Volatile compounds of traditional sorghum beer (tchapalo) produced in Côte d'Ivoire: comparison between wild yeasts and pure culture of Saccharomyces cerevisiae.

In recent years, there had been growing demand for distinctive high quality beer. Fermentation management has a fundamental role in beer quality and the levels of aroma compounds. Use of non-conventional yeast has been proposed to enhance beer flavor. In this study, the bioflavor of traditional sorghum beer from Côte d'Ivoire was investigated. The flavor profile of two beers fermented with wild yeasts and with pure culture of Saccharomyces cerevisiae respectively were studied. The main flavor components of the beer fermented by pure culture of Saccharomyces cerevisiae were different from those of the beer fermented with wild yeasts. The total level of esters and higher alcohols were (173.51 and 128.85 mg/L) respectively in the beer fermented with wild yeasts. These levels were significantly higher than those in the beer fermented with pure culture of Saccharomyces cerevisiae which were 13.08 and 78.26 mg/L for higher alcohols and esters respectively. On the other hand, the beer fermented with pure culture of Saccharomyces cerevisiae had an acid content higher than beer fermented with wild yeasts, i.e. 9.3 mg/L and 7.53 mg/L respectively.

Detection and Identification of Oxidation Markers of the Reaction of Grape Tannins with Volatile Thiols Commonly Found in Wine.

Condensed tannins undergo many modifications during winemaking and the aging of wine. These reactions take place between the various constituent units of the tannins as well with other types of molecules present in wines. This work aimed to highlight the potential reactions of tannins and aromas. After the monomeric standards of the reaction products were synthesized, the study of the reactivity of tannins (dimer B2, trimer C1, and grape seed tannins composed of 23% epicatechin-3-O-gallate) with aromas (3-sufanylhexan-1-ol, 4-methyl-4-sulfanylpentan-2-one, ethanethiol, and furfurylthiol) permitted identification of numerous reaction products. These tannin/aroma oxidation markers, detected after chemical depolymerization, allow for progress in the characterization of tannins in the oenological environment and the understanding of their reactivity toward the molecules present in the samples. A better characterization of tannins will make it possible to better measure the impact of these modifications on the organoleptic qualities of wines.

The reduction of plant sink/source does not systematically improve the metabolic composition of Vitis vinifera white fruit.

The quality of wine grapes depends on the balance between primary and secondary metabolites. Unlike many perennial crops that accumulate starch in the fruits before ripening, the non-climacteric grapes ripe with no previous carbon reserves. Based on the assumption that fruit carbon sink is limiting metabolite accumulation in grapes, bunch thinning is performed to limit plant Sink/Source (S/S). We studied the effects of severe bunch thinning on the accumulation of primary metabolites and on four families of glycosylated aroma precursors (GAPs) at the arrest of fruit phloem unloading of two white grape Vitis vinifera cvs. At plant level, crop reduction resulted in significant losses of metabolites to be accumulated in the fruits: i.e. up to 72% for sugars, 75% for organic acids and GAPs. Nevertheless, S/S manipulation could not modify the balance between GAPs and primary metabolites or increase the concentration in GAPs in the physiologically ripe grape.

Removal of biogenic amines from wines by chemisorption on functionalized silica and effects on other wine components.

The effectiveness of several functionalized silica materials (cation-exchange materials) for the removal of biogenic amines from wines, and the effects on other wine components and organoleptic characteristics were evaluated. Results have shown that mesoporous silica material bi-functionalized with phosphonic and sulfonic acids allowed the removal of histamine, putrescine, cadaverine, spermine and spermidine from wines, although the dose must be adapted for each wine according to the removal requirements and wine characteristics. A plus of the adsorbent developed is that it can be recovered and re-used for at least 3 treatments. Immediately following the treatments, a decrease in the levels of linear ethyl esters (ethyl hexanoate, ethyl octanoate and ethyl decanoate) was observed, although these levels were re-equilibrated after several days reducing this undesired side effect. A slight, but perceptible, effect on wine color was observed, probably due to the slight decrease in the pH of the wine produced by the treatments. On the basis of the sensory analysis that focused only on the aroma of the wines, the proposed technique would be more adequate for wines aged in barrels than for young wines.

