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Aims: This study investigates the traits of three plant growth-promoting (PGP) and antagonistic bacteria, Pseudomonas protegens MP12, Bacillus sp. 3R4, and Bacillus sp. T22, to assess their potential application as biocontrol agents by using the ecofriendly and low-cost substrate Corn Steep Liquor (CSL) medium. Analyses of antagonism through volatile organic compounds (VOCs) production, biofilm formation, and growth performance were carried out., Methods and Results: Dual antagonism assay showed that all strains displayed significant antagonistic activity against Botrytis cinerea through VOCs. Gas chromatography demonstrated that strains in the CSL exhibited higher VOCs production than nutrient medium. Moreover, enhanced biofilm formation analysed by Calgary Biofilm Device, growth, and biomass were noted in CSL cultures. Pseudomonas protegens MP12, which showed higher cell concentration and biomass yield, was selected for freeze-drying treatments. Storage cell viability assays evidenced that it can be effectively preserved for nearly 7 months at 4°C., Conclusion: The results here obtained showed that CLS medium enhanced VOCs production, biofilm formation, growth, and biomass of the antagonistic bacteria of the three strains. Eventually, the more effective strain P. protegens MP12 can be stored for nearly 7 months at 4°C., (© The Author(s) 2024. Published by Oxford University Press on behalf of Applied Microbiology International.)

The need to reduce the use of pesticides in viticulture is increasing the interest in wines produced using fungal-resistant grapevine varieties, which are characterized by relevant contents of both monoglucoside and diglucoside anthocyanins. Aging in wooden barrels induces oxygen permeation into wine, but little is known about diglucoside anthocyanin evolution. Cabernet cortis wine was subjected to addition of oxygen and oak chips, and the anthocyanin changes were followed for 1 month. Decreases of 90% total monoglucosides, 80% acylated monoglucosides, 65% diglucosides, and 90% acylated diglucosides were observed. Monoglucosides formed pyranoanthocyanins, and the lower steric hindrance favored their polymerization with flavanols. Instead, the decrease in diglucosides was correlated to the number of hydroxyl groups of ring B, indicating the predominant oxidation of aglycones. However, three flavonol-anthocyanin-diglucoside derivatives named (epi)catechin-ethyl-Mv-dihexoside, (epi)catechin-ethyl-Pn-dihexoside, and (epi)catechin-Mv-dihexoside A-type were identified in wine for the first time. These research findings are useful for tuning suitable oenological practices to stabilize the color of these wines (type of barrel, aging times, oxygenation practices) and lower the malvin content, which currently is recommended by the OIV at a maximum of 15 mg/L and is a critical issue for their commercialization.

Liquid chromatography/high-resolution mass spectrometry (LC/HRMS) can provide identification of grape metabolites which are variety markers. White grapes are poorer in polyphenolics, and the main secondary metabolites which contribute the sensorial characteristics of wines are the glycosidically bound volatile precursors and their aglycones. The profiles of three white grape juices (Pinot grigio, Garganega, and Trebbiano) were characterized by LC/HRMS, and 70 signals of putative glycosidic terpenols, norisoprenoids, and benzenoids were identified. Four signals found only in Pinot grigio corresponded to a norisoprenoid hexose-hexose, 3-oxo-α-ionol (or 3-hydroxy-β-damascone) rhamnosyl-hexoside, monoterpene-diol hexosyl-pentosyl-hexoside, and hexose-norisoprenoid; three signals were found only in Garganega (putative isopropyl alcohol pentosyl-hexoside, phenylethanol rhamnosyl-hexoside, and norisoprenoid hexose-hexose isomers), and a monoterpenol pentosyl-hexoside isomer only in Trebbiano. These variety markers were then investigated in juice blends of the three varieties. This approach can be used to develop control methods to reveal not-allowed grape varieties and practices in white wines winemaking.

