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Anthocyanin composition in Cabernet Sauvignon red wine vinegar obtained by submerged acetification
Abstract
Vinegars elaborated from white wine can be characterized by their phenolic composition. Indeed, for authenticity purpose, phenolic composition can be used to identify Sherry and Balsamic vinegars. However, the phenolic composition of red wine vinegars has scarcely been studied. Anthocyanin compounds in particular remain largely unknown. This study focuses on the analysis of anthocyanin compounds in red wine vinegar and the effect of acetification with submerged culture on such vinegars.The vinegar used in this study was produced from a young Cabernet Sauvignon wine in a laboratory-scale fermenter. Subsequent analyses of both wine and vinegar included their anthocyanin profile (by LC/MS), and their non-anthocyanin phenolic profile (by LC/DAD). In addition, wine and vinegar anthocyanin extracts were fractionated by CCC to determine the contribution of the fractions to overall antioxidant activity (AA), using ORAC, FRAP and DPPH assays.A total of 20 anthocyanin compounds were identified in the vinegar. As far as we know, this is the first time that anthocyanin-derived pigments (pyranoanthocyanins and ethyl-linked compounds) have been identified in red vinegar in such detail. Moreover, an original contribution of this study is the identification for the first time of catechyl-pyranocyanidin-3-glucoside in vinegar and wine, as well as two anthocyanin compounds not previously reported in vinegar or Cabernet Sauvignon wine: acetyl vitisin B and coumaroyl vitisin B. After the acetification process, vitisin-type and ethyl-linked compounds increased and monomeric anthocyanins, phenolic acids (ferulic acid, caffeic acid and caftaric acid) and flavan-3-ol ((+)-catechin) decreased.Although the proportion by weight of the polymeric compound fraction is similar in wine and vinegar, the AA of these polymers in vinegar is significantly greater (p
... Both TA and TP showed a reduction in their contents, 97% and 28% respectively, with respect to final values determined after alcoholic fermentation. Decrease in these bioactive compounds has been recorded by several authors (Su & Chien, 2007;Cerezo et al., 2010;Ubeda et al., 2013;Davies, 2015;Cunha et al., 2016;Hornedo-Ortega et al., 2017) although ratio varies according to acetification system, contact of the fruit with its skin during alcoholic fermentation, and phenolic composition of the raw material. ...
... The significant reduction in the TA content was attributed to their great susceptibility to oxidation (Cerezo et al., 2010;Ubeda et al., 2013) considering the strong aeration and high processing time, although other researchers attributed this reduction to polymerization reactions with other phenolics (Andlauer et al., 2000;Cerezo et al., 2010). Although anthocyanins are more stable at low pH, the reduction does not prevent the effects of acetic biooxidation (Hornedo-Ortega et al., 2017). ...
... The significant reduction in the TA content was attributed to their great susceptibility to oxidation (Cerezo et al., 2010;Ubeda et al., 2013) considering the strong aeration and high processing time, although other researchers attributed this reduction to polymerization reactions with other phenolics (Andlauer et al., 2000;Cerezo et al., 2010). Although anthocyanins are more stable at low pH, the reduction does not prevent the effects of acetic biooxidation (Hornedo-Ortega et al., 2017). ...
Blueberries are widely recognized for their beneficial health effects due to their bioactive compounds content. In addition, balsamic vinegars trade developed quickly because of their wide acceptance in gourmet food. A novel product made with second quality berries, being suitable for human consumption, i.e., blueberry balsamic vinegar, was evaluated. This work aimed to assess changes in Total Anthocyanins (TA), Total Phenolics (TP), and antioxidant activity during production process of blueberry balsamic vinegar, at the following stages: raw material, blueberries juice after enzyme treatment, blueberries alcoholic substrate, blueberries vinegar, concentrated blueberry juice and blueberries balsamic vinegar. Additionally, three alternative evaporation systems, rotary vacuum evaporator, microwave and vacuum microwave, were evaluated in order to determine the concentration method that best retains TA and TP in blueberry juice for its further use in this process. The highest TA and TP retention was achieved by blueberry juice concentration with a rotary vacuum evaporator. On the other hand, both alcoholic fermentation and acetification negatively affected those compounds and antioxidant activity during vinegar production. However, mixing with concentrated juice to obtain blueberry balsamic vinegar allowed balancing nutrient concentration reductions due to processing. The present study showed that production of blueberry balsamic vinegar gives rise to an interesting possibility to reduce losses due to fruit waste while getting added value products with healthy qualities.
... Nowadays, the separation technique which is commonly applied is liquid chromatography using mainly C18 reversed-phase columns. This technique combined with UV-Vis (PDA (Photodiode array)) and/or mass spectrometry detectors has been used for the determination of anthocyanin content in various matrices [12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28]. One of the most interesting and distinguishing characteristics of the anthocyanins group is that in different pH conditions, their structure changes, resulting in a change of their color as well. ...
... Nowadays, the separation technique which is commonly applied is liquid chromatography using mainly C18 reversed-phase columns. This technique combined with UV-Vis (PDA (Photodiode array)) and/or mass spectrometry detectors has been used for the determination of anthocyanin content in various matrices [12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28]. ...
... HPLC-DAD-MS has been widely used for the analysis of anthocyanins in various samples, such as purple corn cob [17][18][19][20][21][22], while the LC-nano-DESI-MS has been used in red wine analysis [23]. Last but not least, the use of LC-MS/MS has been applied in order to analyze wine grape skins [24], berry skins [22,25], human saliva [26], elderberry extracts [27] and red wine vinegar [28]. ...
Anthocyanins are a group of phenolic compounds with great importance, not only because they play a crucial role in a wine’s quality, but also due to the fact that they can have beneficial effects on human health. In this work, a method was developed for the detection and identification of these compounds in solid wastes of the wine-making industry (red grape skins and pomace), using liquid-liquid extraction (LLE) prior to the liquid chromatography-mass spectrometry technique (LC-MS). The complete process was investigated and optimized, starting from the extraction conditions (extraction solution selection, dried matter-to-solvent volume ratio, water bath extraction duration, and necessary consecutive extraction rounds) and continuing to the mobile phase selection. The extraction solution chosen was a methanol/phosphoric acid solution (95/5, v/v), while three rounds of consecutive extraction were necessary in order to extract the maximum amount of anthocyanins from the byproducts. During the LC-MS analysis, acetonitrile was selected as the organic solvent since, compared with methanol, not only did it exhibit increased elution strength, but it also produced significantly narrower peaks. To enable accurate identification of the analytes and optimization of the developed method, kuromanin chloride and myrtillin chloride were used as standards. Furthermore, the wine variety (Syrah) from which the specific byproducts were produced was analyzed for its anthocyanin content, leading to interesting conclusions about which anthocyanins are transferred from grapes to wine during the vinification procedure, and to what extent. The results of this study showed that the total concentration of anthocyanins estimated in wine byproducts exceeded almost 12 times the equivalent concentration in Syrah wine, while the four categories of detected anthocyanins, simple glucosides, acetyl glucosides, cinnamoyl glucosides, and pyroanthocyanins, were present in different ratios among the two samples, ranging from 18.20 to 1, to 5.83 to 1. These results not only confirmed the potential value of these byproducts, but also indicated the complexity of the anthocyanins’ transfer mechanism between a wine and its byproducts.
... First, the vinification process of wine production promotes several reactions between anthocyanins and other molecules, such as pyruvic acid, vinyl phenol, acetone, and glyoxylic acid, leading to a decrease in free anthocyanin contents and copolymerization reactions between tannins and anthocyanins [23,28]. Second, the acetification process of Sherry wine to a vinegar product [12] was observed with a decrease (~50%) in the content of monomeric anthocyanins during the acetification of red wine. In many studies, the acetification process was related to a decrease in the total phenolic content of 13%. ...
... This result can be explained by the acetification process of red wine vinegar and the loss of t-resveratrol in wood. Additionally, this may be due to polymerization and precipitation [12,29]. ...
