Gluconic acid,its lactones,and SO(2) binding phenomena in musts from botrytized grapes

Intramolecular gluconic acid esterification reactions led to the formation of two lactones, gamma- and delta-gluconolactone (glucono-1,4-lactone and glucono-1,5-lactone). The presence of the first has not yet been reported in must or wine. These lactones are in equilibrium with gluconic acid, gamma- and delta-gluconolactone representing, respectively, 5.8 and 4.1% of the acid level. Correlations between must SO(2) binding power, gluconic acid, and consequently its lactones are shown. The SO(2) affinity of a mixture containing this acid and gamma- and delta-gluconolactone was determined, and gluconic acid appeared to be indirectly responsible for approximately 8% of the bindable SO(2) in musts from botrytized grapes.     

Potential application of a glucose-transport-deficient mutant of Schizosaccharomyces pombe for removing gluconic acid from grape must

Musts from rotten grapes typically contain high levels of gluconic acid, which can raise severe problems in winemaking processes. In this work, the ability of the glucose-transport-deficient mutant YGS-5 of Schizosaccharomyces pombe to completely or partly remove gluconic acid from a synthetic glucose-containing medium and the potential use of this yeast strain for the same purpose in musts and wines were examined. Surprisingly, the S. pombe YGS-5 strain successfully removed 93% of the initial gluconic acid (2.5 gL(-1)) and 80% of the initial malic acid (1.0 gL(-1)) within 30 h after inoculation. Also, the yeast strain produced no volatile compounds other than those obtained in fermentations conducted with the wine yeast Saccharomyces cerevisiae. S. pombe YGS-5 could thus be used to remove gluconic acid present in musts from rotten grapes. On the basis of these results, various ways of using S. pombe YGS-5 to treat musts containing gluconic acid in order to solve the problems due to the high gluconic acid concentrations in botrytized grape must are proposed.     

New method for reducing the binding power of sweet white wines

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 SO 2 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 SO 2 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.     

New methodology for removing carbonyl compounds from sweet wines

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.     

Protection of originality of Tokaji Aszú: amines and organic acids in botrytized wines by high-performance liquid chromatography

Amine and organic acid composition of Aszú wines from the Tokaj region of Hungary, nonbotrytized Hungarian wines from different regions, and foreign botrytized wines were analyzed by high-performance liquid chromatography. Hungarian and foreign wines (36 Hungarian and seven foreign botrytized wines) were compared in different ways by calculation of ratios of given amine compounds, analyses of variance, principal component, and discriminant analysis. In wines, putrescine and in some samples 3-methyl-butylamine and/or phenyl ethylamine were found in remarkable concentrations, while in botrytized wines four other amines were verified in high concentration. Good separation between Aszú and foreign botrytized wines was found by calculation of the amine component's ratio. The first two principal components of the principal component analysis accounted for 77 and 84% of the total variance in the data of amines and acids, respectively. The component scores of samples grouped according to Aszú, foreign botrytized, and nonbotrytized wines. Linear discriminant analysis was used for differentiation of Aszú, foreign botrytized, and normal wines. Using nine amines and two acids as variables, the correct classification was 97.6%. On the basis of results, an objective evaluation method can be elaborated for quality control in order to protect the authenticity and origin of wine specialties made from botrytized grapes.     

Characterization of some mushroom and earthy off-odors microbially induced by the development of rot on grapes

Grape rot is one of the major causes of degradation of many grape components and, thus, of deterioration in wine quality. In particular, the association of Botrytis cinerea with other, less visible, fungi frequently leads to the development of organoleptic defects in grapes and sometimes in wines. This study examines the nature of the volatile compounds responsible for mushroom, mossy, or earthy odors detected by gas chromatography-olfactometry in organic extracts of rotten grapes and musts. 2-Methylisoborneol, (-)-geosmin, 1-octen-3-one, 1-octen-3-ol, 2-octen-1-ol, and 2-heptanol were identified or tentatively identified. Their concentrations in musts were determined, and the impact of alcoholic fermentation by the yeast Saccharomyces cerevisiae was studied. The ability of fungi isolated from rotten grapes (Botrytis cinerea; Penicillium species including P. brevicompactum, P. expansum, P. miczynskii, P. pinophilum, P. purpurogenum, and P. thomii; Aspergillus section nigri; Rhizopus nigricans; and Coniothyrium sp.) to produce some of the identified compounds was evidenced.     