A breeding program to produce new grape varieties tolerant to main vine fungal pathogens (Plasmopara viticola and Erysiphe necator) is carrying out by crossing Vitis vinifera cv. "Glera" with resistant genotypes such as "Solaris," "Bronner," and "Kunleany." Firstly, resistance gene-based markers analyses allowed the identification of five genotypes, which have inherited the resistance loci against mildews. To select those that also inherited the phenotype as close as possible to 'Glera' suitable to be introduced in the Prosecco wine production protocols, the grape glycosidic derivatives were studied by UHPLC/QTOF mass spectrometry. Targeted identification of the metabolites was performed using a database expressly constructed by including the glycosidic volatile precursors previously identified in grape and wine. A total of 77 glycosidic derivatives including many aroma precursors and some variety markers, were identified. Original resistant genotypes had distinct metabolomic profiles and different to 'Glera', while the crossings showed varying similarity degrees to V. vinifera parent. Findings demonstrated the Glera × Bronner and Glera × Solaris crossings are more suitable to produce high-sustainable Prosecco wines. Coupling of glycosidic volatile precursors profiling to multivariate statistical analysis was effective for phenotypic characterization of grapes and to evaluate their enological potential., (© 2023 John Wiley & Sons Ltd.)

Aging of wines and spirits in wooden barrels is an industrial process used to stabilize the color, to improve the limpidity and to enrich the sensorial characteristics of the products. In red wines, the oxygen that permeates through the wood staves promotes the oxidization of polyphenols and the formation of new pigments with consequent stabilization of the wine color. Barrel aging of spirits, such as brandy, whisky, rum, and grappa is finalized to enrich their aroma and improve their sensorial characteristics by the contribute of the compounds released by the wood. Oak is the wood type mostly used in making barrels; however, an increasing interest in the use of chestnut, cherry, acacia, and in less extent, ash and mulberry, has been observed in the recent years. Gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry are the main techniques used to characterize respectively the volatile and polar metabolites released by the wood barrels in the products. In this article are reported the recent advancements in this field., (© 2021 John Wiley & Sons Ltd.)

Background: Somatic mutations in Vitis spp. are relatively frequent and can generate new agronomically interesting phenotypes. We report the discovery, genetic and chemical characterization of 'Glera rosa', a mutant for the berry skin colour of 'Glera', the main white cultivar used to produce Prosecco wine., Results: We ascertained the relationship between the skin colour of 'Glera rosa' and the polymorphisms in the Myb-gene transcription factors involved in polyphenol biosynthesis. We established that VvMybA1 was homozygous (VvMybA1a/VvMybA1a) in 'Glera' but heterozygous (VvmybA1a/VvmybA1b) in the 'Glera rosa' mutant. We verified that the VvMybA1a non-functional allele contained Grapevine Retrotransposon 1 (Gret1), while in the VvmybA1b allele Gret1 was missing, and the gene function was partially restored. The effects of mutation on 'Glera rosa' grape metabolites were studied by high-resolution mass spectrometry and gas chromatography/mass spectrometry analysis. Fifteen anthocyanins and five unique flavonols were found in the 'Glera rosa' mutant. The mutation also increased the contents of trans-resveratrol and its derivatives (i.e., piceatannol, E-ε-viniferin, cis- and trans-piceid) and of some flavonols in grape. Finally, the mutation did not significantly affect the typical aroma precursors of Glera grape such as glycosidic monoterpenes, norisoprenoids and benzenoids., Conclusion: 'Glera rosa' could be an interesting genetic source for the wine industry to produce Prosecco DOC rosé typology (made by adding up to 15% of 'Pinot Noir'), which was introduced to the market in 2020 with a worldwide massive success. © 2022 Society of Chemical Industry., (© 2022 Society of Chemical Industry.)

Wine fermentation processes are driven by complex microbial systems, which comprise eukaryotic and prokaryotic microorganisms that participate in several biochemical interactions with the must and wine chemicals and modulate the organoleptic properties of wine. Among these, yeasts play a fundamental role, since they carry out the alcoholic fermentation (AF), converting sugars to ethanol and CO 2 together with a wide range of volatile organic compounds. The contribution of Saccharomyces cerevisiae , the reference organism associated with AF, has been extensively studied. However, in the last decade, selected non-Saccharomyces strains received considerable commercial and oenological interest due to their specific pro-technological aptitudes and the positive influence on sensory quality. This review aims to highlight the inter-specific variability within the heterogeneous class of non- Saccharomyces in terms of synthesis and release of volatile organic compounds during controlled AF in wine. In particular, we reported findings on the presence of model non- Saccharomyces organisms, including Torulaspora delbrueckii, Hanseniaspora spp, Lachancea thermotolerans, Metschnikowia pulcherrima, Pichia spp. and Candida zemplinina , in combination with S. cerevisiae . The evidence is discussed from both basic and applicative scientific perspective. In particular, the oenological significance in different kind of wines has been underlined.

