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An ultrasound-enzyme-assisted extraction (UEAE) was optimized to extract, simultaneously, the hydrophilic and lipophilic compounds from three berry pomaces (raspberry, strawberry and blackberry). First, an enzyme screening designated a thermostable alkaline protease as the most suitable enzyme to recover, in an aqueous medium, the highest yields of polyphenols and oil in the most efficient way. Secondly, the selected enzyme was coupled to ultrasounds (US) in sequential and simultaneous combinations. The simultaneous US-alkaline enzyme combination was selected as a one-single-step process and was then optimized by definitive screening design (DSD). The optimized parameters were: US amplitude, 20% (raspberry pomace) or 70% (strawberry and blackberry pomaces); pH, 8; E/S ratio, 1% (w/w); S/L ratio, 6% (w/v); extraction time, 30 min; temperature, 60 °C. Compared to conventional extractions using organic solvents, the UEAE extracted all the polyphenols, with around 75% of the active polyphenols (measured by the DPPHâ method) and up to 75% of the initial oil from the berry pomaces. Characterized lipophilic compounds were rich in polyunsaturated fatty acids (PUFAs), tocols and phytosterols. The polyphenolics were analyzed by UPLC-MS/MS; characteristic ellagitannins of the Rosaceae family (sanguiin H-6 or agrimoniin, sanguiin H-10, ) and ellagic acid conjugates were found as the major components.
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In sub-Saharan Africa, chronic malnutrition is often associated with intestinal inflammation and oxidative stress. African green leafy vegetables (GLVs), commonly consumed by these populations and rich in bioactive compounds, may improve the antioxidant status. The aim of this study was to measure the antioxidant capacity using complementary assays (DPPH, FRAP, ABTS, ORAC and NO scavenging) in polar and non-polar leaf extracts of four African GLVs, cassava (Manihot esculenta), roselle (Hibiscus sabdariffa), jute mallow (Corchorus olitorius), and amaranth (Amaranthus spp.), with spinach (Spinacia oleracea) chosen as a reference. Their antioxidant capacity was correlated with their total polyphenol (TPC), flavonoid (TFC), condensed tannin, lutein, and ß-carotene contents. Identification of phenolic compounds by UHPLC-DAD-MS/MS revealed the presence of three main classes of compound: flavonols, flavones, and hydroxycinnamic acids. Cassava and roselle leaves presented significantly higher TPC and TFC than amaranth, jute mallow, and spinach. They also exhibited the highest antioxidant capacity, even higher than that of spinach, which is known for its important antioxidant effect. The antioxidant capacity was 2 to 18 times higher in polar than non-polar extracts, and was more strongly correlated with TPC and TFC (R > 0.8) than with ß-carotene and lutein contents. These findings provide new data especially for cassava and roselle leaves, for which studies are scarce, suggesting an appreciable antioxidant capacity compared with other leafy vegetables.
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In the context of climate change, faba beans are an interesting alternative to animal proteins but are characterised by off-notes and bitterness that decrease consumer acceptability. However, research on pulse bitterness is often limited to soybeans and peas. This study aimed to highlight potential bitter non-volatile compounds in faba beans. First, the bitterness of flours and air-classified fractions (starch and protein) of three faba bean cultivars was evaluated by a trained panel. The fractions from the high-alkaloid cultivars and the protein fractions exhibited higher bitter intensity. Second, an untargeted metabolomic approach using ultra-high-performance liquid chromatography-diode array detector-tandem-high resolution mass spectrometry (UHPLC-DAD-HRMS) was correlated with the bitter perception of the fractions. Third, 42 tentatively identified non-volatile compounds were associated with faba bean bitterness by correlated sensory and metabolomic data. These compounds mainly belonged to different chemical classes such as alkaloids, amino acids, phenolic compounds, organic acids, and terpenoids. This research provided a better understanding of the molecules responsible for bitterness in faba beans and the impact of cultivar and air-classification on the bitter content. The bitter character of these highlighted compounds needs to be confirmed by sensory and/or cellular analyses to identify removal or masking strategies.
