This paper presents the results from an investigation to assess the development of a Riesling and a wooded Chardonnay wine over five years. The wines were bottled either with or without added ascorbic acid and stored under controlled temperature and humidity conditions. Ascorbic acid addition to wine at bottling had little effect on wine aroma and flavour when the wines in this study had been in bottle for 6 months or less. For both wines, at bottle storage times of 3 years or more, addition of ascorbic acid at bottling resulted in wines with no difference in aroma or less oxidised and/or more fresh fruity aromas, even if all the ascorbic acid had been depleted at the time of assessment, compared to wines without addition of ascorbic acid at bottling. in terms of colour, for the Chardonnay wines, the effect of ascorbic acid addition at bottling assessed between two weeks and two years after bottling suggested that wines without addition were browner and had more overall colour intensity. For the Riesling wines, ascorbic acid addition had no significant effect on brownness and overall colour intensity although the Riesling wines with ascorbic acid were generally higher in yellow colour. The A(420). measurements, which are widely used to estimate the brown colour of wines, did not always appear to correlate with the brown scores obtained by visual assessment or colour measures by CIELAB when wines with and without ascorbic acid addition were compared together. For both wines, after three and five years storage, the concentration of the antioxidant sulfur dioxide was either little different or else slightly (statistically significantly) higher in wines to which ascorbic acid was added at bottling than those without addition.

The concentrations of the important oak aroma volatiles guaiacol, 4-methylguaiacol cis- and trans-oak lactone and vanillin in extracts of French and American oak heated under various conditions were measured using stable isotope dilution analyses coupled with gas chromatography-mass spectrometry. Heating resulted in marked increases in the concentrations of guaiacol, 4-methylguaiacol and vanillin, with more formed at higher temperature. Approximately twice as much guaiacol and 4-methylguaiacol and two to five times as much vanillin were formed by heating in the presence of air compared to heating under argon. Oak lactone concentration was less affected by heating. The effects of heating different sized oak pieces were investigated for French and American oak samples. Compared to heating larger oak pieces, heating smaller fragments of oak generated up to twice as much guaiacol and 4-methylguaiacol and two to four times as much vanillin at 235oC for both French and American oak. This effect is ascribed to the exposure of a greater surface area of oak to air when smaller fragments are heated. Variable effects were observed for cis- and trans-oak lactone. Variation in chip size, as well as heating time and temperature, is clearly one way of obtaining different aroma profiles from oak products.

Three C-13-norisoprenoid compounds, 3,6,9-trihydroxymegastigma-4,7-diene (6), 3,4,9-trihydroxymegastigma-5,7-diene (4), and the actiniclols (8), have all been synthesized and subjected to acid hydrolysis. All three were shown to generate (E)-1-(2,3,6-trimethylphenyl)buta-1,3-diene (1) under wine conservation conditions. At 45 degrees C, approximately 4000-5000 ng/L of 1 was formed from 1.0 mg/L of precursor, after 173 days, while at 25 degrees C more wine-like amounts (200-600 ng/L) were observed. A glucoside, 4,5-dihydrovomifoliol-C-9-beta-D-glucopyranoside (9b), was isolated from grapevine leaves by multilayer coil countercurrent chromatography (MLCCC), and its stereochemistry was deduced as being (5R, 6S, 9R) by NMR and CD spectroscopy. Hydrolysis of this glucoside produced 1, but in quantities insufficient to account for the levels observed in wine.

A series of four isomeric 3,9-dihydroxymegastigma-4,6,7-trienes, 8, has been prepared. The (3S,6R,9S) isomer of 8 proved to be identical to an isomer of this compound tentatively identified as an intermediate in the formation of damascenone from an allene triol. Each of the four isomers, when hydrolyzed independently of each other at pH 3.0 and 25 degrees C, produced product mixtures in which the major product was damascenone (1). Contrary to expectation, 3-hydroxydamascone (5) was not observed in any of the hydrolyses. Consequently, the mechanism of formation of damascenone proposed earlier requires modification. In each hydrolysis, the product mixtures showed the presence of a second isomer of 8, produced by epimerization during hydrolysis. Chiral analysis on a Cyclosil B column revealed that this epimerization was occurring at C(3) in each of the hydrolyses.