Grape dehydration is an oenological process used for production of high-quality reinforced and sweet wines. High-resolution mass spectrometry (ultrahigh-performance liquid chromatography/quadrupole time-of-flight [UHPLC/QTOF]) was used to deepen the characterization of some flavonoids previously proposed in Corvina and Raboso Piave withered grapes. By performing a targeted data analysis workflow and orthogonal identification approaches (tandem mass spectrometry [MS/MS]), in silico fragmentation, and calculation of putative retention time), elucidation on the structures of six compounds previously proposed was achieved (taxifolin-pentoside, two tetrahydroxyflavanone-hexoside derivatives, a tetrahydroxy-dimethoxyflavanone-hexoside derivative, a pentahydroxyflavone, and peonidin-O-pentoside); and the structures of four putative new grape flavonoids were characterized (dihydromyricetin-O-hexoside, taxifolin-di-O-hexoside, isorhamnetin, and a pinoquercetin isomer). Findings enlarge the panorama of flavonoids in grape and of their possible biosynthetic pathways., (© 2020 John Wiley & Sons, Ltd.)

Background: Early leaf removal at pre-bloom is an innovative viticultural practice for regulating yield components and improving grape quality. The effects of this technique on vine performance, grape composition and wine sensory profile of Semillon variety were assessed., Results: Pre-bloom leaf removal enhanced canopy porosity, total soluble solids in musts and reduced cluster compactness. This practice had a strong effect on glycoside aroma precursors, in particular by increasing glycoside terpenols and norisoprenoids. Metabolites of linalool were the most responsive to leaf removal. Wine produced from defoliated vines was preferred in tasting trials for its more intense fruity notes and mouthfeel attributes., Conclusion: Pre-bloom leaf removal is a powerful technique for modifying canopy microclimate, vine yield, grape composition and wine quality. The increase of glycoside aroma compounds in treated grapes has potential positive effect in improving the sensory profile of the resulting wines. © 2017 Society of Chemical Industry., (© 2017 Society of Chemical Industry.)

Grape dehydration is an oenological process used for the production of high-quality reinforced and sweet wines. Corvina and Raboso Piave are two red grape varieties used for production of high-quality Italian wines, such as Recioto, Amarone di Valpolicella and Raboso Passito. Changes of polyphenolic composition of the grapes as a consequence of the withering were studied by ultra-high performance liquid chromatography-quadrupole time of flight mass spectrometry (UHPLC/QTOF); for identification of compounds a homemade HR-MS database of grape and wine metabolites, was used. Concomitant with trans-resveratrol and viniferins, relevant increases of other stilbenes (piceatannol, resveratrol trimers and tetramers) and antioxidant compounds (quercetin, syringetin and tamarixetin) were observed. These compounds are part of the induced metabolism occurring during the withering process and in general improve the nutraceutical properties of grapes and wines. On the other hand, longer processes showed to decrease flavan-3-ols and glycoside flavonols. Constant increase of E/Z ε-viniferin ratio was observed in all samples, and this parameter can be used to monitor the process. Copyright © 2016 John Wiley & Sons, Ltd., (Copyright © 2016 John Wiley & Sons, Ltd.)

Previous studies showed that hybrid grapes often have qualitatively and quantitatively higher polyphenolic contents than the common V. vinifera grape varieties. In general, these compounds are studied for grape chemotaxonomy and for nutraceutical purposes due to their relevant antioxidant activity. Non-anthocyanic flavonoid composition of five red hybrid grape varieties produced by crossing of V. vinifera, V. aestivalis, V. cinerea, V. berlandieri, V. labrusca, V. lincecumii, and V. rupestris were studied by liquid chromatography/high-resolution mass spectrometry. Thirty-one compounds were identified, including methylnaringenin, a tetrahydroxy-dimethoxyflavanone-hexoside, two flavonols (quercetin and a pentahydroxyflavone isomer), 20 glycoside flavonols (four quercetin, two myricetin, two kaempferol, three isorhamnetin, one laricitrin, two syringetin, one kaempferide and two dihydroflavonol derivatives; myricetin-glucoside-glucuronide; myricetin-diglucoside; syringetin-dihexoside), three flavan-3-ols (-)-epicatechin, (+)-catechin, (-)-epicatechin gallate) and four proantocyanidins (procyanidin B1, procyanidin B2, procyanidin B3 or B4/B5, procyanidin T2 or T3/T4/C1). Seibel 19881, Seyve Villard 12-347 and Seyve Villard 29-399 were particularly rich in polyphenols. These findings emphasize that these grapes are especially interesting for the production of antioxidant extracts for nutraceutical and pharmaceutical uses.