Effect of Schizosaccharomyces pombe on aromatic compounds in dry sherry wines containing high levels of gluconic acid

Volatile compounds have been determined in control dry sherry wines and those supplemented with gluconic acid, which were inoculated with the Schizosaccharomyces pombe 1379 (ATCC 26760) yeast strain. These compounds were grouped, according to volatiles exhibiting the identical odor quality, into nine groups of the same odor character (aromatic series) as a way of establishing the aroma profile for the studied wines. Control and supplemented wines showed changes in the balsamic, spicy, roasty, and fruity aromatic series, and tasters judged the aroma as typical of wines subjected to biological aging. This fission yeast may be used as a treatment to reduce gluconic acid contents in wines obtained from rotten grapes, making feasible the incorporation of these wines into the biological aging process. In addition, this procedure may also help to accelerate the traditional biological aging in sherry winemaking due to the contribution of some specific compounds by S. pombe to the wine.     

Effect of different strains of Saccharomyces cerevisiae on production of volatiles in Napa Gamay wine and Petite Sirah wine

Napa Gamay grapes were fermented with four different strains of the yeast Saccharomyces cerevisiae (VL1, MI16, Fermirouge, and RA17). Petite Sirah grapes were fermented with seven different strains of the same yeast (BM45, Fermirouge, RA17, NI, CX3079, A350, and A796). Volatile compounds formed in the wines were analyzed by gas chromatography/mass spectrometry. Volatile compounds found in both wines were alcohols, esters, and acids, as well as some miscellaneous compounds. Isoamyl alcohol was the compound found in the highest relative amount with all four yeast strains in the Napa Gamay wines, followed by 2-phenyl ethanol, monoethyl succinate, and hexanoic acid. The relative amounts of isoamyl alcohol ranged from 30.84% (VL1) to 43.28% (RA17). Major volatile compounds found in Petite Sirah wines were isoamyl alcohol, 2-phenyl ethanol, 2-hydroxy ethyl propanoate, monoethyl succinate, and octanoic acid. The several esters, including 2-hydroxyethyl propanoate, may contribute to the fruity flavor of Petite Sirah wines. Overall, the S. cerevisiae yeast strains used to ferment Napa Gamay grapes and Petite Sirah grapes produced the same major components, with certain variations in formation levels.     

Drying of Pedro Ximenez grapes in chamber at controlled temperature and with dipping pretreatments. Changes in the color fraction

The drying of Pedro Ximenez grapes in chamber at a controlled temperature of 40 or 50 degrees C is studied. Compared to traditional sun-drying, the chamber-drying shortened the drying time by about 40% at 50 degrees C. In color terms, the musts obtained from grapes dried at 50 degrees C were closer in CIELab coordinates to those obtained by sun-dried grapes, with similar h(ab) values and slightly lower L* and C(ab)*. To shorten further the drying times at 50 degrees C, the grapes were dipped in olive oil or ethyl oleate emulsions containing potassium carbonate. The ethyl oleate pretreatment shortened additionally the drying time by about 25%, providing musts with chroma, lightness, and hue similar to those without grape pretreatment. In general, except for the phenolic compounds corresponding to the drying with ethyl oleate pretreatment, most of these compounds in the remainding conditions studied increased to a lesser extent than expected because of water losses of the grapes during drying, revealing degradation reactions.     

Off-vine grape drying effect on volatile compounds and aromatic series in must from Pedro Ximénez grape variety

Changes in 36 volatile compounds of must from ripe grapes dried by direct exposure to sun and must from ripe grapes were studied. Compounds not dependent on sampling site in both musts were selected, and their concentration/Brix degree ratio values, were subjected to variance analysis. Only butan-1-ol and isoamyl alcohols showed no differences, while (E)-hex-3-en-1-ol, (Z)-hex-3-en-1-ol, (E)-hex-2-en-1-ol, (E)-hex-2-enal, hexanoic acid, isobutanol, benzyl alcohol, 2-phenylethanol, gamma-butyrolactone, gamma-hexalactone, and 5-methylfurfural, showed significant differences between the two must types, which may be ascribed to the drying process. An approach to describe must odor has been carried out by grouping volatile compounds in aromatic series, increasing their values in the fruity, solvent, sweet, and roasted series and diminishing the herbaceous as a consequence of the drying process.     

Odorous impact of volatile thiols on the aroma of young botrytized sweet wines: identification and quantification of new sulfanyl alcohols

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.     