Impact of agronomic practices on grape aroma composition: a review.

Aroma compounds are secondary metabolites that play a key role in grape quality for enological purposes. Terpenes, C13 -norisoprenoids, phenols, and non-terpenic alcohols are the most important aroma compounds in grapes and they can be found as free volatiles or glycoconjugated (bound) molecules. The non-volatile glycosylated group is the largest, and it is present in all varieties of Vitis vinifera (L.), the most widely used species for wine production. These aroma precursors represent the reserve of aroma molecules that can be released during winemaking. Their relative and absolute concentrations at fruit ripening determine the organoleptic value of the final product. A large range of biotic and abiotic factors can influence their biosynthesis in several ways. Agronomic practices such as irrigation, training systems, leaf removal, and bunch thinning can have an effect at plant level. The spraying of stimulatory compounds on fruit at different developmental stages has also been shown to modify metabolic pathways at fruit level with some impact on the aroma composition of the grapevine fruit. Viticulturists could act to promote aroma precursors to improve the aromatic profile of grapes and the wine ultimately produced. However, agronomic practices do not always have uniform results. The metabolic and physiological changes resulting from agronomic practices are unknown because there has not been sufficient research to date. This review presents the state of the art regarding the influences of vineyard agronomic management on the biosynthesis of grape aroma compounds. Although literature regarding the topic is abundant there are still many unknown biological mechanisms involved and/or that have been insufficiently studied. The aim of this work is therefore to find the gaps in scientific literature so that future investigations can focus on them. © 2018 Society of Chemical Industry.

Rapid quantification of clove (Syzygium aromaticum) and spearmint (Mentha spicata) essential oils encapsulated in a complex organic matrix using an ATR-FTIR spectroscopic method.

Essential oils (EOs) are often encapsulated in various and complex matrices to protect them against potential degradation or to control their release. To achieve an optimum use in food products, their rapid and precise quantification after encapsulation and storage is required. Hence, a rapid ATR-FTIR method was developed and tested with two encapsulated essential oils (EOs): clove (Syzygium aromaticum) and spearmint (Mentha spicata);. Despite, the complexity of the matrix, this method coupled with univariate or multivariate regression models exhibited high potential for global quantification of the two encapsulated EOs. For clove EO, in relation to the major presence of eugenol and eugenol acetate, an analysis based on a unique band (1514 cm-1) was sufficient to obtain a good prediction with RMSEP value of 0.0173 g of EO per g of matrix. For spearmint oil which is characterized by numerous terpenoid compound, three bands (799, 885, and 1680-1676 cm-1) were suitable for a good prediction with RMSEP value of 0.0133. ATR-FTIR method was compared with a reference gas chromatography FID quantitative method in an EO release experiment and its efficiency was evaluated through modeling by the Avrami equation. Beside time saving, the ATR-FTIR method was also capable of monitoring the EO profile. This method could be easily adapted as a routine analysis in the EOs industry as quality control.

Lipids modulate acetic acid and thiol final concentrations in wine during fermentation by Saccharomyces cerevisiae × Saccharomyces kudriavzevii hybrids.

Saccharomyces cerevisiae × Saccharomyces kudriavzevii hybrids are typically used for white wine fermentation because of their cryotolerance. One group of these hybrids presents a unique ability to release thiol varietal aroma products as well as excessive amounts of acetic acid under specific conditions, which is detrimental for wine organoleptic quality. The aim of this work is to better assess the effects of lipids, sugar concentrations and temperature on the production of acetic acid and thiols during wine fermentation. To this end, we used a Box-Behnken experimental design and response surface modeling on the production of acetic acid and thiols in S. cerevisiae × S. kudriavzevii hybrids from the Eg8 family during fermentation of a synthetic must. We showed that these hybrids produced lower levels of acetic acid when the initial lipid concentration was increased, whereas they produced greater levels when the initial sugar concentration was high. Moreover, we found that lipids had a positive impact on the final concentrations of 4-methyl-4-mercaptopentan-2-one and 3-mercaptohexan-1-ol (3MH), giving box tree and citrus flavors, respectively. The increase of 3MH was concomitant with a decrease of 3-mercaptohexyl acetate (3MHA) characterized by a passion fruit aroma, indicating that lipid addition reduces the rate of 3MH acetylation into 3MHA. These results highlight the key role of lipid management in acetic acid metabolism and thiol release by S. cerevisiae × S. kudriavzevii hybrids and underline its technological interest in alcoholic fermentation to avoid the overproduction of volatile acidity while favoring the release of volatile thiols.