The Jerez (Sherry) vinegars, including Vinagre de Jerez, Reserva, and Gran Reserva, are crafted from Sherry wines and are protected under the Denomination of Origin in Spain. The aim of this study was to (i) characterize the physicochemical properties and composition; (ii) investigate the impact of the aging process on color properties, phenolics, volatile compounds, and sensorial profiles; and (iii) find a marker for tracing the authenticity of non-aged (Apto) and aged Jerez vinegars. The phenolic components were identified through LC-MS/MS, whereas the volatile compounds were examined using the GC-MS/MS technique. As the aging progressed, a decrease was observed in the levels of flavonol and phenolic acids, with anthocyanin components being undetectable in non-aged and aged samples. In the Gran Reserva variety, 2-methylbutyl acetate, acetic acid, and ethanol emerged as the predominant volatile substances. The presence of oaklactone and ethyl butanoate components served as marker substances to authenticate the Gran Reserva. Additionally, alterations in color properties were noted, marked by a decrease in yellow content and an increase in the red component depending on aging. Furthermore, novel sensory descriptors, such as vanilla, clove, woody, and nutty notes, and winy character emerged in the samples with prolonged aging.
... Phenolic acids and aldehydes are indicated as useful quality parameters of wine vinegars besides their major components. [4] ...
... Total phenolic and total flavonoid contents of homemade red wine and red balsamic vinegars were considerably higher than other samples. Anthocyanin content of red wine vinegar was investigated in another study [4] and 20 anthocyanin compounds such as catechyl, pyranocyanidin-3-glucoside, acetyl vitisin B, and coumaroyl vitisin B were determined in this type of vinegar. Twenty traditional home-made and five industrial vinegars, produced from grape, grape wine, apple, artichoke, pomegranate, lemon, and sour cherry, were inspected by Ozturk et al. [16] Vinegars had extremely variable total phenolic content values, ranging between 42.04 and 2228.79 mg GAE/L. ...
There has been a growing interest in vinegar, especially after the increasing reports about its beneficial health effects. Bioactive compounds of vinegar are associated with its antimicrobial, antioxidant, antidiabetic, antitumor, and anti-obesity types of activities. Quality of vinegar is related with the authenticity of the product besides the amounts of bioactive compounds in its composition. Addition of cheaper substitutes to higher quality vinegars and false labeling are some common authentication problems for this product. There are various examples of the use of targeted and untargeted methods in authentication studies for vinegars. Specific constituents and properties of vinegars such as molecular isotope ratios and individual volatile compounds were used to detect adulteration with targeted methods. On the other hand, untargeted methods, mostly in the form of the application of spectroscopic techniques, such as infrared and fluorescence spectroscopy in combination with chemometrics, provide an overall measurement. This review mainly focuses on adulteration types and elaborates on different targeted and non-targeted methods used to authenticate vinegars.
... In the production of industrial vinegar, this practice is performed. The results obtained from the vinegar are comparable to Cerezo et al. (2010), which reported a red wine vinegar from Cabernet Sauvignon with antioxidant activity values for ORAC, DPPH and FRAP of 4,630 μmol TE/L, 10,200 μmol TE/L and 1,693 mg AAE/L, respectively (42). ...
... In the production of industrial vinegar, this practice is performed. The results obtained from the vinegar are comparable to Cerezo et al. (2010), which reported a red wine vinegar from Cabernet Sauvignon with antioxidant activity values for ORAC, DPPH and FRAP of 4,630 μmol TE/L, 10,200 μmol TE/L and 1,693 mg AAE/L, respectively (42). ...
Vaccinium meridionale produces fruits with a high content of anthocyanins and polyphenols with great antioxidant capacity. Objective: produce vinegar from V. meridionale alcoholic beverages and to determine the content of bioactive antioxidant compounds, antioxidant capacity, and cytotoxic activity on colorectal cancer cells. Methods: Wine and vinegar samples were obtained by fermentation of V. meridionale berries juice, using three extractive processes: mechanical maceration (MAC), preheating to 80 °C (CAL) and a combination of both (MIX). During acetic fermentation, titratable acidity and acetic acid content were evaluated. Fermentation progress was recorded and compared by measuring the antioxidant potential by DPPH, FRAP, and ORAC. Polyphenols, anthocyanins and hydroxycinnamic acids were quantified. Finally, the antiproliferative activity of vinegar was evaluated in SW480 colon cancer cells.
Results: In acetic fermentation, yield and productivity were independent of extraction, indicating that they do not affect the biotransformation of alcohol into vinegar. The alcoholic beverages showed the highest antioxidant activity; after acetic fermentation, a decrease in antioxidant potential was observed in all three extractive processes valuated. The different vinegar obtained by CAL and MIX, showed the highest values of antioxidant activity, polyphenols, and anthocyanins. The inhibition of the antiproliferative activity of vinegar was dose-dependent and showed an IC50 of 536 μg/mL. Conclusions: The vinegar prepared from V. meridionale berries presented an outstanding antioxidant and antiproliferative activity. The reason is the contents of bioactive compounds and their antioxidant power, which may contribute to chemoprevention in secondary cancer prevention.
... It has been observed in studies that as the amount of anthocyanin decreases due to aging or vinification, there is a shift from red color to more yellow color (Almela 1993, Pascu 2005, Alcalde-Eon et al. 2006, Uysal et al. 2023. Moreover, it has been reported that the concentration of monomeric anthocyanins decreases during acetification process of vinegars because of polymerization reactions (Cerezo et al. 2010). Therefore, although the concentration of some phenolic compounds decreases, the slight change in color can be explained by the low level of anthocyanins. ...
The aged vinegars studied, which are Sherry vinegars from Jerez, Spain, with varying aging periods, are
protected under the Denomination of Origin (DO). The objectives of this study were to (i) examine the impact
of aging on the polyphenolic compound content and color properties of Sherry vinegars, and (ii) determine the
correlation between phenolic compounds and color properties in these samples. Phenolic compounds were
identified and quantified using LC-MS/MS technique, and correlation analysis was conducted between
phenolic content and color properties. The results showed a statistically significant decrease in total phenolic
content with increased aging. Additionally, all colorimetric properties exhibited significant changes across the
samples. A notable shift from yellow to red hues was observed in the vinegars. Significant reductions in caffeic
acid and gallic acid content were also found due to aging. This study is the first to analyze the correlation
between phenolics and color properties in Sherry vinegars, revealing the influence of phenolic compounds on
their color characteristics.
... Other authors found significant losses of anthocyanins during the acetic fermentation process of strawberry vinegars, which they attributed to the oxidative processes that took place in a medium with a large amount of oxygen, as in their study they used submerged fermentation to produce the vinegars [25]. Similar results were found by [26][27][28] when using different alcoholic matrices. In our case, the lower losses with respect to those observed in the above mentioned studies could be due to the lower availability of oxygen during the acetification process, as the surface process was employed. ...
This work aims to determine the effect on the aromatic profile and phenolic content of red wine vinegars produced by surface culture at two different temperatures (30 °C and 37 °C) and using different inocula of acetic acid bacteria (Acetobacter malorum, Gluconobacter oxydans and a mixture of bacteria isolated from a Sherry vinegar). Fifty-seven volatile compounds and 23 polyphenolic and furfural compounds were identified. Vinegars obtained at 37 °C had poorer volatile profiles, with no significant influence of the strain of acetic bacteria. For polyphenolic content, temperature was also the most significant variable, so that the vinegars produced at higher temperatures had lower total anthocyanin contents, while no clear trend was observed regarding the influence of temperature on the low-molecular-weight phenolic constituents. The total tannin content in the vinegars obtained experienced slight increases after acetification, although this was not affected by temperature, and it was observed that when using the mixture of acetic acid bacteria from the Sherry vinegar, the total tannin content was significantly higher than when individual bacteria cultures of Acetobacter malorum or Gluconobacter oxydans were used. Temperature appears as a key parameter for the volatile and phenolic composition of red wine vinegar versus the use of different acetic acid bacteria.
... Other authors found significant losses of anthocyanins during the acetic fermentation process of strawberry vinegars, which they attributed to the oxidative processes that took place in a medium with a large amount of oxygen, as in their study they used submerged fermentation to produce the vinegars [25]. Similar results were found by [26][27][28] when using different alcoholic matrices. In our case, the lower losses with respect to those observed in the above mentioned studies could be due to the lower availability of oxygen during the acetification process, as the surface process was employed. ...