Effect of gluconic acid consumption during simulation of biological aging of sherry wines by a flor yeast strain on the final volatile compounds

Flor yeast Saccharomyces cerevisiae (capensis G1) strain assimilates gluconic acid during the aerobic biological aging process of sherry wines and exerts significant changes on the final volatile compounds of wines, especially a decrease in volatile acidity and butanoic, isobutanoic, 2-methylbutanoic, and 3-methylbutanoic acids. This decrease may have a favorable effect on the quality of sherry wines.     

Relationship between varietal amino acid profile of grapes and wine aromatic composition. Experiments with model solutions and chemometric study

Synthetic solutions containing amino acids, sugar, water, and yeast nutrients have been fermented by Saccharomyces cerevisiae, and the volatile composition of the fermented media has been analyzed by GC. Eleven amino acid compositions imitating the characteristic amino acid profile of 11 different grape varieties were tested. Significant differences in the levels of some important volatile compounds (ethanol, ethyl acetate, acetic acid, higher alcohols and some of their acetates, methionol, isobutyric acid, ethyl butyrate, and hexanoic and octanoic acids) were found. The levels of some of the volatile compounds are well correlated with the aromatic composition of wines made with grapes of the same varieties. A multiple linear regression study produced good models for most of the odorants for which the level was related to the must amino acid composition. Partial least-squares regression models confirm that amino acid composition explains a high proportion of the variance in the volatile composition and show that the relationship between both sets of variables is highly multivariate. According to the different models, the levels of some byproducts of fatty acid synthesis are related to threonine and serine, the level of beta-phenyletanol is closely related to the level of phenylalanine, and methionol is strongly correlated to the must methionine contents. The addition of selected amino acids to different musts confirms the previous observations.     

Impact odorants contributing to the fungus type aroma from grape berries contaminated by powdery mildew (Uncinula necator); incidence of enzymatic activities of the yeast Saccharomyces cerevisiae

Powdery mildew due to the fungus Uncinula necator is an important disease for the vineyard. The development of the fungus at the surface of the berries leads to the occurrence of a very characteristic and sometimes intense mushroom-type odor cited as an important default for grapes quality. Gas chromatography/olfactometry, gas chromatography, and multidimensional gas chromatogaphy/mass spectrometry techniques were used to investigate the most important odorants of grapes diseased by powdery mildew. Among 22 odorants detected, strongly odorant compounds were identified or tentatively identified in purified extracts obtained from grapes diseased by powdery mildew. Aroma extraction dilution analysis (AEDA) analysis revealed that 1-octen-3-one (mushroom odor), (Z)-1,5-octadien-3-one (geranium-leaf odor), and an unidentified odorous zone (fishy-mushroom like odor) were the most potent volatiles of the diseased grapes. In the presence of nonproliferating Saccharomyces cerevisiae yeast cells, and consequently during alcoholic fermentation, the enzymatic reduction of 1-octen-3-one and (Z)-1,5-octadien-3-one to much less odorant compounds, namely 3-octanone and (Z)-5-octen-3-one, was shown. Those results explain to some extent the disappearance of the fungal aroma specific to powdery mildew grapes during alcoholic fermentation.     

Metabolic influence of Botrytis cinerea infection in champagne base wine

Botrytis cinerea infection of grape berries leads to changes in the chemical composition of grape and the corresponding wine and, thus, affects wine quality. The metabolic effect of Botrytis infection in Champagne base wine was investigated through a (1)H NMR-based metabolomic approach. Isoleucine, leucine, threonine, valine, arginine, proline, glutamine, γ-aminobutyric acid (GABA), succinate, malate, citrate, tartarate, fructose, glucose, oligosaccharides, amino acid derivatives, 2,3-butanediol, acetate, glycerol, tyrosine, 2-phenylethanol, trigonelline, and phenylpropanoids in a grape must and wine were identified by (1)H NMR spectroscopy and contributed to metabolic differentiations between healthy and botrytized wines by using multivariate statistical analysis such as principal component analysis (PCA). Lowered levels of glycerol, 2,3-butanediol, succinate, tyrosine, valine derivative, and phenylpropanoids but higher levels of oligosaccharides in the botrytized wines were main discriminant metabolites, demonstrating that Botrytis infection of grape caused the fermentative retardation during alcoholic fermentation because the main metabolites responsible for the differentiation are fermentative products. Moreover, higher levels of several oligosaccharides in the botrytized wines also indicated the less fermentative behavior of yeast in the botrytized wines. This study highlights a metabolomic approach for better understanding of the comprehensive metabolic influences of Botrytis infection of grape berries in Champagne wines.     