The wine aroma loss as a consequence of treatments with bentonite is due to the occurrence of multiple interaction mechanisms. In addition to a direct effect of bentonite, the removal of aroma compounds bound to protein components adsorbed by the clay has been hypothesized but never demonstrated. We studied the effect of bentonite addition on total wine aroma compounds (extracted from Moscato wine) in a model solution in the absence and presence of total and purified (thaumatin-like proteins and chitinase) wine proteins. The results showed that in general bentonite alone has a low effect on the loss of terpenes but removed ethyl esters and fatty acids. The presence of wine proteins in the solution treated with bentonite tended to increase the loss of esters with the longest carbon chains (from ethyl octanoate to ethyl decanoate), and this was significant when the purified proteins were used. The results here reported suggest that hydrophobicity can be one of the driving forces involved in the interaction of aromas with both bentonite and proteins.

Rationale: Grape polyphenols are antioxidant compounds, markers in vine chemotaxonomy, and involved in color stabilization of red wines. Sugar acylation usually confers higher stability on glycoside derivatives and this effect is enhanced by an aromatic substituent such as p-coumaric acid. Until now, only p-coumaroyl anthocyanins have been found in grape., Methods: A method of 'suspect screening analysis' by ultra-high-performance liquid chromatography/high-resolution mass spectrometry (UHPLC/QTOFMS) has recently been developed to study grape metabolomics. In the present study, this approach was used to identify new polyphenols in grape by accurate mass measurement, MS/MS fragmentation, and study of correlations between fragments observed and putative structures., Results: Three putative p-coumaroyl flavonoids were identified in Raboso Piave grape extract: a dihydrokaempferide-3-O-p-coumaroylhexoside-like flavanone, isorhamnetin-3-O-p-coumaroylglucoside, and a chrysoeriol-p-coumaroylhexoside-like flavone. Accurate MS provided structural characterization of functional groups, and literature data indicates their probable position in the molecule. A fragmentation scheme is proposed for each compound., Conclusions: Compounds were identified by overlapping various analytical methods according to recommendations in the MS-based metabolomics literature. Stereochemistry and the definitive position of substituents in the molecule can only be confirmed by isolation and characterization or synthesis of each compound. These findings suggest addressing research of acylated polyphenol glycosides to other grape varieties., (Copyright © 2015 John Wiley & Sons, Ltd.)

Volatile compounds are responsible for the wine "bouquet", which is perceived by sniffing the headspace of a glass, and of the aroma component (palate-aroma) of the overall flavor, which is perceived on drinking. Grape aroma compounds are transferred to the wine and undergo minimal alteration during fermentation (e.g., monoterpenes and methoxypyrazines); others are precursors of aroma compounds which form in winemaking and during wine aging (e.g., glycosidically-bound volatile compounds and C13-norisoprenoids). Headspace solid phase microextraction (HS-SPME) is a fast and simple technique which was developed for analysis of volatile compounds. This review describes some SPME methods coupled with gas chromatography/mass spectrometry (GC/MS) used to study the grape and wine volatiles.

A 'suspect screening analysis' method for grape metabolomics by ultra-high performance-liquid chromatography (UHPLC) and high-resolution quadrupole-time of flight (QTOF) mass spectrometry was recently developed. This method was applied to study grape monoterpene glycosides, the main grape aroma precursors. Since standard compounds were not available, they were tentatively identified by overlapping various analytical approaches, in agreement with the indications recommended in mass spectrometry (MS)-based metabolomics. Accurate mass and isotopic pattern, MS/MS fragmentation, correlation between fragments observed and putative structures and between liquid chromatography coupled with mass spectrometry (LC/MS) and gas chromatography/mass spectrometry signals were studied. Seventeen monoterpene glycosides were identified without performing the hydrolytic artifacts commonly used to study these compounds which may affect sample profile. This is the first time that a detailed study of these aroma precursors has been carried out by direct LC/MS analysis., (Copyright © 2014 John Wiley & Sons, Ltd.)