... Entre las posibles explicaciones a este fenómeno estaría la actividad antocianasa (antocianina-β-glucosidasa) observada en algunas bacterias, por ejemplo en Oenoccocus oeni [46], degradando las antocianinas [47]. Otra posible explicación sería la polimerización de las antocianinas de bajo peso molecular, especialmente cuando su concentración alcanza valores altos [48], generando una disminución de la concentración de las formas monoméricas [49]. En la Figura 6 se presenta el contenido total de fenoles obtenidos en los vinagres A-ch, A-ch+30s y A-ch+60s. ...
... DPPH radical scavenging activity was measured according to Cerezo et al. (2010), and ascorbic acid (0.5 mg/mL) was used as a positive control. DDPH (0.1 mM) was dissolved in ethanol. ...
Blueberry is a characteristic berry fruit shrub of the genus Vaccinium in the Rhododendron family. The fruit is rich in anthocyanins and has a variety of nutritional and health functions. This study aimed to systematically study the effect of exogenous abscisic acid (ABA) application on ripening and metabolites in blueberry fruits. Blueberry fruit ripening was divided into six stages for further analysis. In this study, nontarget metabolomics was performed to demonstrate the effect on metabolite levels. The results showed that 1000 mg/L ABA significantly promoted fruit ripening and increased anthocyanin content. Moreover, exogenous ABA treatment can affect endogenous ABA levels and improve its antioxidant capacity. Important metabolites of the flavonoid pathway were detected, and the results showed that anthocyanin synthesis increased, and some other bioactive metabolite levels decreased. After comprehensive assessments, we believe that 1000 mg/L exogenous ABA application will have positive impacts on blueberry fruit quality and economic benefits.
... Polyphenol content and types in vinegars also differ based on the raw materials and production processes [40]. Fruit-based vinegars contain high amounts of catechins, gallic acid, and some more phenolic compounds, which are low in grain vinegars [22,[41][42][43][44]46]. Chlorogenic acid is found more in apple vinegars which is also present in its source raw material [42,45,47,82]. ...
BACKGROUND
Cherry laurel fruit (CLF) has distinctive bioactive properties, which may yield new food products based on CLF.
OBJECTIVE
This research aimed to realize the production of vinegar from the CLF, thus, valorizing the CLF, which is rich in antioxidants and phenolic substances, and bringing a new nutrient-rich vinegar to the market.
METHODS
Seven types of traditional CLF vinegar (CLFV) from three different species were produced, and their bioactive properties were examined. The bioactivity analyses of total phenolic substance (TPC), total flavonoid (TFC), total antioxidant activity (AA), DPPH ࢫ (Free radical scavenging activity), FRAP (Ferric reducing antioxidant power), ABTS ࢫ + (Radical cation scavenging effect) were conducted. In addition, the composition of phenolic substances was studied.
RESULTS
This study showed that CLFV performed better than controls regarding antioxidant activity, phenolic compounds, and substances. The presence of intense phenolic elements in CLFV significantly impacts its antioxidant activity. The antioxidant activities of CLFV were detected to be greater than the previous reports on bioactivities of vinegar from various fruits.
CONCLUSIONS
High antioxidant and phenolic content were observed in CLFV, similar to the composition of the CLF. The usability of CLFV as a healthy and nutritious food product seems achievable on an industrial scale.
... The absorbance was measured at 517 nm after standing for 30 min at room temperature. The oxygen radical absorbance capacity (ORAC) value was based on the study by Cerezo et al. (2010) ...
Blueberry fruit is famous for its anthocyanin abundance and has high nutritional, medicinal, and economic value. The adaptability of different source cultivars to high temperature in summer has not been systematically explored. The objective of this study was to evaluate the suitability of different blueberry cultivars under different shading environments and explore the effects of different shading intensities on fruit quality and antioxidant substances. In this study, three cultivars respectively belonging to three types (rabbiteye, southern highbush, and northern highbush) of blueberries were shaded, and the fruit size, shape, hardness, nutritional quality index, and antioxidant substances were determined. The results show that excessive shading affects flower bud differentiation, leading to abnormal flowering and fruiting of the blueberry cultivar ‘Chandler’. The fruit firmness of highbush blueberries (‘Primadonna’ and ‘Chandler’) in the one-layer black shading (T1) group was significantly higher than that in the total light (CK) group. Total phenols, flavonoids, anthocyanins, and protein reached the highest values in the T1 treatment for cultivar ‘Brightwell’. Moreover, the malondialdehyde and H2O2 contents and peroxidase activity in the T1 group were significantly lower than those in the two-layer black shading (T2) group, but the catalase and polyphenol oxidase activities in the T1 group were significantly higher than those in the T2 group. There was a correlation between the main antioxidant substances, and different blueberry cultivars had different tolerances to shading. This study provides a practical reference for improving fruit quality and the efficient utilization of antioxidant substances in blueberry production.
... In the same line as our findings, a decrease from 8% to 54.3% of phenolic content was reported during acetification of orange, cider, white, and red grape wines (Andlauer, Stumpf, & Fürst, 2000; Davies et al., 2017). In addition, 12-17% of decrease of the antioxidant activity value was recorded during the acetification of orange and red grape wine, and this reduction was attributed to the changes in chemical composition caused by the bio-oxidative process (Cerezo, Cuevas, Winterhalter, Garcia-Parrilla, & Troncoso, 2010;Davies et al., 2017). However, in the RHV samples, TPC content FRAP and DPPH activity values increased compared to the values of the RHW, ABTS and Fe 2+ chelating activities (84.20 mmol TE/mLand 771.50 μg TE/mL) increased compared to the values of both RHJ and RHW. ...
This study was aimed to be produced rosehip vinegar production from rosehip fruit, which has a limited usage, for the first time, and to monitor in detail the changes in bioactive compounds and volatile compounds, which affected on aroma property of it, during the rosehip vinegar production. Thus, it was aimed to contribute to the modernization of fermented foods and to produce rosehip vinegar as a healthy, aromatic and alternative product. The results showed that the rosehip vinegar had high TPC, TFC contents, and antioxidant activity. And catechin, ellagic-acid, quercetin, taxifolin, 4-hydroxy-benzoic-acid, and salicylic-acid were the important phenolic compounds in the rosehip wine and vinegar. Besides, vitamin-C content increased during the fermentation, and the highest value of vitamin-C was obtained in the rosehip vinegar. And, in the vinegar, it was displayed a total of 27 volatile compounds, the major compounds were acetic-acid, acetoin, pentanoic-acid, propionic-acid, octanoic-acid, followed by vitispirane, phenethyl-alcohol, isobutyric-acid, and 1-p-menthen-9-al. As a result, it has been thought that the rosehip fruit an adequate substrate for the production of rosehip vinegar which is a healthy and aromatic vinegar. Also, rosehip vinegar, obtained from rosehip fruit, which has a limited usage was contributed to the modernization of fermented foods.
... It is possible to buy a spray-dried vinegar powder, which provides maximum vinegar taste and may be rehydrated with water in a ratio of 1:1/vinegar:water. The health benefits of vinegar are due to acetic acid and other organic acids (mainly acetic acid and lactic acid together with malic acid, tartaric acid, citric acid and succinic acid), amino acids, phenolic compounds (e.g., catechin, chlorogenic acid, syringic acid, ferulic acid, protocatechuic acid, caffeic acid, gallic acid and p-coumaric acid), flavanols (e.g., epicatechin), flavonols (e.g., rutin), anthocyanidin (e.g., malvidin-3-glucoside), anthocyanin (e.g., pyranoanthocyanin), carotenoids, vitamins (B group and C), minerals (Al, Ca, Cr, Fe, K, Mn, Mg, Na, P, S and Zn), alkaloids and sugars (glucose, arabinose, fructose, xylose and mannitose) able to induce antioxidant, antitumor, antidiabetic, antihypertensive, antiobesity, antiinflammatory and antimicrobial effects [24,25]. The bioactive compounds' composition and concentration depend on the raw material used to produce the vinegar and the production method [26]. ...
