-aroma. Moreover, the presence of this compound in juice taken from freshly crushed grapes suggests that microorganisms that develop on the grapes may contribute to the presence of this compound in wines.

Sweet fortified wines, traditionally aged under strong oxidation conditions, have a characteristic aroma. An experimental study investigated the aging of white sweet fortified wines under various conditions. The development of various molecules, previously identified as characteristic of the aroma of this type of wine, was monitored by analysis. The development of these compounds during accelerated aging was affected by oxidation and the color of the wine. Aging in oak containers, variable storage temperatures, and variable modes of oxidation affect the formation of many of the volatile compounds responsible for the aging aroma of vins doux naturels (fortified wines). Furfural (1), 5-ethoxymethylfurfural (2), and sotolon (3) always reach concentrations above their perception thresholds in wood-aged wines, especially when new oak is used. The isomers of methyl-gamma-octalactone (4 and 5) are reliable indicators of aging in oak. Among the many identifiable volatile phenols, only the vanillin (7) content increases with aging, particularly if the container is made of wood and there is a high degree of oxidation. This molecule frequently reaches and even exceeds its perception threshold. We show here that vanillin and isomers of methyl-gamma-octalactone have a major impact on the aromas of fortified wines.

Pectolytic enzymatic preparations used in enology come from Aspergillus niger. They have a desirable principal activity and several secondary activities. Among these secondary activities, three classes of esterases were detected: an esterase specific for ester linkage between cinnamic acid and alcohol (cinnamate esterase); an esterase acting on ester linkage between two phenolic rings (depsidase); and an esterase hydrolysing ester linkage between phenolic acids and straight-chain alcohols (phenyl esterase). Only the first class of enzyme is able to hydrolyse the cinnamic acid tartrate ester of the white must. The authors tried to purify the cinnamate esterase from the other esterase of an A niger industrial pectolytic preparation. This purification was done in two steps. A gel filtration on S200 HR Sephacryl was first used. This step eluted two fractions: esterases and pectin esterase. The second step was affinity chromatography on a 4B Sepharose EAH grafted with chlorogenic acid. This step eluted two fractions: an unretained fraction containing the phenyl esterase and the depsidase; and a retained fraction with the cinnamate esterase. This enzyme has a molecular weight of 240 kDa and contains two submits of 120 kDa. A new classification for these three esterases is suggested. © 1998 Society of Chemical Industry.

This study is dedicated to quantification, by gas chromatography combined with mass spectrometry, of some volatile compounds founded during ageing of sweet natural wines. Besides determination of the thresholds olfactory perception enable us knowing better the more active compound in sweet natural wines aroma.The results enable to know better volatile compounds which are able to produce ageing aromas characteristic of sweet natural wines. These products are always rich in sugar and grown up in a more or less oxidising environment. Logically, many of the compounds identified in this work (derived furanic compounds and many others) are Iinked with chemical like Maillard reactions between sugars and amino-acids. Others compounds as a sotolon need oxidising phenomena to increase in the environment.Comparatively, oldest Port wines have been analysed. The compounds measured in these Port wines also exist in French sweet natural wines of type Banyuls and Rivesaltes, keeped under oxidising environment. But the dillerences of concentrations in some compounds discriminate them from the Port wines.