Effect of seasonal climate fluctuations on the evolution of glycoconjugates during the ripening period of grapevine cv. Muscat à petits grains blancs berries.

BACKGROUND: Temperature changes and rainfall fluctuations affect the winemaking industry by altering vine phenology, crop yield, must composition and wine quality. Here, the evolution of the varietal aroma potential during ripening over three consecutive seasons has been analyzed considering climate conditions. The effect of season, ripening date and climatic conditions on aroma precursor accumulation in grapes was studied by multivariate analysis and discussed in regard to the potential aromatic quality of the wine. RESULTS: In contrast to musts obtained from grapes harvested in warm and dry seasons (2014 and 2015), musts obtained from grapes harvested in the coolest and most humid year (2013) showed a lower pH, higher total acidity, higher varietal aroma potential index (IPAv), and higher aromatic potential of linalool, geraniol and nerol (typical of the Muscat flavor). CONCLUSION: Considering the three seasons, grapes synthesized and accumulated more precursors when milder temperatures and late rains throughout veraison were recorded. However, we observed a high fluctuation of aroma precursors during the ripening period, so choosing the correct harvesting date (according to grape aroma potential) may overcome some of the negative effects linked to climate conditions. © 2017 Society of Chemical Industry.

HPLC-UV/DAD and ESI-MS(n) analysis of flavonoids and antioxidant activity of an Algerian medicinal plant: Paronychia argentea Lam.

Paronychia argentea Lam., belonging to the Caryophyllaceae family, is a perennial plant widely distributed in Algeria. Even though this plant is used in the Algerian popular medicine, its phytochemical characterization is incomplete. In this study, the flavonoid profile and the in vitro antioxidant activity of the ethanolic extract, decoction and infusion of P. argentea aerial parts are reported. Flavonoids were analyzed by means of high-performance liquid chromatography coupled with diode array detection and electrospray ionization mass spectrometry. Eleven compounds were identified and six of them, including isorhamnetin-3-O-dihexoside, quercetin-3-O-glucoside, quercetinmethylether-O-hexoside, quercetin, jaceosidin and isorhamnetin, were described in this plant for the first time. The ethanol extract showed the highest flavonoid content, followed by the decoction and the infusion (25.4 ± 0.8 mg/g of DM, 8.4 ± 0.5 mg/g of DM, 0.2 mg/g of DM, respectively), while the best antioxidant activity was shown by the decoction (RC0.5 = 178 µg/mL for reducing power, 72.4% of inhibition of lipid peroxidation, IC50 = 27.38µ g/mL for DPPH radical scavenging activity and 59.7% of inhibition of NO radical). These results showed that P. argentea decoction could be considered as a valuable source of flavonoids and antioxidants that might contribute to the valorization of the phytotherapeutic potential of this plant.

Aromatic evolution of wine packed in virgin and recycled PET bottles.

The evolution of the aromatic profile of a rosé wine packed in glass, virgin and recycled PET bottles was studied. Wine stored in PET and glass bottles was clearly differentiated after 5months of storage but only by a limited number of compounds. More pronounced decrease of oxygen sensitive compounds such as methionol was observed in PET bottles as well as the apparition of oxidative and ageing aroma compounds such as ethyl pyruvate, furfural or dioxanes in higher concentration. Compared to virgin PET bottles, recycled PET bottles induced slight changes favouring the presence of esters and alcohols. The chemical evolution of wine was the most important phenomenon that explains the loss of flavour rather than the sorption into PET. Because of their moderate oxygen permeability, the use of virgin PET and recycled PET bottles could be adapted for short conservation of wine but detrimental to aromatic quality if long conservation is intended.

The use of active PET to package rosé wine: Changes of aromatic profile by chemical evolution and by transfers.