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Color is a major quality trait of rosé wines due to their packaging in clear glass bottles. This color is due to the presence of phenolic pigments extracted from grapes to wines and products of reactions taking place during the wine-making process. This study focuses on changes occurring during the alcoholic fermentation of Syrah, Grenache and Cinsault musts, which were conducted at laboratory (250 mL) and pilot (100 L) scales. The color and phenolic composition of the musts and wines were analyzed using UV-visible spectrophotometry, and metabolomics fingerprints were acquired by ultra-high performance liquid chromatography-high-resolution mass spectrometry. Untargeted metabolomics data highlighted markers of fermentation stage (must or wine) and markers related to the grape variety (e.g., anthocyanins in Syrah, hydroxycinnamates and tryptophan derivatives in Grenache, norisoprenoids released during fermentation in Cinsault). Cinsault wines contained higher molecular weight compounds possibly resulting from the oxidation of phenolics, which may contribute to their high absorbance values.
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Vitis , Vino , Vino/análisis , Antocianinas/química , Fermentación , Cromatografía Líquida de Alta Presión , Frutas/química , Color , Vitis/química , Fenoles/químicaRESUMEN
High-quality dark chocolates (70% cocoa content) can have shades from light to dark brown color. This work aimed at revealing compounds that discriminate black and brown chocolates. From 37 fine chocolate samples from years 2019 and 2020 provided by Valrhona,8 dark black samples and 8 light brown samples were selected. A non-targeted metabolomics study was performed based on ultra-high performance liquid chromatography-high resolution mass spectrometry/mass spectrometry experiments, univariate, multivariate, and feature-based molecular networking analyses. Twenty-seven overaccumulated discriminating compounds were found for black chocolates. Among them, glycosylated flavanols including monomers and glycosylated A-type procyanidin dimers and trimers were highly representative. Fifty overaccumulated discriminating compounds were found for brown chocolates. Most of them were B-type procyanidins (from trimers to nonamers). These phenolic compounds may be partially related to the chocolate colors as precursors of colored compounds. This study increases the knowledge on the chemical diversity of dark chocolates by providing new information about the phenolic profiles of black and brown chocolates.
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Rosé wines show large color diversity, due to different phenolic pigment compositions. However, the mechanisms responsible for such diversity are poorly understood. The present work aimed at investigating the impact of fermentation on the color and composition of rosé wines made from Grenache, Cinsault, and Syrah grapes. Targeted MS analysis showed large varietal differences in must and wine compositions, with higher concentrations of anthocyanins and flavanols in Syrah. UV-visible spectrophotometry and size exclusion chromatography data indicated that Grenache and Cinsault musts contained oligomeric pigments derived from hydroxycinnamic acids and flavanols which were mostly lost during fermentation due to adsorption on lees. Syrah must color was mainly due to anthocyanins which were partly converted to derived pigments through reactions with yeast metabolites with limited color drop during fermentation. This work highlighted the impact of must composition, reflecting varietal characteristics, on changes occurring during fermentation and consequently wine color.
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Vitis , Vino , Vino/análisis , Polifenoles/análisis , Antocianinas/análisis , Fermentación , Color , Vitis/química , Saccharomyces cerevisiaeRESUMEN
Concentrations of anthocyanins and tannins after extraction from berries in wines and from skin macerations in model solutions have been studied for two grape varieties, two maturation levels and two vintages berries. Characterization of the cell wall polysaccharides has also been performed, the classical method based on the analysis of the neutral sugars after depolymerization being completed by a comprehensive microarray polymer profiling (CoMPP). Extraction was lower in model solutions than in wines, with the same ranking: non acylated anthocyanins> tannins > p-coumaroylated anthocyanins. The polysaccharidic composition suggested a role of homogalacturonans, rhamnogalacturonans and extensins in the extraction process. A global explanation of the interactions between anthocyanins, tannins and polysaccharides is proposed.