Spices, condiments and extra virgin olive oil (EVOO) are crucial components of human history and nutrition. They are substances added to foods to improve flavor and taste. Many of them are used not only to flavor foods, but also in traditional medicine and cosmetics. They have antioxidant, antiviral, antibiotic, anticoagulant and antiinflammatory properties and exciting potential for preventing chronic degenerative diseases such as cardiomyopathy and cancer when used in the daily diet. Research and development in this particular field are deeply rooted as the consumer inclination towards natural products is significant. It is essential to let consumers know the beneficial effects of the daily consumption of spices, condiments and extra virgin olive oil so that they can choose them based on effects proven by scientific works and not by the mere illusion that plant products are suitable only because they are natural and not chemicals. The study begins with the definition of spices, condiments and extra virgin olive oil. It continues by describing the pathologies that can be prevented with a spicy diet and it concludes by considering the molecules responsible for the beneficial effects on human health (phytochemical) and their eventual transformation when cooked.
... DPPH radical scavenging activity were measured by the following method and the ascorbic acid (0.5 mg/ml) was used as positive control 33 . DDPH(0.1 mM) was dissolved in ethanol. ...
Background: Blueberry is well known for its high content of bioactive metabolites, including anthocyanins, flavonols, and phenolic acids. This study aims to systematically study the effect of exogenous ABA application on ripening fruits in fruit growth, quality and anthocyanins content. The ripening process of blueberry fruit is divided into six stages for further analysis.
Results: In this article, nontarget metabolomics were performed to demonstrate the effect on metabolites level. Basic results showed that 1000 mg/ml ABA significantly promoted fruit ripening, accelerated fruit colouration and increased soluble solid and anthocyanins content. At the same time, the fruit firmness and the content of some bioactive metabolites were also reduced. In metabolites level, a total of 1145 metabolites and 575 metabolites were detected and annotated in the positive model and the negative model, respectively. Principal component analysis and endogenous ABA content shows the exogenous ABA application is mainly concentrated on the green fruit turning into red fruit, after which the effect begins to decrease. The important metabolites of flavonoid pathway were detected and the result shows that anthocyanins synthesis was increased and parts of other bioactive metabolites were decreased.
Conlusion: After comprehensive assessments, we believe that 1000 mg/ml exogenous ABA will have positive impacts on blueberry fruit quality and economic benefits. This finding provides a reference for different cultivation methods to improve the anthocyanin content of blueberry. Also, it provides a good research foundation for the next step of precise breeding for specific active compound of blueberry.
... The phenolic compounds in different vinegars such as traditional balsamic vinegar (TBV) [26], persimmon vinegar [27], strawberry vinegar [28], and SAV [29,30] were also studied. In addition, other bioactive compounds including ligustrazine [31] and 5-hydroxy-4-phenyl-butenolide [32] in cereal vinegar, caffeoylsophorose in purple sweet potato vinegar [33], tryptophol in black soybean vinegar [34], amino acids [35], vitamins [36], melanoidins [37][38][39], polysaccharides [6,40], and anthocyanin [41] were also studied. ...
Vinegar is one of the most widely used acidic condiments. In recent decades, rapid advances have been made in the area of vinegar research, and the intellectual structure pertaining to this domain has significantly evolved. Thus, it is important that scientists keep abreast of associated developments to ensure an appropriate understanding of this field. To facilitate this current study, a bibliometric analysis method was adopted to visualize the knowledge map of vinegar research based on literature data retrieved from the Web of Science Core Collection (WoSCC) database. In total, 883 original research and review articles from between 1998 and 2019 with 19,663 references were analyzed by CiteSpace. Both a macroscopical sketch and microscopical characterization of the whole knowledge domain were realized. According to the research contents, the main themes that underlie vinegar research can be divided into six categories, that is, microorganisms, substances, health functions, production technologies, adjuvant medicines, and vinegar residues. In addition to the latter analysis, emerging trends and future research foci were predicted. Finally, the evolutionary stage of vinegar research was discerned according to Shneider's four-stage theory. This review will help scientists to discern the dynamic evolution of vinegar research, as well as highlight areas for future research.
... With positive ion mode, HPLC-FT-ICR-MS was used to detect anthocyanins, and the results were presented in Table 2 H. Suo, et al. Food Research International 123 (2019) 440-449 high mass accuracy measurements, these anthocyanins could be identified as malvidin-3-O-glucoside-4-vinyl-catechol, delphinidin-3-O-glucoside pyruvic adduct, peonidin-3-O-glucoside-4-vinyl-phenol, malvidin-3-O-glucoside-4-vinyl-phenol, malvidin-3-O-glucoside-4-vinylguaiacol (Anab, Elyana, Peter, Mcarmen, & Anam, 2010). Peak 53 showing an ion with m/z of 565.11427 and fragment ion with m/z of 271.05950 coincident with formulas C 26 H 29 O 14 was identified as pelargonidin-3-O-sambubioside. ...
High-molecular-mass polymeric polyphenols (HPPCs) is the major group of polyphenols in red wine. However, owing to the diversity and structural complexity, its compositional characterization remains a difficulty. In this study, purified high-molecular-mass polymeric polyphenols (PHPPCs) was isolated by solid phase extraction combined with semi-preparative HPLC from red wine. Different chemical degradation methods (NaOH, HCl and benzyl mercaptan degradation) were used to decompose the PHPPCs into low molecular weight fragments. The chemical structures of the degradation fragments were verified by HPLC/UPLC−DAD and HPLC-FT-ICR-MS. The results showed that three proanthocyanidins, five proanthocyanidins benzylthioether, quercetin and fifteen anthocyanins were detected by degradation in the presence of benzyl mercaptan. Nine bound phenolic acids were found by NaOH degradation and twelve bound amino acids were proved by HCl. Among these different fragments detected,delphinidin-3-O-glucoside pyruvic adduct, four acylated anthocyanins, four hydroxyphenyl pyranoanthocyanins, quercetin, protocatechuic acid, vanillic acid, and cinnamic acid were first found in the PHPPCs. For the first time amino acids as constitutive units of polymeric polyphenols in red wines were verified. Based on the degradation fragments, the possible compositional characterization of HPPCs in red wine was postulated.
... A similar value, 16.8%, was reported for a red wine acetification process, using the latter methodology. Researchers attributed this reduction to changes in chemical composition caused by biooxidative process (Cerezo et al., 2010). ...
Citrus fruits are significant sources of bioactive compounds, such as ascorbic acid, polyphenols and carotenoids, due to their antioxidant properties important for human nutrition. In addition, since oranges possess high sugar content (8-15%), making vinegars from alcoholic orange substrates, with functional characteristics is a possible development of novel products. The aim of this research work was to analyze changes in ascorbic acid, total phenolics, total carotenoids and antioxidant activity during orange vinegar processing. In order to analyze the influence of acetification and aging in these characteristics, samples were taken in three stages: orange alcoholic substrate for acetification (SNA), young orange vinegar or recently obtained (Vn0) and orange vinegar after six month-aging in bottles (Vn6). Statistically significant differences (p < 0.05) were found among bioactive compounds concentrations; antioxidant activity decreased along the process, but total phenolics and carotenoids remained constant during aging period (Vn0-Vn6). The highest reduction was recorded during the acetification stage, possibly due to components oxidation caused by continuous air flow to the system. A higher contribution (p < 0.05) to antioxidant activity was associated to ascorbic acid and phenolic compounds concentration.
... These reactions include selfassociation and co-pigmentation, such as the formation of polymeric anthocyanins with flavan-3-ols and proanthocyanidins, as well as the formation of new pigments, such as pyranoanthocyanins (Brouillard, Chassaing, & Fougerousse, 2003;Jackson, 2008;Wrolstad, Durst, & Lee, 2005). Acetification process of red wine also modifies anthocyanin composition, increasing vitisin-type and ethyl-linked compounds and decreasing the monomeric anthocyanins (Cerezo, Cuevas, Winterhalter, Garcia-Parrilla, & Troncoso, 2010b). However, the impact to anthocyanin composition of the gluconic fermented matrix products has not been studied. ...