Carotenoid-derived aroma compounds play an important role in the composition of aroma and grapes, and consequently of wine. The volatile composition of forty-five grape varieties harvested in 2011 and 2012 was investigated by solid phase extraction of samples and gas chromatography-mass spectrometry (GC-MS) analysis. In grape extracts of cultivars Barbera, Refosco dal Peducolo Rosso, Ribolla gialla and Rossese, the C9-norisoprenoid compound β-isophorone (3,5,5-trimethyl-3-cyclohexen-1-one) was found and quantified. This carotenoid-derived compound is characterised by a saffron aroma and is here reported in grape for the first time., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Triglyceride profile of seed oil samples from 32 hybrid grape varieties not studied before was investigated. A new method for the analysis of triacylglycerols (TAGs) has been developed based on the direct infusion in the electrospray ionization (ESI) source and employing tetrahydrofuran/methanol/water (85:10:5 v|v|v) as solvent; the formation of [M + Na](+) ions in high yield has been observed. TAGs were identified by ESI-tandem mass spectrometry analysis, and the matrix-assisted-laser-desorption-ionization and time-of-flight profile of samples was determined. Six were the principal TAGs identified in seed oil: trilinolein (LLL) was the most abundant (43%), followed by dilinoleoyl-oleoylglycerol (LOL, 23%), and dilinoleoyl-palmitoylglycerol (LPL, 15%). Compounds present in lower concentration were LSL and LOO (11%), LOP (6%), and LSP (2%). Compared with seed oils produced from V. Vinifera grapes, some significant differences in the relative abundances of TAGs were found, in particular hybrid grape seed oils showed higher LOL and lower LPL content, respectively. Among the samples studied, a particularly high content of LLL (rich in unsaturated fatty acids) was found in seed oils from two red varieties., (Copyright © 2012 John Wiley & Sons, Ltd.)

Rationale: Anthocyanins confer the color to red wines. During wine aging, new anthocyanin derivatives with peculiar chromatic characteristics are formed. A fast and selective method for screening the anthocyanin composition of wine has been developed., Methods: Direct-infusion electrospray ionization tandem mass spectrometry (ESI-MS/MS) analysis of wine extracts has been performed by operating in positive ion mode with a low spray capillary voltage (0.5 kV) to detect only the species already present in ionic form. The method has been called direct-infusion pneumatic spray (DIPS) mass spectrometry. The anthocyanin profiles of thirteen red wines at different aging stages were studied. Using malvidin-3,5-diglucoside as internal standard, the indices of wine color and of wine color evolution were estimated., Results: By decreasing the spray capillary voltage a dramatic increase in selectivity toward anthocyanins has been observed and the related peaks are the most abundant in the spectra. Several anthocyanins and anthocyanin derivatives (pyranoanthocyanins and derivatives formed by reaction with flavan-3-ols) have been identified in the wines. The younger wines showed higher total anthocyanin index. The aged wines showed color evolution index higher than 20% while it was lower in the younger samples., Conclusions: The anthocyanin fingerprint is effective for estimating the aging state of wine. The color evolution index can be correlated to barrel conditions during wine aging and used to distinguish between aged and younger wines. The study of pyranoanthocyanins and anthocyanin-flavanol derivatives can be useful to predict wine color stability., (Copyright © 2012 John Wiley & Sons, Ltd.)

DNA studies supported by matrix-assisted laser desorption ionization-time of flight mass spectrometry analysis of seed proteins showed that the Vitis vinifera red grape variety Raboso Veronese is the progeny of a spontaneous cross between Raboso Piave (red) and Marzemina Bianca (white) varieties. In the present work, the main secondary grape metabolites of Raboso varieties were studied, and their enological potential was evaluated and compared with that of other red varieties reported in the literature. In general, Raboso grapes had high flavonoid contents and high percentages of polyphenols extractable in winemaking and substantial contents of norisoprenoid aroma precursors. Raboso Veronese stood out for its high content of cyanidin and had higher (+)-catechin and (-)-epicatechin contents than Raboso Piave and abundant quercetin glucoside, indicating substantial plant biosynthesis toward compounds dihydroxylated in the B-ring. Study of secondary grape metabolites is confirmed as an effective tool in differentiating similar varieties, in particular on the basis of polyphenol profiles.

