Polyphenolic Profiling, Browning, and Glutathione Content of Sparkling Wines Produced with Nontraditional Grape Varieties: Indicator of Quality During the Biological Aging.

Sparkling wines were elaborated with the nontraditional varieties Villenave, Niagara, Manzoni, and Goethe, and monitored in relation to the changes in phenolic composition, browning index, and glutathione content during 18 months of biological aging (sur lies). Important changes in the phenolic profile, browning index, and glutathione content were observed in the sparkling wines during the over-lees aging period. The major phenolic compound in the sparkling wines was tyrosol, followed by caffeic, trans-caftaric, and gallic acids, catechin and epicatechin. The biological aging led to an increase in the individual phenolic compounds, especially caffeic, gallic, and ellagic acids, and an increase in the browning index was also observed during the aging period. Caffeic acid was significantly correlated with browning and aging period in all sparkling wines, which indicates that this compound can be useful as a quality marker to monitoring the biological aging profile of white sparkling wines. The results obtained indicate that the aging period (sur lie) had an important influence on the changes in the unique phenolic profile of the sparkling wines elaborated with nontraditional varieties. PRACTICAL APPLICATION: In sparkling wines production, the secondary fermentation occurring in the sealed bottle during the vinification contributes greatly to their quality and sensory complexity. The Vitis labrusca and hybrid grapes varieties represent most of the grapes cultivated in Brazil being employed in the elaboration of juices and wines. These varieties present a great oenological potential and have not been explored yet regarding to the production of white sparkling wines. The use of these nontraditional grape varieties cultivated in South Brazil may be a viable alternative in the production of white sparkling wines with biological aging potential and particular bioactive properties.

Digestion behavior and antidepressant-like effect promoted by acute administration of blueberry extract on mice.

The aim of this study was to evaluate the antidepressant-like effect of the acute administration of blueberry extract in mice. In addition, the digestion behavior of individual phenolic compounds using an in vitro digestion model was also investigated and the main bioaccessible compounds were determined. During digestion, important changes were observed in the polyphenols concentrations and antioxidant capacity upon the passage through the gastric and enteric phases. Bioactive compounds such as chlorogenic and ferulic acids, catechin, epicatechin, quercetin and malvidin were highly bioaccessible from the blueberry. The in vivo experiment was carried out with males Swiss mices; for the evaluation of the minimum effective dose of the extract, mices were treated with different concentrations (200, 300 and 400 mg/kg) of the blueberry extract. The animals were submitted to behavior tests and the minimum effective dose of the blueberry extract was established as 300 mg/kg. The results indicated a decrease in the immobility time of mice in the tail suspension test without any effect on the locomotor activity in the open field test when treated with the minimum effective dose. This dose was then chosen to carried out the tests of hepatotoxicity and results showed no evidences of toxic effects of blueberry extract. The acute administration of the blueberry extract also led to a significant decrease Thiobarbituric Acid Reactive Substances (TBARS) in mices hippocampus. The results observed suggest that the neuroprotective and antidepressant-like effects might be related to the phytochemical composition of the blueberry, particularly due to the high flavonols and anthocyanins concentrations.

Quantification of hydroxycinnamic derivatives in wines by UHPLC-MRM-MS.

A UHPLC-MS/MS method was developed for the quantification of the main compounds involved in oxidation reactions occurring in white musts and wines such as hydroxycinnamic acids, their glutathione and cysteinylglycine adducts (GRP, GRP2, 5-(S-glutathionyl)-trans-caftaric acid, 2-(S-cysteinylglycyl)-trans-caftaric acid, and 2-(S-glutathionyl)-trans-caffeic acid), and reduced and oxidized glutathione (GSH, GSSG) in wine. Since oxidation is the main concern in white wine-making, directly affecting its quality, the developed method was then applied in a series of white wines made with different pre-fermentation treatments to limit oxidation at must stage. The glucose esters and/or glucosides of hydroxycinnamic acids were quantified as glucogallin equivalent. The developed method led to an overall improvement in the limits of detection (LODs) and quantification (LOQs) for all the compounds studied in comparison to other methods such as high-performance liquid chromatography with fluorescence detection (HPLC-FLD) or diode array UV detection (HPLC-DAD). LOD values ranged from 0.0002 to 0.0140 mg/L and LOQs from 0.0005 to 0.0470 mg/L. The recoveries ranged between 80 and 110% in wines, and the relative standard deviation (RSD) for precision intra- and inter-day was below 15%. The accuracy and intra- and inter-day precision met the acceptance criteria of the AOAC international norms. As far as we know, this study is the first report of quantification of GRP, 2-(S-cysteinylglycyl)-trans-caftaric acid, and 2-(S-glutathionyl)-trans-caffeic acid using these non-commercially available compounds as external standards. Those compounds represent a significant proportion of hydroxycinnamic acid derivatives in wines. The methodology described is suitable for the analysis of hydroxycinnamic derivatives in wines.

Synthesis, Identification, and Structure Elucidation of Adducts Formed by Reactions of Hydroxycinnamic Acids with Glutathione or Cysteinylglycine.

Grape polyphenols, especially hydroxycinnamic acids such as caftaric and caffeic acid, are prone to enzymatic oxidation reactions during the winemaking process, forming o-quinones and leading to color darkening. Glutathione is capable of trapping these o-quinones and thus limiting juice browning. In this study, the addition of glutathione or cysteinylglycine onto caftaric or caffeic acid o-quinones formed by polyphenoloxidase-catalyzed reactions was investigated by UPLC-DAD-ESIMS and NMR data analyses. Complete identification of adducts has been achieved via NMR data. The results confirmed that the favored reaction is the substitution of the sulfanyl group of cysteine at C-2 of the aromatic ring. Several minor isomers, namely, the cis-isomer of the 2-S adduct and trans-isomers of the 5-S and 6-S adducts, and the 2,5-di-S-glutathionyl adducts were also identified and quantified by qNMR. With the exception of 2-(S-glutathionyl)- and 2,5-di(S-glutathionyl)-trans-caftaric acid, these products had never been formally identified. In particular, the 5-S and 6-S derivatives are reported here for the first time. The first formal identification of 2-S cis-derivatives is also provided. Moreover, NMR and UPLC-DAD-ESIMS analysis showed that signature UV and MS spectra can serve as markers of the conformation and substitution position in the aromatic ring for each of the isomers.

A comprehensive investigation of guaiacyl-pyranoanthocyanin synthesis by one-/two-dimensional NMR and UPLC-DAD-ESI-MS(n).

In red and rosé wines, the grape anthocyanins are progressively converted to more stable pigments, including phenylpyranoanthocyanins. One-/two-dimensional NMR and UPLC-DAD-ESI-MS(n) measurements were used to monitor the synthesis of guaiacylpyranomalvidin 3-O-glucoside from malvidin 3-O-glucoside and vinylguaiacol in model solutions and identify the products formed during the reaction. The highest conversion rates (30%, determined by (1)H qNMR) were obtained with a small excess of vinylguaiacol in methanol/water (70/30) at pH 3 and 35°C. Two reaction pathways competed with the formation of guaiacylpyranomalvidin 3-O-glucoside. The first one only concerns malvidin 3-O-glucoside and consists in C-ring cleavage with formation of malvone and smaller molecular weight breakdown products. This pathway is favored at higher pH and incubation temperature. At lower pH values or in the presence of large vinylguaiacol excess, faster consumption of malvidin 3-O-glucoside resulted from the formation of more complex pyranoanthocyanins substituted by vinylguaiacol oligomers.