... The aim of the present work was to optimize a nano-liquid chromatographic method for the separation of catechin, malvidin-3-glucoside and pigments formed by their mutual condensation in the presence of acetaldehyde (following reaction described elsewhere [24]) and to compare it with a conventional chromatographic method. Pigments produced by linkage of anthocyanins with flavanols appear in significant content in different foods such as red wine vinegard [25] and red wine [26][27][28]. This study represents one of the initial steps in development of a comprehensive analytical platform for targeted monitoring of condensation of anthocyanins in micro-samples of plant material and related food. ...
Nano-liquid chromatography and conventional HPLC were used for the separation of diastereomers of (+)-catechin-ethyl-malvidin-3-glucoside. Those bridged anthocyanin dyes were obtained by reaction of (+)-catechin with malvidin-3-glucoside in the presence of acetaldehyde. Both diastereomers were isolated with semipreparative chromatography and their structures were confirmed by nuclear magnetic resonance and mass spectrometry. In-laboratory prepared capillary columns packed with fully porous particles Chromosphere C18, dp=3μm, core-shell particles Kinetex C18, dp=2.6μm (100μm i.d.) and monolithic column Chromolith CapRod (100μm i.d.) were used for the separation of (+)-catechin, malvidin-3-glucoside and both diastereomers. Chromosphere C18 stationary phase provided the best chromatographic performance. Mobile phase containing water:acetonitrile (80:20) acidified with trifluoroacetic acid (0.1%, v/v/v) was used in an isocratic elution mode with a flow rate of 360nLmin(-1). Separation of studied compounds was achieved in less than 7min under optimized conditions. The nano-liquid chromatographic method and a conventional HPLC one using the same fully porous particles (Chromosphere C18, 3μm, 100mm×4.6mm) were compared providing higher separation efficiency with the first analytical method and similar selectivity. A better peak symmetry and higher resolution of the studied diastereomers was achieved by conventional chromatography. Nevertheless, nano-liquid chromatography appeared to be useful for the separation of complex anthocyanin dyes and can be utilized for their analysis in plant and food micro-samples. The developed method was used for analysis of red wine grape pomace.
... The result reported in our study was about 12% which was alike of the red wine vinegars. The decrease in total phenolic content can be attributed to polymerisation or condensation reactions with other phenols, a similar phenomenon in vinous and berry substrates [20]. Accordingly CCV showed a decrease in the total phenolics content but the percent decrease was lower than cider vinegar and higher than white wine vinegars. ...
Vinegar made from corncob, an agricultural waste product of corn, is of interest in terms of its potential as a new functional condiment with physiological characteristics derived from polyphenols. The advent of food out of waste using lignocellulosic substrates is a modern biotechnological approach to enhance sustainability. The fermentation parameters for production of fermented vinegar from corncobs were optimized. The ethanolic fermentation was completed by Saccharo-myces cerevisiae in 52 hours at 36˚C producing 3.16% (v/v) ethanol. The acetic acid fermentation was carried out by Acetobacter aceti in 48 hours at 34˚C for producing vinegar having 3.91% (w/v) acetic acid. Total phenolic compound of corncob wine and vinegar was reported as 49 mg/100ml and 43 mg/100ml respectively. Total flavonoid content was determined to be about 12 mg/100ml of corncob wine and 9 mg/100ml of corncob vinegar. Corncob wine and vinegar showed highest antioxidant activity with 39% and 37.94% respectively. The structural change during the two step fermentation was also confirmed by scanning electron microscope (SEM). The Hunter color value of the corn cob vinegar was also evaluated. With the current trend of shifting to natural products, corncob vinegar with better health benefits and economic significance, certainly scores high above its synthetic counterpart.
... In the open system the degradation of phenolics was lower than that in the closed system for the four compounds studied (C-3-G, C-3-R, orientin, and homorientin) ( Fig. 7a and b). The degradation in an aerobic environment could be explained to acetification by AAB (Cerezo et al., 2010). Su and Silva (2006) also reported drastic decreases in anthocyanins, total polyphenols, and antioxidant activity during the acetification of blackberry wines for 96 h at 15 • C in a closed system with a supply of oxygen. ...
Açai (Euterpe oleracea) fruit (EOF) are widely commercialized in the Brazilian Amazon. These fruit contain a high bacterial load and are transported on boards stowed inside or outside the holds of small boats. In this context, postharvest parameters were assessed under conditions that simulated these two methods of EOF transport: stowage in closed polystyrene boxes, simulating the inside of cargo holds, i.e., transport in a closed system; and open baskets, simulating transport in an open environment, i.e., transport in the prow or bow of the boat. EOF suffered spontaneous fermentation of alcoholic, acetic, and lactic types in the closed system, which is the most common type of transportation of this fruit. In the closed system, there was a predominance of lactic acid bacteria over acetic acid bacteria, with 82% and 95% of the initial content of d-glucose and d-fructose being consumed, respectively, after 27 h of experiment. The weight loss reached 1.7% and there was a logarithmic decrease of the major phenolic compounds of the fruit in the closed system, with losses of 78% of cyanidin-3-rutinoside, 88% of cyanidin-3-glucoside, 78% of homorientin, and 72% of orientin after 27 h, which was higher than in the open system (58%, 66%, 73% and 62%, respectively). Analyses on EOF stowed in a closed system indicated that the respiratory rate was characteristic of a non-climacteric fruit, i.e., it showed a logarithmic decay in the production of CO2 (R2 = 0.995; P < 0.05). Thus, transport in a closed system results in more drastic nutritional and functional changes on EOF than when transport is carried out in an open system, suggesting that transportation in continuous aerobic conditions and a short period of time between picking and processing are preferable.
... The ORAC antioxidant capacity values of mothers of apple and pomegranate vinegars were higher than the values of vinegar varieties that are stated in the literature in general and that are produced from different raw materials. ORAC values were found to be around 4.63 mM Trolox in red wine vinegar[49], 1479 to 2111 mmol TE/kg in Asian persimmon vinegar ...
Objective:
Mother vinegar is extracellular cellulose and is a thick, hard layer formed by the acetic acid bacteria on the surface of vinegar. The aim of the study was to determine the bioactive components of mother vinegar produced from various vinegars.
Methods:
Mothers of vinegar were produced during vinegar productions using surface culture method from apple and pomegranate juices. Titration acidity, pH, total dry matter, ash, mineral substances, total carbohydrate, total phenolic substance, phenolic components, and total antioxidant activity were determined in samples.
Results:
It was found that mother of pomegranate vinegar had higher antioxidant capacity and total phenolic substance compared to samples of mother of apple vinegar. According to standards, gallic acid and chlorogenic acid were dominant phenolic compounds in mother of apple vinegar, whereas gallic acid was the major phenolic compounds in mother of pomegranate vinegar. The mother vinegars had high Fe contents.
Conclusion:
It was concluded that mother of vinegar produced by natural acetic acid bacteria contains significant bioactive substances.
... C. Ubeda et al. / LWT -Food Science and Technology xxx (2012) 1e7 5 501 502 503 504 505 506 507 508 509 510 511 512 513 514 515 516 517 518 519 520 521 522 523 524 525 526 527 528 529 530 531 532 533 534 535 536 537 538 539 540 541 542 543 544 545 546 547 548 549 550 551 552 553 554 555 556 557 558 559 560 561 562 563 564 565 566 567 568 569 570 571 572 573 574 575 576 577 578 579 580 581 582 583 584 585 586 587 588 589 590 591 592 593 594 Winterhalter, Garcia-Parrilla, & Troncoso, 2010b). Again, as occurred in alcoholic fermentation, we observed the lowest decreases in all of these parameters in the 2010 samples. ...
... A young, monovarietal, Cabernet Sauvignon red wine, a 2007 vintage, produced under controlled experimental conditions by the "Rancho La Merced" research center (Jerez de la Frontera, Spain), was used to produce the vinegar samples under conditions described in a previous study. 25 The resulting vinegar had 8.97 g/100 mL of acetic acid and an alcoholic degree of 1.33°(%, v/v). ...