2'-Aminoacetophenone (o-AAP) was identified as the main cause of the aging note called 'hybrid note' or 'foxy smell' which is typical of non-Vitis vinifera grapes. Together with methyl anthranilate (MA), this compound contributes to the typical foxy taint of wines made with non-Vitis vinifera grapes. 3-Alkyl-2-methoxypyrazines in grapes, with their herbaceous note and very low sensory thresholds, contribute to the aroma of several wines. In this study, a solid-phase microextraction gas chromatography/ion trap tandem mass spectrometry (SPME-GC/IT-MS/MS) method for simultaneous detection of o-AAP, MA and ethyl-, isopropyl-, sec-butyl- and isobutylmethoxypyrazine in grape juice was developed. The method was applied to the study of several grape juices: the time required for analysis was less than 24 min, and the method was considered to be suitable for analysis of 'foxy compounds' and methoxypyrazines in grape juice. The high levels of MA and o-AAP found in Clinton and Siebel grapes confirmed the 'hybrid' character of these varieties., (Copyright 2010 John Wiley & Sons, Ltd.)

In a previous work, direct-infusion electrospray ionization ion trap tandem mass spectrometry (ESI-IT-MS/MS) was applied to the study of anthocyanins in extracts from the skins of Clinton grapes, a non-Vitis vinifera red grape variety qualitatively and quantitatively rich in anthocyanins. A good characterization of anthocyaninins was obtained, but it was impossible to differentiate some compounds with the same nominal mass but with different elemental composition. In this work, the capabilities of quadrupole time-of-flight mass spectrometry (QTOF-MS) coupled with Chip-liquid chromatography (LC-Chip) were applied to the study of Clinton anthocyanins and this method provided the complete sample anthocyanin fingerprint in less than 5 min. Multi-stage mass spectrometry (MS(n); n >2) was not necessary to identify isobaric compounds, nor were deuterium-exchange experiments necessary to distinguish between compounds containing the same aglycone. The fast separation bypasses the problem of petunidin-3-O-(6-O-acetyl)monoglucoside and delphinidin-3,5-O-diglucoside quantification, present in the direct-infusion ESI-ITMS approach, due to overlapping with matrix interferences.

Aging in wooden barrels is a process used to stabilize the color and enrich the sensorial characteristics of wine. Many compounds are released from wood into the wine; oxygen permeation through the wood favors formation of new anthocyanin and tannin derivatives. Recently, polyphenols and volatile compounds released from acacia, chestnut, cherry, mulberry, and oak wood used in making barrels for spirits and wine aging were studied. Here, changes in volatile and polyphenolic compositions of a red wine aged for 9 months in acacia, cherry, chestnut, mulberry, and oak barrels are studied. Mulberry showed significant decreases of fruity-note ethyl esters and ethylguaiacol and a great cession of ethylphenol (horsey-odor defect). Cherry promoted the highest polyphenol oxidation, making it less suitable for long aging. LC/ESI-MS(n) showed the relevant presence of cis- and trans-piceatannol in mulberry-aged wine, a phytoalexin with antileukemia and antimelanoma activities.

Resveratrol (3,5,4'-trihydroxystilbene) and piceatannol (3,4,3',5'-tetrahydroxy-trans-stilbene) are phytoalexins present in red grapes and wines. In vitro studies have revealed that piceatannol blocks LMP2A, a viral protein-tyrosine kinase implicated in leukemia, non-Hodgkin's lymphoma and other diseases associated with the Epstein-Barr virus, and has an antimelanoma effect on human melanoma cells. Resveratrol has several beneficial effects on human health, such as anticancer, cardioprotection, antioxidant, inhibition of platelet aggregation and anti-inflammatory activity. In this investigation, the collisional behaviour of deprotonated resveratrol and piceatannol obtained under electrospray conditions is described. The mechanisms involved in the fragmentation pattern of [M-H](-) species of the two compounds were investigated by performing MS(n) experiments, deuterium labelling and accurate mass measurements.