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Vitis , Vino , Taninos/análisis , Antocianinas/análisis , Frutas/química , Vino/análisis , Polisacáridos/análisis , Pared Celular/químicaRESUMEN
Dehydrodicatechins resulting from (epi)catechin oxidation have been investigated in different foods and natural products, but they still offer some analytical challenges. The purpose of this research is to develop a method using ultra-high performance liquid chromatography coupled with trapped ion mobility spectrometry and tandem mass spectrometry (UHPLC-ESI-TIMS-QTOF-MS/MS) to improve the characterization of dehydrodicatechins from model solutions (oxidation dimers of (+)-catechin and/or (-)-epicatechin). Approximately 30 dehydrodicatechins were detected in the model solutions, including dehydrodicatechins B with ß and ε-interflavanic configurations and dehydrodicatechins A with γ-configuration. A total of 11 dehydrodicatechins B, based on (-)-epicatechin, (+)-catechin, or both, were tentatively identified in a grape seed extract. All of them were of ß-configuration, except for one compound that was of ε-configuration. TIMS allowed the mobility separation of chromatographically coeluted isomers including dehydrodicatechins and procyanidins with similar MS/MS fragmentation patterns that would hardly be distinguished by LC-MS/MS alone, which demonstrates the superiority of TIMS added to LC-MS/MS for these kinds of compounds. To the best of our knowledge, this is the first time that ion mobility spectrometry (IMS) was applied to the analysis of dehydrodicatechins. This method can be adapted for other natural products.
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Productos Biológicos , Catequina , Catequina/química , Cromatografía Líquida de Alta Presión , Cromatografía Liquida , Espectrometría de Movilidad Iónica , Polifenoles/análisis , Espectrometría de Masas en TándemRESUMEN
The color of rosé wines is extremely diverse and a key element in their marketing. It is due to the presence of anthocyanins and of additional pigments derived from them and from other wine constituents. To explore the pigment composition and determine its links with color, 268 commercial rosé wines were analysed. The concentration of 125 polyphenolic compounds was determined by a targeted metabolomics approach using ultra high-performance liquid chromatography coupled to triple quadrupole mass spectrometry (UHPLC-QqQ-MS) analysis in the Multiple Reaction Monitoring (MRM) mode and the color characterised by spectrophotometry and CieLab parameters. Chemometrics analysis of the composition and color data showed that although color intensity is primarily determined by polyphenol extraction (especially anthocyanins and flavanols) from the grapes, different color styles correspond to different pigment compositions. The salmon shade of light rosé wines is mostly due to pyranoanthocyanin pigments, resulting from reactions of anthocyanins with phenolic acids and pyruvic acid, a yeast metabolite. Redness of intermediate color wines is related to anthocyanins and carboxypoyranoanthocyanins and that of dark rosé wines to products of anthocyanin reactions with flavanols while yellowness of these wines is associated to oxidation.
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Color , Metabolómica , Polifenoles/química , Vino/análisis , Antocianinas/química , Quimiometría/métodos , Cromatografía Líquida de Alta Presión , Espectrometría de Masas , Metabolómica/métodos , Vitis/químicaRESUMEN
Tapirira guianensis (Anacardiaceae) is a natural resource from the Amazonian Forest and is locally known in French Guiana as "loussé" (creole), "tata pilili" (wayãpi), or "ara" (palikur). The tree is used by indigenous populations for medicinal purposes. To increase the potential of this tree for cosmetic, agro-food, or pharmaceutical uses, extracts were obtained through ultrasound-assisted extraction (UAE) from T. guianensis leaves using various extraction solvents such as water, methanol, and methanol-water (85/15; v/v). Chemical (DPPH, TEAC, ORAC) tests were applied to assess the anti-radical potential of these extracts. The polyphenol contents were determined by spectrophotometric (UV/Visible) and by means of chromatographic (UPLC-DAD-ESI-IT-MSn) methods. Tapirira guianensis leaf hydromethanolic extract produced the highest polyphenol content and exhibited antiradical activities in chemical assays (DPPH, TEAC, and ORAC) similar to (or higher than) those of a well-known antiradical plant, green tea. In T. guianensis, two classes of polyphenols were evidenced: (1) galloylquinic acids (identified for the first time in the studied species) and (2) flavonols and flavanols (present in small amounts). Flavonols seemed to play a major role in the antioxidant activity of DPPH. These findings provide a rationale for the use of T. guianensis in traditional medicine and to pave the way for seeking new biological properties involving this Amazonian tree.