Wood shavings are widely employed in vinegar making to reduce aging time. Accordingly, this study aims to evaluate the effects of using shavings from different wood species (acacia, cherry, chestnut, and oak) and of toasting on the release of phenolic compounds into vinegar during the aging process. The study involved aging vinegars using previously toasted shavings and untoasted ones, at 0.5% and 1% (w/v), and collecting samples at 15 and 30 days. The phenolic compounds were analyzed by LC-DAD during the aging process. As a result, wood markers naringenin and kaempferol (cherry), robinetin and fustin (acacia), and isovanillin (oak) were identified for the first time in vinegars. The results also showed that toasting wood shavings decreases the concentration of most flavonoid wood markers (e.g., (+)-taxifolin, naringenin, and fustin) in vinegar, but that it is essential for the highest releases of aldehyde compounds (syringaldehyde, protocatechualdehyde, and vanillin). Remarkably, 15 days was sufficient to obtain the highest increases of most polyphenol compounds in the vinegar. Statistical analysis (linear discriminant analysis) proved that the phenolic compounds identified in vinegars are useful for discriminating vinegars regarding the wood species of the shavings used to accelerate aging.
... As shown in Table 2, the malvidin was the most abundant anthocyanidin in MB and CS samples while the cyanidin derivatives showed the lowest proportion, confirming its behavior observed in previous studies (Cerezo, Cuevas, Winterhalter, García-Parrilla, & Troncoso, 2010;Fanzone et al., 2010;González-Neves et al., 2007). ...
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Fermented foods represent an important segment of current food markets, especially traditional or ethnic food markets. The demand for efficient utilization of agrowastes, together with advancements in fermentation technologies (microbial- and enzyme-based processing), are stimulating rapid growth and innovation in the fermented food sector. In addition, the health-promoting benefits of fermented foods are attracting increasingly attention. The microorganisms contained in many common fermented foods can serve as “microfactories” to generate nutrients and bioactives with specific nutritional and health functionalities. Herein, recent research relating to the manufacture of fermented foods are critically reviewed, placing emphasis on the potential health benefits of fermentation-enabled wellness foods. The importance of the correct selection of microorganisms and raw materials and the need for precise control of fermentation processes are explored. Major knowledge gaps and obstacles to fermented food production and market penetration are discussed. The importance of integrating multidisciplinary knowledge, communicating with consumers, establishing regulatory frameworks specifically for fermentation-enabled wellness foods and functional fermented foods, are highlighted.
Vinegars are one of only a few acidic condiments throughout the world. Vinegars can mainly be considered grain vinegars and fruit vinegars, according to the raw materials used. Both grain vinegars and fruit vinegars, which are fermented by traditional methods, possess a variety of physiological functions, such as antibacteria, anti-infection, antioxidation, blood glucose control, lipid metabolism regulation, weight loss, and anticancer activities. The antibacteria and anti-infection abilities of vinegars are mainly due to the presence of organic acids, polyphenols, and melanoidins. The polyphenols and melanoidins also provide the antioxidant abilities of vinegars, which are produced from the raw materials and fermentation processes, respectively. The blood glucose control, lipid metabolism regulation, and weight loss capabilities from vinegars are mainly due to acetic acid. Besides caffeoylsophorose (inhibits disaccharidase) and ligustrazine (improves blood circulation), other functional ingredients present in vinegars provide certain health benefits as well. Regarding anticancer activities, several grain vinegars strongly inhibit the growth of some cancer cells in vivo or in vitro, but related functional ingredients remain largely unknown, except tryptophol in Japanese black soybean vinegar. Considering the discovering of various functional ingredients and clarifying their mechanisms, some vinegars could be functional foods or even medicines, depending on a number of proofs that demonstrate these constituents can cure chronic diseases such as diabetes or cardiovascular problems.
We performed mass spectrometry (MS)-based metabolite profiling of Cheonggukjang (CGJ) and three types of garlic (normal, sprouted, and fermented) added CGJ (G-CGJ). Metabolite profiling suggested that the major distinguishing factor between the four types of CGJ lay in whether garlic was added, although different metabolic states were observed in G-CGJ. Among the discriminant metabolites between CGJ and G-CGJ, the levels of four amino acids such as l-valine, l-isoleucine, l-leucine, and glycine were decreased in G-CGJ compared to CGJ because garlic inhibited the protease activity of Bacillus subtilis during fermentation. In addition, the relative contents of l-cysteine, s-allyl-cysteine, s-allyl-cysteine sulfoxide, soyasaponin βg, and soyasaponin γg, which showed positive correlation with antioxidant activities, were high in G-CGJ. These results suggest that MS-based metabolite profiling could be a useful tool for understanding the metabolic differences of fermented foods according to the additives, and their relationship with antioxidant activity.
Sherry vinegars are appreciated products reaching higher prices in the market than Sherry wine. Actually, the Protection of Designations of Origin is recognized since 1995. Their elaboration encompasses the acetification process to reach the required acetic degree and aging in wood. Phenolic compounds proved to be valid markers to differentiate vinegars according to their origin and elaboration process. Multivariate analysis of phenolic composition data including Linear Discriminant Analysis (LDA) and Artificial Neural Networks trained by Backpropagation (BPANN) classifies correctly vinegar according to the acetification process (LDA=92.5, BPANN =99.6) and origin (LDA=88, BPANN= 96.5). Good recalling classification rates were also obtained for aging periods. Indeed, phenolic aldehydes as syringaldehyde, vanillin, coniferaldehyde increase their concentration during aging. New trends in Sherry vinegars elaboration intends to shorten the production time. This is achieved by obtaining the acetic degree with submerged culture or by accelerating aging with chips. This communication presents the impact of both strategies on phenolic profile. Nowadays certain innovations to produce high quality vinegars include the type of wood used. Compounds released from it as (+)-taxifolin in the case of cherry wood or (+)-dihydrorobinetin for acacia wood are suitable chemical markers to characterize vinegars aged in these woods.
Vinegar is one of the oldest acetic acid-diluted solution products in the world. It is produced from any fermentable sugary substrate by various fermentation methods. The final vinegar products possess unique functions, which are endowed with many kinds of compounds formed in the fermentation process. The quality of vinegar is determined by many factors, especially by the raw materials and microbial diversity involved in vinegar fermentation. Given that metabolic products from the fermenting strains are directly related to the quality of the final products of vinegar, the microbial diversity and features of the dominant strains involved in different fermentation stages should be analyzed to improve the strains and stabilize fermentation. Moreover, although numerous microbiological studies have been conducted to examine the process of vinegar fermentation, knowledge about microbial diversity and their roles involved in fermentation is still fragmentary and not systematic enough. Therefore, in this review, the dominant microorganism species involved in the stages of alcoholic fermentation and acetic acid fermentation of dissimilar vinegars were summarized. We also summarized various physicochemical properties and crucial compounds in disparate types of vinegar. Furthermore, the merits and drawbacks of vital fermentation methods were generalized. Finally, we described in detail the relationships among microbial diversity, raw materials, fermentation methods, physicochemical properties, compounds, functionality, and final quality of vinegar. The integration of this information can provide us a detailed map about the microbial diversity and function involved in vinegar fermentation.
Strawberry is widely harvested in Spain. It is a highly perishable fruit and surplus production may be used to produce innovative foods. This paper studies the influence of gluconic fermentation by Gluconobacter japonicus on the non-anthocyanin content and antioxidant activity of strawberry. A total of 43 non-anthocyanin phenolic compounds were identified. To the best of our knowledge, this paper reports five compounds for the first time in strawberry and its derivatives, tentatively identified as: monogalloyl diglucose, 5-hydroxy feruloyl hexose, dihydrokaempferol hexoside, kaempferol neohesperidoside and (−)chicoric acid. It was further observed that gluconic fermentation leaves in vitro antioxidant activity practically unchanged.
Gluconic fermentation by Gluconobacter japonicus can be considered a potential tool for producing fermented beverages. It transforms glucose into gluconic acid, which allows diabetics to consume the drink, while maintaining bioactive compound concentration and antioxidant activity.