Extracts from acacia, chestnut, cherry, mulberry, and oak wood, used in making barrels for aging wine and spirits were studied by GC/MS positive ion chemical ionization (PICI). Wood chips were extracted by a 50% water/ethanol solution and a tartrate buffer pH 3.2-12% ethanol (model wine) solution. The principal compounds identified in extracts were guaiacol-containing aldehydes and alcohols, such as benzaldehyde and derivatives, vanillin and syringaldehyde, cinnamaldehyde and coniferaldehyde, eugenol and methoxyeugenol, guaiacol and methoxyguaiacol derivatives. PICI using methane as reagent gas produced a high yield of the protonated molecular ion of volatile phenols, compound identification was confirmed by collision-induced-dissociation (CID) experiments on [M + H](+) species. MS/MS fragmentation patterns were studied with standard compounds: guaiacol-containing molecules were characterized by neutral methyl and methanol losses, benzaldehyde derivatives by CO loss. Acacia wood extracts contained significant syringaldehyde and anisaldehyde, but no eugenol and methoxyeugenol. Significant syringaldehyde, eugenol and methoxyeugenol, and high vanillin were found in chestnut and oak wood extracts; low presence of volatile benzene compounds was found in mulberry wood extracts. Cherry wood extracts were characterized by the presence of several benzaldehyde derivatives and high trimethoxyphenol.

A new sensitive and selective analytical method for the analysis of ochratoxin A (OTA) in grape and wine was developed by coupling liquid chromatography and surface activated chemical ionization and mass spectrometry with multistage fragmentation (LC/SACI-MS(3)). A high flow gradient was used to strongly reduce the matrix effect phenomenon, and the wine sample was directly injected onto the chromatographic column without sample pre-concentration or purification steps. The amount of OTA was determined for two grape extracts and the amount of OTA, percent accuracy error and percent precision error were analyzed for 15 wine samples. An excellent limit of detection of 0.02 ng/mL was achieved, and the limit of quantification was at least 20-fold lower than the maximum legal limit for OTA (2 ppb). Due to the low limit of quantification, this novel method is a potential tool for official OTA screening purposes., (Copyright 2007 John Wiley & Sons, Ltd.)

Controls in food industry are fundamental to protect the consumer health. For products of high quality, warranty of origin and identity is required and analytical control is very important to prevent frauds. In this article, the "state of art" of mass spectrometry in enological chemistry as a consumer safety contribute is reported. Gas chromatography-mass spectrometry (GC/MS) and liquid-chromatography-mass spectrometry (LC/MS) methods have been developed to determine pesticides, ethyl carbamate, and compounds from the yeast and bacterial metabolism in wine. The presence of pesticides in wine is mainly linked to the use of dicarboxyimide fungicides on vineyard shortly before the harvest to prevent the Botrytis cinerea attack of grape. Pesticide residues are regulated at maximum residue limits in grape of low ppm levels, but significantly lower levels in wine have to be detected, and mass spectrometry offers effective and sensitive methods. Moreover, mass spectrometry represent an advantageous alternative to the radioactive-source-containing electron capture detector commonly used in GC analysis of pesticides. Analysis of ochratoxin A (OTA) in wine by LC/MS and multiple mass spectrometry (MS/MS) permits to confirm the toxin presence without the use of expensive immunoaffinity columns, or time and solvent consuming sample derivatization procedures. Inductively coupled plasma-mass spectrometry (ICP/MS) is used to control heavy metals contamination in wine, and to verify the wine origin and authenticity. Isotopic ratio-mass spectrometry (IRMS) is applied to reveal wine watering and sugar additions, and to determine the product origin and traceability.

A new method has been developed to determine acetaldehyde, 2,3-butanedione (diacetyl) and 3-hydroxy-2-butanone (acetoin) in wine by solid-phase microextraction (SPME) and positive ion chemical ionization GC/MS analysis of O-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine (PFBOA) derivatives. For SPME, a 65-microm PEG/DVB fibre was used; chemical ionization was performed with methane as reagent gas. The best analysis-time/sensitivity compromise was to perform the PFBOA reaction at 50 degrees C for 20 min, followed by 5-min SPME at the same temperature. Quantitative analysis was performed in SCAN mode using o-chlorobenzaldehyde as internal standard (IS), on the signal of the [M + H](+) ion at m/z 240 for acetaldehyde, 266 for acetoin (corresponding to the [M + H - 18](+) ion), 282 for diacetyl (protonated mono-derivatized compound), and 336 for IS. The accuracy and repeatability of the method were suitable for the study aims, and linearity was good in the range of concentration studied, with correlation coefficients of calibration curves 0.997, 0.998 and 0.988 for acetaldehyde, diacetyl and acetoin respectively. Due to the higher polarity of acetoin with respect to other two compounds, lower sensitivity in the detection of this compound was observed. By following the variation of the three carbonyl compounds, malolactic fermentations (MLF) were monitored in Merlot wines and this was carried out in the laboratory by two different bacteria strains.