Enantioselective analysis of free and glycosidically bound monoterpene polyols in Vitis vinifera L. cvs. Morio Muscat and Muscat Ottonel: evidence for an oxidative monoterpene metabolism in grapes

The enantiomeric ratios of various free and glycosidically bound monoterpene polyols in musts of the aromatic grapes Vitis vinifera L. cvs. Morio Muscat and Muscat Ottonel were determined by means of enantioselective multidimensional gas chromatography-mass spectrometry. Reference compounds of defined stereochemistry were synthesized and permitted the unequivocal determination of the elution order of the target compounds on chiral columns with modified cyclodextrins as stationary phases. It could be shown for the first time that the linalool-derived polyol 3,7-dimethylocta-1,7-dien-3,6-diol occurs predominately as the (3S,6S)-configured stereoisomer, providing evidence that this compound is generated by an enzymatic process in grape berries. The involvement of a cytochrome P450 monooxygenase in the oxidative metabolism of monoterpenes in grapes is dicussed.     

Levels of stilbene oligomers and astilbin in French varietal wines and in grapes during noble rot development

Phenolics from grapes and wines can play a role against oxidation and development of atherosclerosis. Stilbenes have been shown to have cancer chemopreventive activity and to protect lipoproteins from oxidative damage. A method for the direct determination of stilbene oligomers (viniferin and pallidol) as well as astilbin in different types of wine using high-performance liquid chromatography with UV detection is described. In a survey of 21 commercial wines from the south of France, levels of pallidol and viniferin are reported for the first time in different types of wines. Viniferin was found to be present only in red and botrytized sweet white wines with levels between 0.1 and 1.63 mg/L; pallidol was not found in dry and sweet white wines but only in wines made by maceration with stems, with levels between 0.38 and 2.22 mg/L. Highest levels of astilbin were found in Egiodola (15.13 mg/L), Merlot (11.61 mg/L), and Cabernet Sauvignon (8.24 mg/L) for red wines and in Sauvignon (5.04 mg/L) for white varietal wines. Astilbin levels are highest for recent vintages, but pallidol is not found in older vintages. During noble rot development in Sauvignon or Sémillon grapes from the Sauternes area, levels of trans-astringin, trans-resveratrol, trans-piceid, and pallidol are quite low (<0.5 mg/kg of grapes). Viniferin and astilbin levels become optimum at 2 and 30 mg/kg, respectively, during spot grape and speckle grape stages.     

Fungal flora and ochratoxin a production in grapes and musts from france

Eleven samples of grapes and musts used in red table wines were investigated for the occurrence of potential ochratoxin A (OTA)-producing molds. From these samples, 59 filamentous fungi and 2 yeasts were isolated. Among the 30 genera isolated, Deuteromycetes were the most frequent (70%) followed by Ascomycetes (10%). Six of the eleven grapes samples were contaminated by potentially ochratoxinogenic strains (Penicillium chrysogenum and Aspergillus carbonarius). When cultivated in vitro on solid complex media, the 14 strains of A. carbonarius produced OTA. No other species produced OTA under the same conditions. Among must samples, eight of eleven were found to be contaminated by OTA (concentrations from <10 to 461 ng/L). There is a strong correlation between the presence of ochratoxin-producing strains on grapes and OTA in musts. These findings should be connected with the OTA contamination of human blood in these areas and in France.     

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.     

Determination of carotenoid profiles in grapes, musts, and fortified wines from Douro varieties of Vitis vinifera.

beta-Carotene and six xanthophylls (lutein, neoxanthin, violaxanthin, luteoxanthin, cryptoxanthin, and echinenone) have been identified and semiquantitatively or quantitatively determined in musts and port wines for the first time. An HPLC method was developed and compared with that of one based on thin layer cromatography with scanning densitometry. The most abundant carotenoids present in red grape varieties are beta-carotene and lutein. In wines, significant quantities of violaxanthin, luteoxanthin, and neoxanthin were found. This study was done with berries (skin and pulp), musts, and fortified wines. Some experiments were performed to follow carotenoid content from grapes to wines. Although the levels of beta-carotene and lutein found in fortified wines were lower than those found in musts, other xanthophylls, such as neoxanthin, violaxanthin, and luteoxanthin, exist in appreciable amounts in young ports.