Industrial relevance
This paper has industrial relevance in three main aspects:
-As strawberry is a highly perishable product, fruits spoil quickly, leading to substantial economic losses. Therefore, the transformation of strawberry surplus into new, longer-lasting products is a financially worthwhile solution for the industry and producers.-Our gluconic beverages were elaborated by traditional process using exclusively strawberry as raw material easily transferable to industrial scale.-The main innovation aspect relies on developing an innovative product, aiming to fulfil consumers demand who are permanently seeking for different taste and flavors. At he same time its composition in sugars (non-glucose, original fructose content) makes these products very suitable for dietetic purposes.
researcher at the Institute of Food Research, Norwich, England, is using a Marie Curie Intra-European Fellowship for Career Development to investigate dietary polyphenols and vascular endothelial growth factor signaling. Funded under the European Union's Seventh Framework Pro-gramme, the fellowships enable researchers with a PhD or at least 4 years of full-time research experience to gain advanced training. Dr Cerezo's PhD research in nutrition and food science under the supervision of Ana, led to 6 peer-reviewed articles. She studied the effect of acetification and aging in wood barrels on the phenolic composition of red wine vinegar. 1 The group also identi-fied anthocyanin-derived pigments in red wine and red wine vinegar and described the changes in phenolic com-pounds as a result of the acetification process. 2 It also described the phenolic compounds in red wine, red wine vinegar, and strawberry, including their antioxidant activity and bioaccessibility using in-vitro simulated digestion. 3 Dr Cerezo was awarded her PhD in December 2009 and then applied for a postdoctoral fellowship outside Spain "for several reasons, all relating to my desire to become a research leader in Spain in the future." She adds, "The complementary skills I will acquire during this fel-lowship will prepare me for the demands of being an independent group leader. As a result, I will have sufficient professional independence and experience in research management to initiate an independent research career." The Marie Curie fellowship pays Dr Cerezo's salary for 2 years and provides some funding for research, training, and travel. The Institute of Food Research focuses on the health benefits of polyphenols using molecular nutritional approaches and has links with organisations in the United Kingdom, Europe, and worldwide and the experience of European Union research programmes. Dr Cerezo's project is being supervised by Paul Kroon, PhD, who has carried out research on polyphenols for >12 years. Dr Cerezo will test the hypothesis that certain dietary polyphenols can modulate the function of vascular endothelial cells and reduce cardiovascular disease risk by inhibiting vascular endothelial growth factor sig-naling. Dr Kroon's group has identified a novel mechanism of inhibition of vascular endo-thelial growth factor signaling by polyphenols and has shown that some dietary poly-phenols present in tea, pome-granate, cocoa and dark choco-late, and apples are potent inhibitors at physiologically relevant concentrations. Dr Cerezo says, "Our project will advance understand-ing of the molecular mechanisms by which polyphenols protect against cardiovascular disease and improve our knowledge of polyphenolic compounds with health proper-ties for future exploitation as antivascular endothelial growth factor ingredients in foods and beverages." References
In the Italian oenological industry, the regular practice used to naturally increase the colour of red wines consists in blending them with a wine very rich in anthocyanins, namely Rossissimo. In the Asian market, on the other hand, anthocyanins extracted by black rice are frequently used as correctors for wine colour. This practice does not produce negative effects on health; however, in many countries, it is considered as a food adulteration. The present study is therefore aimed to discriminate wines containing anthocyanins originated from black rice and grapevine by using reliable spectroscopic techniques requiring minimum sample preparation. Two series of samples have been prepared from five original wines, that were added with different amounts of Rossissimo or of black rice anthocyanins solution, until the desired Colour Index was reached. The samples have been analysed by FT-NIR and (1)H NMR spectroscopies and the resulting spectra matrices were subjected to multivariate classification. Initially, PLS-DA was used as classification method, then also variable selection/classification methods were applied, i.e. iPLS-DA and WILMA-D. The classification with variable selection of NIR spectra permitted to classify the test set samples with an efficiency of about 70%. Probably these not excellent performances are due to the matrix effect, together with the lack of sensitivity of NIR with respect to minor compounds. On the contrary, very satisfactory results were obtained on NMR spectra in the aromatic region between 6.5 and 9.5 ppm. The classification method based on wavelet-based variables selection, permitted to reach an efficiency in validation greater than 95%. Finally, 2D correlation analysis was applied to FT-NIR and (1)H NMR matrices, in order to recognise the spectral zones bringing the same chemical information.
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Aims: The aim of this paper is to study the anthocyanin profile of the monovarietal young red wines from the Appellation of Origin Navarra. Differentiation of wines according to age and grape variety (Tempranillo, Grenache and Cabernet-Sauvignon) was procured using the multivariate statistical methods.
Methods and results: The anthocyanin composition of wines was analysed by HPLC's technology. Then, the data were analysed statistically. In this way, principal component analysis and stepwise discriminant analysis classified correctly samples belonging to the same category. The anthocyanin 3-monoglucosides appeared as key factor in the differentiation of wines according to age. Largest relative concentrations in these anthocyanins were found in the youngest wines. In addition, a separation of wines according to variety is obtained in terms of their relative contents on the anthocyanin acetate derivatives.
Conclusion: A minimum number of anthocyanin compounds made classification of wines according to both age and grape variety possible in this work. Cabernet-Sauvignon is the variety that appeared to differ most from the rest, because it is the one that presents the major levels of the MvAc anthocyanin. The malvidin 3-monoglucoside was variable the highest discriminant power according to age. Using this variable exclusively, 80 % of correct classification was achieved.
Significance and impact of study:The importance of the anthocyanin compounds on the global quality of the young wine (1 or 2 years-old), has driven us to realize this work. It is important to know the evolution that these compounds suffer throughout the years in order to apply new technologies as for example the microoxygenation.
Two new malvidin-derived pigments, referred to as A and B, were detected in red wine made from
Vitis vinijera grapes (var. Carignane) and characterised. The results reported herein indicate that they
are formed by covalent binding of major wine anthocyanins [malvidin 3-monoglucoside and malvidin
3-(6-p-coumaroyl)monoglucoside] with 4-vinylphenol. Synthetic products obtained by reaction between
these reagents were shown to be identical with the natural compounds on the basis of their UV-visible,
mass and 'H NMR spectra. Their formation involves cyclisation between C-4 and the hydroxy group at
C-5 of the original flavylium moiety and the vinylphenol double bond. Subsequent oxidation leads to
pigment A or B. Their structure can yield two flavylium mesomeric forms, one corresponding to the
malvidin type and the other to the pelargonidin type. The pigments' colour suggests that the latter is the
predominant form under our conditions.
The antioxidant properties of traditional balsamic vinegar as regards its phenolic and flavonoid content comparing it to selected vinegars and red wines have been investigated. The polyphenols were separated from interfering compounds utilizing C18 columns. The polyphenolic content was determined utilizing both Folin–Ciocalteu and peroxidase assays. The antioxidant capacity was quantified using both ABTS and FRAP assays. The results show that traditional balsamic vinegar has lower antioxidant activity and phenolic and flavonoid content than Nero d’Avola but higher than the other tested products. The antioxidant capacity of wines and vinegars is highly correlated with their phenolic content, measured by peroxidase assay and it is also highly correlated with their flavonoid content while in traditional balsamic vinegar and balsamic vinegar this correlation diminishes. The study describes a simple and fast method of separating from other compounds and of measuring polyphenols in the analysis of red wines and vinegars with complex composition such as traditional balsamic vinegar.
A new method, rapid and simple to apply, has been developed to measure antioxidant activity. It is based on the electrochemical oxidation of 2,2-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) and gives reliable results, with the monitoring of only absorbance and time. It has been compared with the total antioxidant status test and gives similar but more repeatable results. The method has been applied to wines, brandies and vinegars. It has been confirmed that the antioxidant activity of these products is highly correlated with their polyphenolic content, and that other majority components in the samples, such as ethanol, SO2 or acetic acid, do not interfere in the method.
Traditional balsamic vinegar (TBV) is a natural product prepared with cooked and concentrated locally grown grape must. It
has been demonstrated that TBV contains phenols and shows antioxidant activity. In this study we investigated the antioxidant
properties of TBV in relation to its content of phenolic compounds, polymeric tannins and Maillard reaction products (MRPs).
Results show that TBV has a high antioxidant activity measured with both FRAP and ABTS assays, which is higher or equal to
those obtained in some red wines. About 45% of the antioxidant activity of TBV is due to the total polyphenolic fraction.