Active Polyethylene Terephthalate (PET) bottles containing 1 or 3% of oxygen scavenger (named 1osPET and 3osPET) were used to pack rosé wine. Changes in the aromatic profiles were monitored during 12months and compared to those of a wine packed in glass bottles. Wine in 1osPET bottles was differentiated from wine in glass or 3osPET bottles by ten aging markers such as cis-dioxane, ethyl pyruvate or furfural. Only trans-1,3-dioxolane allowed to discriminate wine in glass and in 3osPET bottles. Methionol, an oxygen sensitive aroma compound, was preserved in glass and 3osPET bottles but was slightly degraded (15%) in 1osPET bottles. Chemical reactions were the main cause of the aroma compound degradation. Indeed, the total amount of compounds sorbed only reached 160µg considering the bottles and the joint of cap after 12months of storage. The use of PET with 3% of oxygen scavenger is adapted to pack wine for at least 12months.

Influence of volatile thiols in the development of blackcurrant aroma in red wine.

A strong blackcurrant aroma was recently perceived in some red wines originating from the same appellation. Varietal thiols such as 4-mercapto-4-methyl-2-pentanone (4MMP), 3-(mercapto)hexyl acetate (3MHA) and 3-mercapto-1-hexanol (3MH) are compounds potentially responsible for the development of this aroma. In order to demonstrate the correlation between thiols concentrations in red wines and blackcurrant aroma intensity, a multiple variable analysis was realised with thiols concentrations obtained by chemical analysis and blackcurrant aroma intensities obtained by descriptive sensory analysis. The 4MMP concentration was very well correlated to the blackcurrant aroma, and 3MHA and 3MH present at high concentrations act as enhancers of the perception of this aroma. This correlation was further supported after performing a sensory comparison by classification test. The different factors that could impact on the development of blackcurrant aroma in red wine were discussed.

Evolution of S-cysteinylated and S-glutathionylated thiol precursors during oxidation of Melon B. and Sauvignon blanc musts.

Thiol precursor content in Melon B. and Sauvignon blanc grape juices obtained under vacuum was determined by quantifying cysteinylated and glutathionylated conjugates of 3-mercaptohexan-1-ol (3MH) and 4-methyl-4-mercaptopentan-2-one (4MMP). This characterization allowed the study of thiol precursor evolution during ripening of Sauvignon blanc grapes in several viticultural situations together with grape reaction product (GRP) and the main substrate of polyphenoloxidase, that is, caftaric acid. Concentration of precursors greatly increased during ripening except for the cysteinylated conjugate of 4MMP. Precursor evolution was also monitored during the oxidation of grape juice. Addition of oxygen to a grape juice set off the enzymatic oxidation of hydroxycinnamic acids but did not negatively affect precursor concentrations. Part of the glutathionylated precursor of the 3MH was produced during prefermentative operations (up to 140% in Sauvignon blanc). Consequently, this precursor naturally occurring in grapes was also formed during prefermentative operations. The proportion of biogenetic and prefermentary formation of the glutathionylated precursor of 3MH was different under industrial conditions depending on the grape variety considered. Addition of glutathione and hexenal in grape juices of Melon B. and Sauvignon induced an increase of the production of 3MH and consequently of its acetate in the resulting wines. Residual glutathione in must has to be preserved to enhance the aromatic potential of grapes.

Validation of a nanoliquid chromatography-tandem mass spectrometry method for the identification and the accurate quantification by isotopic dilution of glutathionylated and cysteinylated precursors of 3-mercaptohexan-1-ol and 4-mercapto-4-methylpentan-2-one in white grape juices.