Différents essais de laboratoire sont utilisés depuis longtemps pour évaluer le risque d'apparition d'un trouble protéique. Les auteurs comparent ces différents tests en utilisant les méthodes récentes de mesure de la limpidité (néphelométrie) et de dosage des protéines (CLHP).Les résultats obtenus montrent que le test à la chaleur (80° C-30 mn) reste l'essai de laboratoire le plus fiable, car il est simple à mettre en oeuvre et il se rapproche le plus des conditions d'apparition des troubles protéiques dans la pratique.+++Various laboratory stability tests have been used for a long time to check the risks of protein turbidity. The authors have been comparing those different tests with the help of more modern methods of measuring out cloudiness (nephelometry) and protein (HPLC).Six tests were examined :- The test consisting in heating for 5 minutes at 80° C in a double-boiler.- The test consisting in heating for 30 minutes at 80° C in a double-boiler.- The test consisting in heating for 10 days at 35° C in an oven.- The adding of 0.5 9 of tannin per litre.- The adding of a reagent to phosphomolybdic acid (bentotest).- The adding of trichloracetic acid.The results are as follows :- For the tests involving heat, the longer the heating at 80° C, the higher the measures of the turbidity are; the cloudiness observed for the test consisting in heating at 35° C for 10 days is quite important. If the results obtained with these heating tests are to be compared to the real protein values, the most efficient test consists in heating 30 minutes at 80° C.- For the tests consisting in adding tannins, a high variation of turbidity values must be related to the results obtained through high performance liquid chromatography. Moreover, the important cloudiness observed when the tannins were added does not correspond to the small difference observed between the chromatograms of the wine streated with the tanins and those of the original samples.- The reagent to phosphomolybdic acid (bentotest) and the trichloracetice acid test create an important turbidity. After chromatographic examination, the use of these reagents proved to be acting more thoroughly on every sort of protein than the use of heat in the heating tests. For two out of the four wine-samples examined, the bentotest was more drastic than the addition of trichloracetic acid.As a conclusion the heating test (80° C for 30 minutes) remains the most reliable laboratory test, because it is sample and easy to make; it is also very close to the conditions in which protein turbidity may appear in reality.

Three new flavour-active mercapto-alcohols have been identified in Sauvignon blanc wines: 4-mercapto-4-methylpentan-2-ol, 3-mercaptohexan-1-ol and 3-mercapto-3-methylbutan-1-ol. The first two have a perception threshold of the order of 60 ng/l in an aqueous alcohol solution and their respective odours are reminiscent of citrus zest and grapefruit. The perception threshold of 3-mercapto-3-methylbutan-1-ol, with its odour of cooked leeks, is higher (1500 ng/l in the same solution). These three compounds may contribute towards the typical aroma of Sauvignon blanc wines.

Volatile thiols were purified from a dichloromethane extract of Sauvignon blanc wine by the reversible combination of the thiols with p-hydroxymercuribenzoate, fixation of the resulting complex in an anion exchange column, and finally release of the thiols with cysteine. By analyzing the purified thiol extract from 500 mL of wine, using gas chromatography coupled with mass spectrometry, it was possible to measure the concentrations of five volatile compounds at once: 4-mercapto-4-methylpentan-2-one, 3-mercaptohexyl acetate, 3-mercaptohexan-1-ol, 4-mercapto-4-methylpentan-2-ol, and 3-mercapto-3-methylbutan-1-ol. Analysis of 10 typical Sauvignon Blanc wines (Bordeaux, Sancerre) showed that the first three compounds listed above are expected to be involved in varietal aroma, as they may be present at concentrations greatly in excess of their respective perception thresholds. Keywords: Volatile thiol; aroma; Sauvignon blanc wine; Vitis vinifera; p-hydroxymercuribenzoate

Toasting wood to be used in barrels for aging wine and brandy produces a great number of volatile and odiferous compounds. Some of these have a "toasty caramel" aroma. Analysis by high-performance gas chromatography of toasted oak extracts, combined with olfactory detection, enabled various Chromatographic peaks with these specific aromas to be isolated. These same odors were simultaneously studied by heating glucose both with and without proline. Aromatic compounds of interest were identified thanks to a combination of gas chromatography and both mass and infrared spectrometry. In addition to already-known substances such as 2-hydroxy-3-methyl-2-cyclopenten-1-one (cyclotene) (1) and 3-hydroxy-2-methyl-4H-pyran-4-one (maltol) (2), we identified, for the first time, 2,3-dihydro-3,5-dihydroxy-6-methyl-4H-pyran-4-one (DDMP) (3), 4-hydroxy-2,5-dimethyl-3(2H)-furan-3-one (furaneol) (4), and 2,3-dihydro-5-hydroxy-6-methyl-4H-pyran-4-one (dihydromaltol) (5) as compounds which actively contribute to the "toasty caramel" aroma of heated oak. Their role in the aroma of wines and spirits is thus well worth studying. These molecules were absent from the glucose pyrolysis but were relatively plentiful after heating in the presence of proline. Therefore, Maillard reactions were seen to be the cause of these substances in the heated oak wood.