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Addition of oenological tannins claims to have a positive impact on wine stability, protection from oxidation and likely sensory persistence. However, their role on red wine aroma during oxidation is controversial. The present study aims at investigating the effect of addition of oenological tannins on wine flavour (mainly aroma) before and after air exposure. Temporal Dominance of Sensations, a dynamic sensory evaluation, was coupled with a dynamic chemical measurement (nosespace analysis) using a Proton-Transfer-Reaction Mass-Spectrometer connected to the nasal cavity of 17 assessors. Results showed that the oxidation of a non-oaked Pinot Noir red wine decreases the fruity aroma dominance and increases the maderised and prune one. A contextual decrease of the fruity ethyl decanoate and increase of oxidative Strecker aldehydes are observed. Ellagitannins but not proanthocyanidins preserved perception of fruitiness and prevented increase of maderised notes. Moreover, ellagitannins increase the aroma persistence mainly in the non-oxidized wine.
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Odorantes , Vino , Odorantes/análisis , Percepción , Taninos , Gusto , Vino/análisisRESUMEN
RATIONALE: The calculation of centroids from profile mass spectra is one of the very first steps in the processing of mass spectra. The output is a signal and a m/z value. We focus on the accuracy of the prediction of the centroids' m/z values. METHODS: A calculation based on the Savizky-Golay algorithm was evaluated on an Orbitrap mass spectrum. Reference m/z values were identified manually. Experimental centroids were extracted (1) automatically using our algorithm or the MSconvert algorithm and (2) manually using the Xcalibur software from Thermo. The three series of experimental m/z values were compared with the reference m/z values. RESULTS: Our algorithm improved the determination of the m/z values compared with MSconvert. However, no improvement was observed over Xcalibur. CONCLUSIONS: Our algorithm improved the automatic estimation of m/z values in the profile-to-centroid calculation. This is of importance when the goal is to determine raw compositions from the experimental m/z values. Nevertheless, the algorithms led to almost the same m/z values on a higher resolution mass spectrum.
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Gallotannins extracted from gallnuts are commonly added to wine to improve its properties. They consist of mixtures of galloylester derivatives of glucose. However, their composition and properties are not well-established. In this study, methods based on liquid chromatography coupled to ultraviolet-visible detection and mass spectrometry, size-exclusion chromatography, and one-dimensional (31P) and two-dimensional (1H diffusion ordered spectroscopy, 31P total correlated spectroscopy, and 1H/13C heteronuclear single-quantum correlation and heteronuclear multiple-bond correlation) nuclear magnetic resonance spectroscopies have been implemented for extensive chemical characterization of three commercial gallnut tannin extracts. Differences in the proportions of the different constituents (gallic, digallic, and trigallic acids and galloylglucose derivatives) and in the structure and molecular weight distributions of gallotannins were demonstrated between the three extracts, with chains containing 8.5, 12.2, and 12.4 galloyl groups on average for TAN A, TAN B1, and TAN B2, respectively. The antioxidant capacities of the extracts, evaluated using the 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) method, were similar and related mostly to their total tannin content, with only a limited impact of the tannin composition.