This paper presents the results from an investigation to assess the development of a Riesling and a wooded Chardonnay wine over five years following the imposition of several treatments at bottling. The wines were bottled under a screw cap closure, two different natural corks, a synthetic closure and in a glass ampoule. In addition, the effect of storage orientation was investigated. The bottled wines were stored under controlled temperature and humidity conditions. Various analyses were carried out on replicate bottles from each treatment, including sulfur dioxide and ascorbic acid concentration, sensory analysis of appearance and aroma attributes, and spectral measures. The largest treatment effect resided with the nature of the closure. Wines sealed with the synthetic closure were relatively oxidised in aroma, brown in colour, and low in sulfur dioxide compared to wines held under the other closures. A struck flint/rubber (reduced) aroma was discernible in the wines sealed under the screw caps or in glass ampoules. Wines sealed under natural bark corks in this study showed negligible reduced characters. The bottle orientation during storage under the conditions of this study had little effect on the composition and sensory properties of the wines examined.

The compounds causing cork taint and the factors affecting their transmission from cork to wine are discussed. These factors include: the solubilities of the taint compounds in wine, their affinity for the surface and the interior parts of the cork; their location on the surface of and within the closure; the rates at which they can migrate through the cork matrix; the volume of wine in contact with a closure(s); and whether taint transmission is taking place in bottled wine or with corks soaked in wine for screening purposes. 2,4,6-Trichloroanisole (TCA) has been the primary topic of investigations reported in the general literature and is therefore the main focus of this article.

A stable isotope dilution assay has been developed for quantification of (E)-1-(2,3,6-trimethylphenyl)buta-1,3-diene (4) in wine using a [(2)H(6)]-analogue. Using this method, 4 was found in 96 out of 97 white wines, but in none of 12 red wines analyzed. 4 was found to be most prevalent in Semillon wines, followed by Chardonnay, with Riesling showing the least amount of 4 among these three varieties. 4, like 1,1,6-trimethyldihydronaphthalene (TDN, 3), appears to be formed during the aging process. 4 was found to be unstable in model wine, and in both white and red wine, with the order of stability being model > white > red. In a PVPP-stripped red wine, the rate of degradation of 4 was substantially lessened, with the final concentrations very close to those observed in model wine. When treated with either grape or wine tannin extracts in model wine, the concentration of 4 was found to decrease to levels very close to those observed with an untreated red wine. When white wine was heated at 45 degrees C, 4 was formed, indicating the presence of precursor forms. The amounts formed were much higher than those found in a commercial white wine. 4 was also observed in red wine heated to 45 degrees C, but the concentration produced was much less than that with white wine.

The rates of formation of both cis- and trans-oak lactone from the corresponding isomers of 3-methyl-4-hydroxyoctanoic acid have been measured in model wine at room temperature for a range of pH values. The half-life for formation of the trans-isomer at pH 2.9 was calculated to be 3.1 h, whereas that for the cis-isomer, at the same pH, was calculated to be 40.5 h. The k(trans)/k(cis) ratio in model wine was found to 12.86 +/- 1.34 over the range of pH values employed. A reason for the more facile formation of the trans-isomer, based on conformational reasons, has been proposed. In acidic aqueous media the equilibrium between the oak lactones and their corresponding ring-opened analogues was found to favor the former entirely, with no evidence for the latter being found. Implications of the present study for the future analysis of oak samples, as well as for the interpretation of existing data, are discussed.

The effect of geographical origin and place of seasoning and coopering of oakwood on the concentration of 20 compounds extracted into, or formed in, Chardonnay, Cabernet Sauvignon and model wines during barrel maturation is described. The oak from which the barrels were fabricated was sourced from the Vosges and Limousin regions and the Tronçais forest in France, and from Ohio in the USA, and was seasoned in either Australia, France or the USA. Wines matured in Vosges oak barrels contained the highest concentrations of cis and trans-oak lactone and eugenol. The Limousin oak barrels imparted lower levels of cis-oak lactone and eugenol to the wines than did the other French oaks. However, the Limousin-oaked wines were richer in these compounds than the American-oaked wines. These results reflected the previously reported composition profiles of the oak-wood from which the barrels were fabricated. Oak seasoned and coopered in Australia generally imparted more cis-oak lactone, eugenol and the coopering products vanillin and furfural into the wines than did the oak seasoned in France or the USA. Although medium toast had been specified for all barrels, there was considerable variability in the concentration of compounds formed by coopering in the wines. Apparent random microbiological activity in the wines also contributed substantially to variation in wine composition. As a likely result of coopering and microbiological variability, few consistent origin or seasoning effects on the compounds resulting from coopering or microbiological action during oak maturation were observed.