Yeast lees isolated from wine or a culture medium after fermentation have the particular property of being able to adsorb certain volatile thiols contained in a hydroalcoholic wine-like solution. Yeast cell-walls are also able to adsorb the same thiols when prepared by mechanical disruption of whole cells in the presence of a reducing agent such as dithiothréitol (DTT). Thiols adsorbed in this manner may be re-released from the cell-walls by the addition of DTT in the medium. On the other hand, yeast cell-walls prepared under the same conditions lose their adsorption capacity following hydrolysis with a beta-glucanase preparation able to release mannoproteins.These results indicate that volatile thiols combine with the yeast cell-walls by means of disulphide bonds with the cystein contained in mannoproteins.

4-mercapto-4-methylpentan-2-one (4-MMP), a strongly odorant compound responsible for the « boxtree » or « broom plant » odour of the Sauvignon wines, can be enzymaticaly released in vitro from an odourless must extract. The enzyme source used is a cell-free extract of the gastrointestinal bacterium Eubacterium limosum. This crude preparation exhibits a cysteine β-lyase activity which requires the presence of pyridoxal phosphate. The release of 4-MMP is inhibited when the substrate is previously treated with N-hydroxysuccimide acetate which reacts with a primary amine. The same bacterial extract is also able to release 4-MMP, pyruvic acid and ammonium, from S-(4-méthylpentan-2-one)-L-cysteine. On the other hand, the cleavage of S-(4-méthylpentan-2-one)D,L-homocysteine and S-(4-méthylpentan-2-one)- glutathione is very limited. These results suggest that the precursor of 4-MMP in Sauvignon must is a S-cysteine conjugate. Such an aroma precursor in grapes or in other fruits has never been round berore.

International audience; Volatile thiols, compounds that contribute strongly to the varietal aroma, are present in much higher concentrations in sweet wines than in dry wines. This positive effect, due to the presence of Botrytis cinerea on the berries, in fact results from a strong enrichment of cysteine S-conjugate precursors in botrytized berries. In the present study, a convenient model was investigated to reproduce and therefore study this phenomenon. A Vitis vinifera cell culture was used as a simple model, and we focused on S-3-(hexan-1-ol)-l-cysteine (P-3SH), the cysteinylated precursor of 3-sulfanylhexanol. We demonstrated that grapevine cells were able to produce P-3SH and that the presence of B. cinerea considerably increased the precursor level (up to 1000-fold). This positive result was determined to be due to metabolites secreted by the fungus. These molecules were temperature sensitive, unstable over time, and their production was activated in the presence of grapevine cells. Moreover, part of the pathway leading to P-3SH was deciphered: it was directly derived from the cleavage of S-3-(hexan-1-ol)-l-glutathione, which itself was generated after a conjugation of glutathione on (E)-2-hexenal.

Vinylphenols (4-vinylphenol and 4-vinylguaiacol) are natural constituents of wine and can play a role in wine aroma. However, only white wines contain important quantities of these volatile substances which, beyond a certain concentration (limit threshold = 725 μg litre−1 of 4-vinylguaiacol+4-vinylphenol (1:1)), can be responsible for a depreciating ‘phenolic’ or ‘pharmaceutic’ characteristic, Saccharomyces cerevisiae possesses a type-(E) enzymic activity, substituted cinnamate carboxy-lyase (SCD), which is capable of transforming, by non-oxidative decarboxylation, the phenolic acids in the must, (E) p-coumaric and (E) ferulic acids, into corresponding vinylphenols. This endocellular activity is constitutive, it is only expressed during alcoholic fermentation and with a variable intensity depending on the yeast strain. Furthermore, the enzyme is rapidly inhibited by catechic tannins, which explains why, in comparison with white wines, red and rose wines contain low levels of vinylphenols despite having more precursors. A yeast strain with a weak SCD activity has been selected and its use in vinification should eliminate the appearance of the phenolic taint in white wines coming from grapes rich in decarboxylable hydroxycinnamic acids.