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Taninos Hidrolizables/química , Extractos Vegetales/química , Quercus/química , Cromatografía Líquida de Alta Presión , Espectroscopía de Resonancia Magnética , Nueces/química , Espectrometría de Masas en TándemRESUMEN
Even though non-Saccharomyces yeasts were regarded as spoilage microorganisms for a long time, their abilities to improve and diversify the aromatic profile of wines are now well recognized. Consequently, their use in combination with S. cerevisiae strains during winemaking has attracted substantial attention over the last decade. However, our limited understanding of the metabolism and physiology of these species remains a barrier to promoting efficient exploitation of their full potential. In this study, we further explored the metabolism involved in the production of fermentative volatile compounds of two commercial non-Saccharomyces strains, T. delbrueckii Biodiva™ and M. pulcherrima Flavia®, in comparison with the reference wine yeast S. cerevisiae Lalvin EC1118®. After growing these strains in the presence of 24 different N-compounds, particular attention was paid to the influence of the nitrogen source on the profile of aroma compounds synthesized by these yeasts (higher alcohols and acids, medium-chain fatty acids and their acetate or ethyl esters derivatives). A comprehensive analysis of the dataset showed that these three species were able to produce all the fermentative aromas, regardless of the nitrogen source, demonstrating the key contribution of the central carbon metabolism to the formation of volatile molecules. Nevertheless, we also observed some specific phenotypic traits for each of the strains in their assimilation capacities for the various nitrogen nutrients as well as in their response to the nature of the nitrogen source in terms of the production of volatile molecules. These observations revealed the intricacy and interconnection between the networks involved in nitrogen consumption and aroma production. These differences are likely related to the genetic backgrounds of the strains. Overall, this study expands our understanding of the metabolic processes responsible for the formation of volatile compounds during wine fermentation and their variations according to species and the nature of the nitrogen source. This knowledge provides a new platform for the more efficient exploitation of non-Saccharomyces strains during winemaking, improving the management of the fermentation.
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Nitrógeno/metabolismo , Odorantes , Saccharomycetales/metabolismo , Compuestos Orgánicos Volátiles/metabolismo , Fermentación , Odorantes/análisis , Fenotipo , Saccharomyces cerevisiae/metabolismo , Saccharomycetales/clasificación , Especificidad de la Especie , Compuestos Orgánicos Volátiles/análisis , Vino/análisis , Vino/microbiologíaRESUMEN
The study was designed to evaluate how the distillation process is able to affect the composition and bioactivity of oligosaccharides contained in the grape seeds. Different oligosaccharidic fractions have been extracted both before and after grape pomace distillation in order to valorize this by-product. A multistep solid-phase extraction approach (C-18 and carbograph cartridges) has been applied to purify and fractionate the oligosaccharidic compounds. Chemical characterization of the fractions was performed using a UPLC-ESI-MSn method. Complex oligosaccharides consist principally of neutral oligosaccharides rich in arabinose and glucose. Then, the oligosaccharides contained in the different fractions as potential functional ingredients with prebiotic activity toward well-known probiotic bacteria, such as Lactobacillus acidophilus and Lactobacillus plantarum, were evaluated. Data showed how, in some combination, oligosaccharidic fractions obtained may be considered a novel "functional ingredient" with potential prebiotic activity mainly towards L. acidophilus.
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Destilación/métodos , Extracto de Semillas de Uva/química , Oligosacáridos/química , Oligosacáridos/farmacología , Prebióticos , Fraccionamiento Químico , Extracto de Semillas de Uva/análisis , Lactobacillus acidophilus/efectos de los fármacos , Lactobacillus plantarum/efectos de los fármacos , Oligosacáridos/análisis , Prebióticos/análisis , Probióticos , Extracción en Fase Sólida/instrumentación , Extracción en Fase Sólida/métodos , Espectrometría de Masa por Ionización de ElectrosprayRESUMEN
This work aims to sort cocoa beans according to chocolate sensory quality and phenolic composition. Prior to the study, cocoa samples were processed into chocolate in a standard manner, and then the chocolate was characterized by sensory analysis, allowing sorting of the samples into four sensory groups. Two objectives were set: first to use average mass spectra as quick cocoa-polyphenol-extract fingerprints and second to use those fingerprints and chemometrics to select the molecules that discriminate chocolate sensory groups. Sixteen cocoa polyphenol extracts were analyzed by liquid chromatography-low-resolution mass spectrometry. Averaging each mass spectrum provided polyphenolic fingerprints, which were combined into a matrix and processed with chemometrics to select the most meaningful molecules for discrimination of the chocolate sensory groups. Forty-four additional cocoa samples were used to validate the previous results. The fingerprinting method proved to be quick and efficient, and the chemometrics highlighted 29 m/ z signals of known and unknown molecules, mainly flavan-3-ols, enabling sensory-group discrimination.