The compound responsible for a "fungal must" taint evident in industry assessments of wine corks was identified as 2-methoxy-3,5-dimethylpyrazine. The identification was made on the basis of gas chromatography/odor analyses, collection of material using micropreparative techniques, determination of chemical properties of collected material, and comparison by gas chromatography/mass spectrometry with an authentic sample, synthesized from 2-hydroxy-3,5-dimethylpyrazine. 2-Methoxy-3,5-dimethylpyrazine is an extremely potent compound with an unpleasant, musty, moldy aroma and an aroma threshold in a white wine of 2.1 ng/L. While its contribution to the frequency and intensity of cork taint in bottled wine is yet to be established, it has been assessed by some wine industry personnel as second only to 2,4,6-trichloroanisole as a cause of cork taint in Australian wine.

Correlations were explored between the composition and aroma properties of a Chardonnay and Cabernet Sauvignon wine, each matured in 24 new oak barrels over 55 and 93 weeks respectively. The concentration of volatile components derived during oak maturation had previously been measured for these wines using gas-chromatography/mass spectrometry and the aromas of the wines were profiled using descriptive analysis techniques, with intensities being ranked rather than rated. A number of significant and logical correlations were observed and conditions under which a number of commonly perceived oak-wood characters are perceived are suggested.

The β-d-glucopyranosides of all four stereoisomers of 3-methyl-4-hydroxyoctanoic acid have been prepared. The (3S,4S) and (3R,4R) species were prepared from cis-5-n-butyl-4-methyl-4,5-dihydro-2(3H)-furanone (cis-oak lactone) by a process involving ring-opening with base and protection of the carboxyl function as its benzyl ester. The glucose unit was introduced by a modified Koenigs–Knorr procedure. A different strategy was necessary for synthesis of the (3S,4R) and (3R,4S) compounds. This was based on the reductive ring-opening of trans-oak lactone and subsequent protection of the primary alcohol as its t-butyldiphenylsilyl ether. Separation of the individual glucosides was effected by preparative thin layer chromatography. Those corresponding to the nature-identical isomers of oak lactone have been shown to produce oak lactone under both acidic hydrolysis and pyrolysis conditions. The galloyl-β-d-glucoside of the cis-species, obtained as a natural isolate from the wood of Platycarya strobilacea, was also found to produce cis-oak lactone upon both acid hydrolysis and pyrolysis. Both the nature-identical (4S,5S) cis-oak lactone and its non-natural (4R,5R) enantiomer have been prepared from their corresponding glycosides and their aroma thresholds in white wine were determined to be 23 and 82 μg/L (ppb) respectively. The aroma threshold of the nature-identical isomer in a red wine was 46 μg/L.

Damascenone has been shown to undergo reaction with common wine components. Following the action of acid and heat alone, two bicyclic compounds, 4,9,9-trimethyl-8-methylenebicyclo[3.3.1]non-6-en-2-one (2) and 4,4,9-trimethyl-8-methylenebicyclo[3.3.1] non-6-en-2-one (3), were isolated. However, this conversion takes place only very slowly, if at all, under milder conditions (45 degrees C). When treated with a variety of nucleophiles at pH 3.0 and 5.5, the concentration of damascenone in buffered aqueous ethanol decreased by minor amounts (10-20%) except for cysteine and 2-mercaptoethanol addition at pH 5.5 (approximately 40 and approximately 30%, respectively) and SO2 (>90% at pH 3.0; 100% at pH 5.5). An adduct from this last combination was prepared and shown to be the C9 sulfonic acid derivative of damascenone. A detailed investigation into the effect of SO2 demonstrated that loss of damascenone in model wine was directly related to the concentration of added SO2 but was essentially unaffected by small changes in pH.

In situ absorbance of visible light by white wine in bottles was determined with a modified spectrophotometer. A linear correlation was obtained between absorbance at 420 nm (A420) measured in a cuvette (10 mm pathlength) and absorbance of that same wine measured in a 750 mL Flint bottle (colourless transparent glass). In addition, 5 types of coloured bottles, Emerald Green, Classic Green, French Green, Georgia Green and Cobalt Blue, also yielded strong correlations. A420 of white wine in bottles of Antique Green or Amber glass could not be measured directly due to a strong absorbance of that wavelength by the glass. However, a strong correlation was established between measurement of A420 (cuvette) and A540 for white wine in Antique Green bottles and between A420 (cuvette) and either A540 or A600 for white wine in Amber bottles. The method employed a standard UV-Visible spectrophotometer with an inexpensive modified sample port, and proved applicable to bottles with diameters ranging from 62 mm (375 mL capacity half bottles) up to 81 mm (750 mL capacity Burgundy bottles). In situ absorbance measurements plus subsequent chemical analysis and sensory assessment of a Chardonnay wine in Antique Green bottles showed that the method provided an estimate of oxidation in this white wine. Wine absorbance spectra over the full visible range were obtained in the Flint bottle. Measurements of the absorbance of visible light by the glass of empty bottles could also be obtained and used as a form of quality control for glass bottle manufacture.