International audience; A compound associated with oxidized flavor in red wines was recently-identified as 3-methy1-2,4-nonanedione (MND). In order to quantify it, positive chemical ionization (PCI) in an ion trap was studied using conventional liquid reagents such as methanol, acetonitrile, and acetone, as well as non-conventional liquid reagents such as ethyl acetate, diethyl ether, pentane, isohexane, and heptane. Under laboratory conditions, very different response factors were obtained with MND depending on the gas. We also compared the detection limit of conventional Cl with hybrid chemical ionization (HCI). Finally, this compound was quantified in red wines by liquid/liquid extraction without any derivatization steps, followed by GC/MS-CI analysis, using methanol as the reagent gas. Coelutions of compounds with the same. m/z were checked using methanol-d(4). The method we developed was linear in the 10-300 ng/L range of MND concentrations, with satisfactory repeatability. The detection limit was 4.3 ng/L, over 3 times lower than the olfactory perception threshold of this compound (16 ng/L). The suitability of this method for assaying this diketone in red wine was demonstrated by the analyzing many wines from different vintages. (C) 2011 Published by Elsevier B.V.

International audience; Sotolon (3-hydroxy-4,5-dimethyl-2(5H)-furanone) is a chiral furanone, an aroma compound known to be responsible for premature-aging flavor in dry white wines. Sotolon generally results from mild oxygenation during bottle aging, and until now, its formation pathways had not been elucidated. The ability of the main precursors described in the literature under very different experimental conditions to produce sotolon was tested. In model wine solution maintained at 40 degrees C for 6 months, sotolon was produced by the oxidative degradation of ascorbic acid. By use of GC-MS, 2-ketobutyric acid, produced by the oxidative degradation of the ascorbic acid in the model wine solution, was identified as a potent precursor of sotolon in this pathway. Ascorbic acid is an exogenous compound, added before bottling, but 2-ketobutyric acid was found even in white wines that had not been supplemented. Consequently, this sotolon formation pathway is also valid in white wines with no added ascorbic acid. In addition, we showed that Saccharomyces cerevisiae strains were capable of producing variable concentrations of this ketone during alcoholic fermentation. In model wine solution, certain yeast strains released large quantities of 2-ketobutyric acid, similar to those found in oxidized dry white wines. In view of these results, the role of yeast strains in this premature-aging phenomenon of dry white wines is discussed. Finally, these investigations revealed that one chemical mechanism responsible for the low concentrations of sotolon found in prematurely aged white wines made from various grape varieties was an aldol condensation between 2-ketobutyric acid and acetaldehyde.

International audience; This work outlines the results from an investigation to determine the effect of the oxygen dissolved at bottling and the specific oxygen barrier properties of commercially available closures on the composition, color and sensory properties of a Bordeaux Sauvignon Blanc wine during two years of storage. The importance of oxygen for wine development after bottling was also assessed using an airtight bottle ampule. Wines were assessed for the antioxidants (SO(2) and ascorbic acid), varietal thiols (4-mercapto-4-methylpentan-2-one, 3-mercaptohexan-1-ol), hydrogen sulfide and sotolon content, and color throughout 24 months of storage. In addition, the aroma and palate properties of wines were also assessed. The combination of oxygen dissolved at bottling and the oxygen transferred through closures has a significant effect on Sauvignon Blanc development after bottling. Wines highly exposed to oxygen at bottling and those sealed with a synthetic, Nomacorc classic closure, highly permeable to oxygen, were relatively oxidized in aroma, brown in color, and low in antioxidants and volatile compounds compared to wines sealed with other closures. Conversely, wines sealed under more airtight conditions, bottle ampule and screw cap Saran-tin, have the slowest rate of browning, and displayed the greatest contents of antioxidants and varietal thiols, but also high levels of H(2)S, which were responsible for the reduced dominating character found in these wines, while wines sealed with cork stoppers and screw cap Saranex presented negligible reduced and oxidized characters.