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Cacao/química , Chocolate/análisis , Espectrometría de Masas , Polifenoles/análisis , Flavonoides/análisis , Calidad de los Alimentos , Espectrometría de Masas/métodos , Extractos Vegetales/química , Reproducibilidad de los Resultados , SensaciónRESUMEN
The presence of monomeric and dimeric flavan-3-ol monohexosides was investigated in grapes and wines. Polyphenol extracts were prepared from grape seeds and skins (Syrah, Merlot, and Cabernet-Sauvignon) sampled at three different developmental stages. Different wines (Tannat, Alicante, Syrah, Merlot, and Grenache) were also studied. The different samples obtained were analyzed by UPLC-ESI-IT-MS. Specific molecular ions corresponding to flavan-3-ol hexosides were detected by using targeted molecular ions with specific m/z values: 451 for (epi)catechin hexosides, and 739 for procyanidin dimer hexosides. 4'-O-ß-glucosyl-(+)-catechin and 7-O-ß-glucosyl-(+)-catechin were obtained by using a glucosyl transferase from apple, UGT71A15, and their structures determined by NMR. These glucosylated monomers and the dimers were identified in all analyzed grape seed and several skin extracts at the different stages and in wines made from different varieties.
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Glicósidos/análisis , Vitis/química , Vino/análisis , Catequina/química , Cromatografía Líquida de Alta Presión , Dimerización , Flavonoides/química , Espectroscopía de Resonancia Magnética , Conformación Molecular , Extractos Vegetales/química , Semillas/química , Semillas/metabolismo , Espectrometría de Masa por Ionización de Electrospray , Vitis/metabolismoRESUMEN
Two series of compounds showing mass signals at m/z 605 and 893 (negative ionization mode) have been detected in fermented cocoa beans. This study objective is to identify these mass signals and characterize their structure in fermented cocoa samples. Our hypothesis is that these signals may correspond to ethyl-bridged flavan-3-ols resulting from flavan-3-ol condensation with acetaldehyde which is a microbial metabolite. Mass spectrometry was used to compare the retention times and mass fragmentation patterns between a model solution using epicatechin and procyanidin dimer B2, the major flavan-3-ols of cocoa, as precursors and extracts of fermented cocoa. Their identification was confirmed: four isomers of ethyl-linked epicatechin as well as several isomers of epicatechin-ethyl-procyanidin B2, in which B2 was mostly linked through its upper unit, were characterized in cocoa. This study demonstrates the presence of flavan-3-ol acetaldehyde condensation products in fermented cocoa beans and provides the first report of epicatechin-ethyl-procyanidin B2.
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Cacao/química , Flavonoides/química , Biflavonoides/análisis , Biflavonoides/química , Reactores Biológicos , Cacao/metabolismo , Catequina/análisis , Catequina/química , Cromatografía Líquida de Alta Presión , Dimerización , Flavonoides/análisis , Isomerismo , Polifenoles/química , Polifenoles/aislamiento & purificación , Proantocianidinas/análisis , Proantocianidinas/química , Espectrometría de Masa por Ionización de ElectrosprayRESUMEN
This work seeks to understand the kinetics of O2 and SO2 consumption of air-saturated red wine as a function of its chemical composition, and to describe the chemical changes suffered during the process in relation to the kinetics. Oxygen Consumption Rates (OCRs) are faster with higher copper and epigallocatechin contents and with higher absorbance at 620nm and slower with higher levels of gallic acid and catechin terminal units in tannins. Acetaldehyde Reactive Polyphenols (ARPs) may be key elements determining OCRs. It is confirmed that SO2 is poorly consumed in the first saturation. Phenylalanine, methionine and maybe, cysteine, seem to be consumed instead. A low SO2 consumption is favoured by low levels of SO2, by a low availability of free SO2 caused by a high anthocyanin/tannin ratio, and by a polyphenolic profile poor in epigallocatechin and rich in catechin-rich tannins. Wines consuming SO2 efficiently consume more epigallocatechin, prodelphinidins and procyanidins.
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Oxígeno/química , Dióxido de Azufre/química , Vino , Cinética , PolifenolesRESUMEN
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.