A rapid nanoLC-MS/MS method was developed and validated for the simultaneous determination of glutathionylated and cysteinylated precursors of 3-mercapto-hexan-1-ol (3MH) and 4-methyl-4-mercaptopentan-2-one in grape juice using stable isotope dilution assay (SIDA). The analytes were extracted from must using a cation exchange resin and purified on C18 cartridges. They were chromatographically separated on a reverse phase column and finally analyzed by tandem mass spectrometry in selected reaction monitoring mode (SRM) using deuterated analogues as standards except for glutathionylated conjugate of 4MMP which was analyzed by external calibration. The method was validated according to the International Conference on Harmonization recommendations by determining linearity, accuracy, precision, recovery, matrix effect, repeatability, intermediate reproducibility, LODs and LOQs. Calibration for each precursor was determined by performing Lack-of-Fit test and the best fitting for 3MH precursors was a quadratic model whereas a linear model was better adapted for 4MMP precursors. All calibration curves showed quite satisfactory correlation coefficients (R(2)>0.995 for SIDA quantification and R(2)>0.985 for external calibration). Quantification by SIDA and external calibration allowed a high level of accuracy since the averaged value ranged from 80 to 108%. Quantification of aroma precursors was accurate and reproducible over five days since intermediate precision (same analyst, same sample and same apparatus), which was evaluated by the calculation of RSD was inferior to 16%. Limits of quantification for G3MH and G4MMP were closed to 0.50 and 0.07 nmol/L and as 4.75 and 1.90 nmol/L for Cys3MH and Cys4MMP respectively. This method was applied to the quantification of precursors into several types of grape juices: Melon B., Sauvignon, Riesling and Gewurztraminer.

Improved method to quantitatively determine powerful odorant volatile thiols in wine by headspace solid-phase microextraction after derivatization.

A solid-phase microextraction (SMPE) method coupled to a gas chromatography-mass spectrometry analysis was optimized to analyze the pentafluorobenzyl bromide (PFBBr) derivatives of the volatile thiols 4-methyl-4-mercapto-2-pentanone (4MMP), 3-mercaptohexyl acetate (3MHA) and 3-mercaptohexanol (3MH) in wine. This method used deuterated analogue compounds as internal standards. It allowed us to significantly reduce the matrix effect, resulted in good repeatability for all the compounds (RDS<9.5% for 4MMP; <6% for 3MH and <4.1% for 3MHA) with limits of detection below their odour thresholds. The method was validated using white, rosé and red wines. When applied to analyze different wines, quantities closed to the odour threshold were determined.

Fate of prions in soil: adsorption and extraction by electroelution of recombinant ovine prion protein from montmorillonite and natural soils.

Prions, the infectious agents thought to be responsible for transmissible spongiform encephalopathies, may contaminate soils and have been reported to persist there for years. We have studied the adsorption and desorption of a model recombinant prion protein on montmorillonite and natural soil samples in order to elucidate mechanisms of prion retention in soils. Clay minerals, such as montmorillonite, are known to be strong adsorbents for organic molecules, including proteins. Montmorillonite was found to have a large and selective adsorption capacity for both the normal and the aggregated prion protein. Adsorption occurred mainly via the N-terminal domain of the protein. Incubation with standard buffers and detergents did not desorb the full length protein from montmorillonite, emphasizing the largely irreversible trapping of prion protein by this soil constituent. An original electroelution method was developed to extract prion protein from both montmorillonite and natural soil samples, allowing quantification when coupled with rapid prion detection tests. This easy-to-perform method produced concentrated prion protein extracts and allowed detection of protein at levels as low as 0.2 ppb in natural soils.

Field-based supercritical fluid extraction of hydrocarbons at industrially contaminated sites.

Examination of organic pollutants in groundwaters should also consider the source of the pollution, which is often a solid matrix such as soil, landfill waste, or sediment. This premise should be viewed alongside the growing trend towards field-based characterisation of contaminated sites for reasons of speed and cost. Field-based methods for the extraction of organic compounds from solid samples are generally cumbersome, time consuming, or inefficient. This paper describes the development of a field-based supercritical fluid extraction (SFE) system for the recovery of organic contaminants (benzene, toluene, ethylbenzene, and xylene and polynuclear aromatic hydrocarbons) from soils. A simple, compact, and robust SFE system has been constructed and was found to offer the same extraction efficiency as a well-established laboratory SFE system. Extraction optimisation was statistically evaluated using a factorial analysis procedure. Under optimised conditions, the device yielded recovery efficiencies of >70% with RSD values of 4% against the standard EPA Soxhlet method, compared with a mean recovery efficiency of 48% for a commercially available field-extraction kit. The device will next be evaluated with real samples prior to field deployment.