4-Methyl-4-sulfanylpentan-2-one (1; 4MSP) provides a characteristic aroma compound of wines made from Vitis vinifera L. cv. Sauvignon blanc. 4MSP has a strong box-tree odor with a very low perception threshold and is derived from the cysteinylated precursor S-(1,1-dimethyl-3-oxobutyl)cysteine (4; P-4MSP). P-4MSP is transformed into 4MSP during alcoholic fermentation and is an excellent marker of varietal aroma potential. An improved synthesis of P-4MSP as well as of its deuterium-labeled analogue [D(6)]-P-4MSP is described. Several analytical methods (NMR, IR, LSI-MS, GC/MS, ESI-MS(n)) were combined to elucidate spontaneous reversible structural changes of P-4MSP at different pH values. At low pH, P-4MSP has a linear keto form. The keto-enol tautomerism was observed at neutral pH. At pH 8, the formation of N-substituted intramolecular hemiaminal was characterized by ESI-MS and ESI-MS(n) experiments. The hemiaminal loses H(2)O at high pH to produce a cycloimine, which is easily opened by acid hydrolysis. The keto-enol tautomerism explained the incorporation of only six D-atoms during the preparation of the P-4MSP deuterated standard even if [D(10)]mesityl oxide was used. Derivatization conditions for GC/MS analysis strongly affected the ratio of the monosilylated intramolecular cyclic form and the disilylated linear form of P-4MSP. The structural changes of P-4MSP may have a considerable impact on the development of methods of measuring varietal aroma potential.

International audience; Sulfur dioxide is now considered to be a toxic chemical by most world health authorities. However, it remains an irreplaceable additive in enology for wine conservation, combining antioxidant and antibacterial properties. Sweet white wines from botrytized grapes retain particularly high SO2 levels due to their high sulfur dioxide binding power. This paper presents a new method for reducing this binding power by removing some of the carbonyl compounds responsible, which are naturally present in these wines. The main carbonyl compounds responsible for the SO2 binding power of sweet wines were removed, that is, acetaldehyde, pyruvic acid, 2-oxoglutaric acid, and 5-oxofructose. The method retained was selective liquid-solid removal, using phenylsulfonylhydrazine as a scavenging agent. The scavenging function was grafted on different classes of porous polymer supports, and its efficiency was evaluated on sweet white wines under conditions intended to conserve their organoleptic qualities. The results obtained showed that the method was efficient for removing carbonyl compounds and significantly reduced the binding power of the wines. Sensory analysis revealed that this process did not deteriorate their organoleptic qualities.

International audience; The diastereoisomeric distribution of S-3-(hexan-1-ol)cysteine (P-3SH), the cysteinylated precursor of 3-sulfanylhexan-1-ol (3SH) in Vitis vinifera grape juice, was determined by a new method. This procedure is based on the purification of P-3SH in a small volume of must (500 μL) by affinity chromatography, followed by the separation of chiral molecules in derivative forms by gas chromatography coupled with ion trap tandem mass spectrometry (GC–MS/MS). The diastereoisomers were easily separated using heptafluorobutyric anhydride and heptafluorobutanol (HFBA and HFOH) as derivatization reagents. Method validation was conducted using samples of grape juice, synthetic must, fermenting must, and wine that were fortified with P-3SH at concentrations of 0.6 and 2.5 μM. The relative standard deviation (RSD) and limit of detection (LOD) of the GC–MS/MS method were 4.6% and 1.5 nM, respectively. P-3SH assays in Bordeaux white grape juice affected by Botrytis cinerea showed an unusually increased proportion of the RS form of the precursor (approximately RR:RS = 30:70) as compared to a diastereoisomer ratio (in the vicinity of 50:50) in healthy grape juice.