(E)-1-(2,3,6-Trimethylphenyl)buta-1,3-diene (TPB) was identified as a potent odorant in acid hydrolysates of crude glycoconjugate fractions isolated from grapes and grape vine leaves. TPB was also identified in a Semillon wine, using gas chromatography/mass spectrometry, by co-injection with an authentic sample. TPB had an aroma detection threshold of 40 ng/L in a neutral white wine and the concentration of TPB in four out of five white wines analyzed ranged from 50 to 210 ng/L.

A reverse phase HPLC method has been developed for the quantitative analysis of pigmented polyphenolic polymers in red vines. Pigmented polymers were well separated from anthocyanins and other simple wine pigments and eluted last as a single peak, The polymeric and polyphenolic nature of this peak was confirmed by its precipitation with gelatine and its behaviour during Ultrafiltration and chromatography on Sephadex LH20. This method correlates well with spectrophotometric measures of total pigmented polymers and indices of wine age. The proportion of the pigmented material incorporated into polymers increased with increasing wine age.

Deuterium-labelled trichloroanisole (d(5)-TCA) added to the surface of wine corks in bottles did not contaminate wine after more than three years of bottle storage. Most of the added d(5)-TCA was lost, presumably by evaporation. That remaining was largely confined to the outer portion of the Closures, Under the conditions of this study, the cork closures were highly effective barriers to the transmission of exogenous TCA.

9-Hydroxymegastigma-3,5-dien-7-yne 8a was synthesised and shown to be identical to an intermediate found in the acid-catalysed conversion of 3,5,9-trihydroxymegastigma-6,7-diene 4 to β-damascenone 1, 3-hydroxydamascone 5 and megastigma-5-en-7-yne-3,9-diol 6. When subjected to acid hydrolysis, 8a produced β-damascenone 1, in high yield. Importantly, the hydrolysate was completely free of 3-hydroxydamascone 5.

Natural bark corks which were exposed to an atmosphere saturated with deuterium-labelled 2,4,6-trichloroanisole (d5-TCA) absorbed the d5-TCA rapidly. A commercially applied surface treatment did not prevent the ingress of the d5-TCA into the corks. d5-TCA was lost from contaminated corks by aeration relatively slowly. Nevertheless, the observation that TCA can be desorbed in this manner suggests that aeration, albeit under modified conditions, may yet prove useful in improving the quality of wine corks. Most of the absorbed d5-TCA was localised in the outer 2 mm of the cork cylinder, but a significant amount migrated to the interior of the cork cylinder after as little as twenty-four hours of exposure. Significantly more d5-TCA was found in the older growth compared to the younger growth bark after this time.

The hydrolysis, in model wine at pH 3, of the allylic, homoallylic, and propargylic glycosides, geranyl-beta-D-glucopyranoside, [3'-(1' '-cyclohexenyl)-1'-methyl-2'-propynyl]-beta-D-glucopyranoside, (3'RS, 9'SR)-(3'-hydroxy-5'-megastigmen-7-yn-9-yl)-beta-D-glucopyra noside, (3',5',5'-trimethyl-3'-cyclohexenyl)-beta-D-glucopyranoside, E-(7'-oxo-5',8'-megastigmadien-3'-yl)-beta-D-glucopyranoside (3-hydroxy-beta-damascone-beta-D-glucopyranoside), and their corresponding aglycons has been studied. In general, aglycons were more rapidly converted to transformation products than were the corresponding glucosides. Glycoconjugation of geraniol in grapes is a process that reduces the flavor impact of this compound in wine, not only because geraniol is an important flavor component of some wines but also because the rate of formation of other flavor compounds from geraniol during bottle-aging is reduced. However, when flavor compounds such as beta-damascenone are formed in competition with flavorless byproducts, such as 3-hydroxy-beta-damascone, by acid-catalyzed hydrolytic reactions of polyols, then glycoconjugation is a process that could enhance as well as suppress the formation of flavor, depending on the position of glycosylation. (3'RS, 9'SR)-(3'-Hydroxy-5'-megastigmen-7'-yn-9'-yl)-beta-D-glucopy ranoside hydrolyzed more slowly but gave a higher proportion of beta-damascenone in the products than did the aglycon at 50 degrees C. Reaction temperature also effected the relative proportion of the hydrolysis products. Accelerated studies do not parallel natural processes precisely but only approximate them.