International audience; GC-MS in electron ionization mode (EI) was used as a simple, sensitive method for assaying sotolon [4,5-dimethyl-3-hydroxy-2(5) H-furanone] in various dry white wines. The impact of barrel-aging conditions, that is, whether yeast lees were present or not, on the formation of sotolon in dry white wines was then studied. The sotolon content was highest in dry white wines aged in new barrels without lees, often exceeding the perception threshold (8 microg/L). These results demonstrated that yeast lees were capable of minimizing the formation of sotolon in dry white wines during aging. The sotolon and oxygen contents of several bottle of the same white wine were also compared 7 years after bottling. At the range of dissolved oxygen concentrations generally measured, between 5 and 100 microg/L, the sotolon content remained below its perception threshold in wine. The perception threshold was exceeded only in wines with oxygen concentrations above 500 microg/L. The presence of dissolved oxygen in the wine samples analyzed also resulted in a decrease in their free sulfur dioxide content.

International audience; The enantiomers of sotolon, a flavor compound typical of oxidized white wines, were separated by preparative HPLC to determine their perception thresholds and distribution in wines. The enantiomeric ratios of chiral sotolon were evaluated in several dry white wines using gas chromatography and a chiral column (β-cyclodextrin) connected to a 2 m precolumn (BP20). The perception threshold of (S)-sotolon (0.8 µg/L) in model wine solution was 100 times lower than that of the (R) form (89 µg/L), indicating that (S)-sotolon contributes to the characteristic aroma of prematurely aged dry white wines. Both enantiomers are detected in white wines. Analysis of commercial dry white wines from various vintages and origins revealed three types of distribution patterns: the racemic form, an excess of R, and an excess of S. The proportions found in these wines may be partially explained by the slow racemization kinetics (20 months) of optically active sotolon.

International audience; Beta-damascenone, a C-13 norisoprenoid compound, is usually presented as an impact odorant in red wines. Its direct contribution to their aroma was investigated. Both free beta-damascenone and beta-damascenone precursors were isolated from various French red wines and then analyzed by gas chromatography-mass spectrometry, revealing concentrations in the vicinity of 1 and 2 µ*g/L for free compounds and both forms, respectively. Gas chromatography-olfactometry analyses were also performed on dilutions of both red wine extracts and pure beta-damascenone. The very low detection threshold in olfactometry for this compound explains why it is found at the highest dilution factor in aroma extract dilution analysis methods. Moreover, determination of beta-damascenone's odor thresholds confirmed the huge importance of the matrix: Beta-damascenone is characterized by a very low perception threshold in hydroalcoholic solution as compared to red wine, where it is over 1000-fold higher. In hydroalcoholic solution, beta-damascenone enhanced fruity notes of ethyl cinnamate and caproate and masked the herbaceous aroma of IBMP. Globally, these results suggested that beta-damascenone has more an indirect than a direct impact on red wine aroma.

International audience; Sweet white wines from botrytized grapes present high SO2 levels because of their high sulfur dioxide binding power. The objective of this work was to develop a new method for reducing this binding power by partially eliminating the carbonyl compounds naturally present in these wines that are responsible for this phenomenon. A selective liquid-solid removal technique was developed. Phenylsulfonylhydrazine was selected as the best candidate for removing carbonyl compounds. Its reactivity in the presence or absence of sulfur dioxide was verified in model media containing acetaldehyde, pyruvic acid, and 2-oxoglutaric acid, some of the main carbonyl compounds responsible for the SO2 binding power of sweet wines. The scavenging function was grafted on porous polymer supports, and its efficiency was evaluated in model wines. Dependent upon the supports used, different quantities of carbonyl compounds (over 90% in some cases) were removed in a few days. The presence of sulfur dioxide delayed removal without changing its quality. The results obtained showed that the method removed carbonyl compounds efficiently and was applicable to wines at any stage in winemaking.

International audience; Specific extraction of volatile thiols using sodium p-hydroxymercuribenzoate revealed the presence of three new sulfanylalcohols in wines made from Botrytis-infected grapes: 3-sulfanylpentan-1-ol (II), 3-sulfanylheptan-1-ol (III), and 2-methyl-3-sulfanylbutan-1-ol (IV). The first two have citrus aromas, whereas the third is reminiscent of raw onion. In addition, 2-methyl-3-sulfanylpentan-1-ol, which has a raw onion odor, was tentatively identified. Like 3-sulfanylhexan-1-ol (I), already reported in Sauternes wines, compounds II, III, and IV were absent from must. They were found in wine after alcoholic fermentation, and their concentrations were drastically higher when Botrytis cinerea had developed on the grapes. In the commercial botrytized wines analyzed, the mean levels of II, III, and IV were 209, 51, and 103 ng/L, respectively. Despite their low odor activity values, sensory tests showed additive effects among I, II, and III, thus confirming their olfactory impact on the overall aroma of botrytized wines.

In dry white wines, two different forms of instability occur: (i) substantial yellow or yellow-green deposits are observed principally due to flavonol quercetin; and (ii) protein instability leads to protein casse. Polyvinyl polypyrrolidone (PVPP) is used to adsorb phenols from beverages, and bentonite is used to eliminate heat instable protein. However, in both cases, their effects are still largely unknown. This study uses a multitechnique approach to gain a better molecular understanding of the association of polyphenol aglycones with PVPP compared to that of glucosides with PVPP. The work demonstrates, that with aglycones, three forces drive complex formation: hydrophobic interaction, H bonds, and van der Waals bonds. With glucosides, the sugar moiety removes or reduces these driving forces. Thus, if the interaction between proteins and polyphenols is responsible for haze and precipitates, as is classically assumed, PVPP could prevent quercetin sedimentation.

The effect of Saccharomyces cerevisiae strains on the amount of 4-mercapto-4-methylpentan-2-one, a major varietal aroma of Sauvignon blanc wines, was demonstrated by previous research work. However, the influence of different alcoholic fermentation parameters on the levels of volatile thiols (4-mercapto-4-methylpentan-2-one, 3-mercaptohexan-1-ol and 3-mercaptohexyl acetate) in wines has not yet been investigated. The impact of fermentation temperature on the final amount of volatiles thiols and on some other analytical parameters (ethanol, total acidity, residual sugars, volatile acidity) was determined in a model medium and in grape juice. Interaction between fermentation temperature and yeast strain was also tested. The fermentation temperature influenced the amount of volatile thiols irrespective of the yeast strain used. The final levels of 4MMP and 3MH in model medium and in wines were higher when the alcoholic fermentation is conducted at 20 degrees C than at 13 degrees C. The 3MHA, which was correlated with the amount of 3MH determined in wines, was also higher when the alcoholic fermentation was conducted at 20 degrees C. From a technological point of view, the choice of yeast strain and fermentation temperature has a decisive influence on the concentrations of the varietal aromas of Sauvignon blanc wines.

Geosmin (trans-1,10-dimethyl-trans-9-decalol), an earthy-musty compound, has been identified in wines and in grape juice, in which its presence is highly detrimental to the aromatic quality. Geosmin has a biological origin, and the analysis of rotten grape microflora has been done on two grape varieties (Semillon, Cabernet Sauvignon) from six parcels of the Bordeaux region over 3 years (1999, 2000, 2001). Forty-three Penicillium-related species have been analyzed by gas chromatography-mass spectrometry (GC-MS) for their geosmin production. GC-MS analysis has demonstrated that the earthy odor was always correlated with the presence of geosmin. Phenotypic characterization of Penicillium spp. being ambiguous, a molecular characterization by rDNA internal transcribed spacer (ITS1) sequencing was performed for all strains. The results evidenced that all strains producing geosmin belonged to only one species, P. expansum, and that the other strains, not producing geosmin, belonged to three species: P. purpurogenum, P. thomii, and Talaromyces wortmanii.

A method to measure specific β(1,3)-glucanase activity in wines has been developed, and is based on the measurement of the kinetics of glucose release in the presence of laminarin (a β(1,3)-glucan from Laminaria digitata). The reaction time and substrate amount have been optimised to allow for measurements in wine conditions. The optimised method has been used to measure the efficiency of a commercial enzyme preparation in wines in relation to filterability. The results indicate that despite the inhibition of wine constituents, β-glucanase activities were present in all wines after enzyme addition. The filterability of the wines significantly increased after enzyme addition as measured by a standardised procedure (Vmax index).

The effects of powdery mildew (Uncinula necator) on grape yield, juice and wine quality were quantified for cultivar Cabernet Sauvignon (CSa) in 1997 and 1999, and for Sauvignon blanc (Sa) in 1999. Analyses were carried out on batches of healthy berries to which known percentages (0–50%) of diseased berries were added, and on natural clusters that were classified into four visual classes from low (C1) to high (C4) disease severity. CSa diseased berries showed an average weight reduction of 12% (1997) and 20% (1999). The direct consequence of a higher percentage of smaller, diseased berries was a reduction in yield. The accompanying loss of weight in must from C1 to C4 clusters increased from 10 to 45%. Sugar content in diseased berries was not significantly different from disease-free berries in 1997, but was 20–21% (CSa) and 14% (Sa) higher in 1999. Severely infected batches also showed a higher total acidity than healthy ones. The total anthocyanin content of CSa was decreased by 0·91% (1997) and 0·66% (1999) per percentage mildewed berries added by weight. In Sa wines the concentration of 3-mercaptohexanol, a component of varietal aroma, was decreased by powdery mildew. Multidimensional analyses, based on all the variables studied, successfully grouped batches of CSa according to disease severity. Using directional triangular tests wine experts were able to recognize CSa wines produced from berries with ≈25% of powdery mildew; the threshold for nonexperts was 50%. CSa wines obtained from samples with more than 30% of diseased berries by weight were significantly classified as the worst according to preference order criteria, but below this value the preference was not significant. Sa wines with

White wines experimentally produced from the white grape varieties Loureira, Dona Branca, and Treixadura have been analyzed over four consecutive harvests. The contents of monoterpenes, volatile phenols, alcohols, sulfur components, acetates, fatty acids, and ethyl esters were determined by gas chromatography (FID) and gas chromatography-mass spectrometry. The mean values from four vintages confirmed that these wines have characteristic profiles. Loureira wines are characterized by a high content of free terpenes, 1-hexanol, ethyl acetate, and fatty acids. Dona Branca wines present the highest concentrations of methanol and sulfur constituents, and the lowest concentrations of higher alcohols, acetates, diethyl succinate, and ethyl esters. The levels of monoterpenes in Treixadura wines are very low, but they have the highest concentrations of volatile phenols, principally due to the vanillin, diethyl succinate, ethyl lactate, and ethyl esters. These results were confirmed by principal component and linear discriminant analysis, which show a clear differentiation among these wines as a function of the varietal origin.

Furfurylthiol (FFT) is formed in white wines during alcoholic fermentation in the barrel from the furfural released by toasted staves. The quantity of furfural released into the must has a decisive effect on the quantity of FFT in the finished wine. Wines fermented in new barrels thus contain larger quantities of FFT than those fermented in used barrels. Fermentation conditions favorable to an excess production of H(2)S (hydrogen sulfide) by the yeast promote the formation of this volatile thiol. The presence of this volatile thiol in white wines is, therefore, closely related to the yeast's sulfur metabolism.