Among polyphenols, tannins contribute to about 50% of the antioxidant activity of the total polyphenolic fraction. The residual
antioxidant activity of TBV is due to the melanoidins (about 45%) synthesized during the boiling of the must and the ageing
of TBV and to other compounds such as low molecular weight MRPs. When we investigated the effect of heating on the browning
and on the formation of antioxidant MRPs in must model systems, we observed a major formation of antioxidant MRPs for the
model system containing both amino acids and sugars with respect to the model system containing only sugars. We also tested
the effect of some representative phenolic compounds present in must. Only polyphenols were stable in the model solution;
however, at our experimental conditions they did not influence the browning and the formation of MRPs. Independent of their
bioavailability, dietary antioxidants play an important role in protecting the gastrointestinal tract from oxidative damage
and also possibly against a buildup of peroxides and their assimilitation in the digestive tract.
Antioxidant activity of commercial red (n = 5) and white (n = 5) grape juices and wine vinegars (n = 5) were determined by the oxygen radical absorbance capacity (ORAC) assay using fluorescein (FL) as fluorescent probe. The ORAC-FL values varied from 14.6 to 25.0 μmol of trolox equivalents/ml for red grape juices, from 3.5 to 11.1 μmol of trolox equivalents/ml for white grape juices, and from 4.5 to 11.5 μmol of trolox equivalents/ml for wine vinegars. Differences in the antioxidant activities among grape juice, wine, and vinegar were attributed to their different phenolic contents and compositions and to other non-phenolic antioxidants present in the samples. These data confirm grape juice and wine vinegar as good dietary sources of antioxidants.
Nowadays, there is considerable interest in finding out about antioxidants that are consumed in the habitual diet. It is known that polyphenols are involved in reducing the risk of diseases associated with oxidative stress. The in vitro antioxidant activity of the principal wine polyphenolic compounds (catechins, procyanidins, anthocyanins and pyranoanthocyanins) was studied in this work. Four distinct methods were used to assess the antioxidant capacity of the tested compounds: inhibition of peroxynitrite mediated tyrosine nitration, TEAC (Trolox equivalent antioxidant capacity assay), FRAP (Ferric reducing/antioxidant power assay) and TBARS (thiobarbituric acid reactive substances) methods. In general, it could be concluded that procyanidins were, among the in vitro tested groups, the ones which showed more antioxidant capacity using the four different methods, followed by anthocyanins and pyranoanthocyanins. On the basis of the simple regression testing, there was a statistically significant relationship between these different methods used in aqueous phase (r > 0.92). However, no correlation was found between the results obtained in lipid media with the TBARS method and those obtained in the aqueous media (peroxynitrite scavenging activity, TEAC and FRAP methods).
Several red wines were elaborated to assess the effect of the degree of grape ripening on wine color and on the levels of flavanol and anthocyanin compounds, which are chiefly responsible for the wine color attributes. Two different cultivars and three different degrees of ripening were studied in two consecutive years. The wines were aged for 1 year in American oak barrels of medium-high char followed by 6 months in the bottle. The results showed that the wines made from more mature grapes had generally higher free anthocyanin content, and during aging the decrease of the free anthocyanins and flavanols took place in conjunction with an increase in the levels of the anthocyanin derivatives or "new pigments", which are responsible for maintaining color intensity and adding violet hues in aged wines. From the results obtained, it seems to be clear that the characteristics and composition of grapes harvested later (7-8 days in this region and for these varieties) than the usual time are quite beneficial to obtaining quality aged wines. The phenolic composition of wines made from the last harvested grapes is mainly responsible for the stability of their color, which is extremely important in product acceptance with a significant increase hence of product quality.
Triple Quadrupole The Q-TOF The MALDI TOF–TOF References
A high-performance liquid chromatography (HPLC) method for the separation of anthocyanins in red wine has been developed. Sixty-six different anthocyanins were detected in a single red wine sample produced in 1997 by coupling HPLC and an electrospray interface with a mass spectrometer. These 66 anthocyanins were mostly well-known mono- and diglucosides of wines. In addition, the rare acetic acid ester and coumaric acid ester of the diglucosides could be identified. Some recently described and some new anthocyanin-derived pigments formed by wine maturation were also detected. Catechin dimers as well as pyruvic acid and acetaldehyde derivatives of delphinidin, cyanidin, petunidin, peonidin, and malvidin were present in the one-year-old wine, the latter also in their acetylated and coumarylated forms.
Microoxygenation was applied to a red wine for five months following the end of alcoholic fermentation, and its effects on the concentration of anthocyanin and anthocyanin-derived compounds were studied by high-pressure liquid chromatography-electrospray ionization-mass spectrometry (HPLC-ESI-MS). Monomeric anthocyanins were detected together with direct anthocyanin-flavanol adducts, ethyl-linked anthocyanin-flavanol compounds, and pyranoanthocyanins. Microoxygenation resulted in wines with a lower concentration of monomeric anthocyanins and a higher concentration of ethyl-linked compounds and vitisin-related pigments than the control wine, while no effect was observed on the concentration of the direct adducts. Differences were also observed in the chromatic characteristics of the wine, with microoxygenated wines showing higher color intensity, a parameter that was highly correlated with the higher presence of pyranoanthocyanins. Copyright © 2006 by the American Society for Enology and Viticulture. All rights reserved.
The anthocyanin profile of young wines made from Vitis vinifera cv. Graciano was determined by liquid chromatography/electrospray ionization-mass spectrometry (LC/ESI-MS) and compared with that of Vitis vinifera cv. Tempranillo and cv. Cabernet Sauvignon. Thirty-four anthocyanins and anthocyanin-derived pigments, including pyruvic acid, 4-vinylphenol, and vinylflavanol, plus direct and acetaldehyde-mediated condensation products, were found by direct analysis. Of particular interest was the presence of the cis isomer of malvidin-3-(6"-p-coumaroylglucoside), reported here in wine for the first time. Anthocyanins in Graciano wines were characterized by a high level of peonidins and equal distribution between acetyl and cinnamoyl glucosides in comparison with Tempranillo and Cabernet Sauvignon wines. The occurrence of anthocyanin-derived pigments in the different wines appeared to be related to the concentration of the corresponding anthocyanin precursors.
A laboratory scale fermenter was used to produce wine vinegar in a submerged culture acetic fermentation. The aim was to establish the optimal experimental conditions for three important acetification factors in order to obtain high concentrations of acetic acid within the shortest period of time. These factors were stirring speed, substrate loading and working volume. The effect of each single factor taking part in the process and the effect of the possible interaction among these was evaluated. For this purpose an experimental factorial design with a multiple linear regression (MLR) model resolved with a CSS-Statistics programme was applied. The results indicate that to obtain a high fermentation yield the stirring speed was the most important factor and the loading proportion the most important factor to achieve a better rate of acetification.
Phenolic composition of 92 wine vinegars produced from different wines from the south of Spain (Jerez, Montilla, El Condado) is determined by HPLC with diode array detection. Pattern recognition techniques were applied to distinguish between different methods of elaboration (slow traditional methods with surface culture or quick methods carried out in bioreactors with submerged culture) or wines employed as substrate. Multivariate analysis of data includes principal component analysis, cluster analysis, and linear discriminant analysis (LDA) as well as artificial neural networks trained by back-propagation (BPANN). The classification depending on the acetification process leads to good recalling rates in both LDA (mean = 92.5) and BPANN (mean = 99.6). With respect to the classification on the basis of the geographical origin, the obtained recalling rates were 88.8 for LDA and of 96.5 for BPANN (mean values). Keywords: Vinegar; phenols; discriminant analysis; artificial neural network; HPLC
Grape anthocyanin-3-glucosides and unreported natural pigments characterized as vinylphenol anthocyanin-3-glucoside adducts were studied. Our investigations were undertaken to compare color and stabilities when processed and stored under identical conditions. Studies of molecular concentration, color density and Hunter color values were done at pH levels. Grape anthocyanin-3-glucosides were less stable than their 4-vinylphenol derivatives and the color stability of the unreported pigments was higher than that of anthocyanin-3-glucosides. Moreover, the compounds were resistant to SO2 discoloration whereas anthocyanins were completely bleached.
The quality of a wine vinegar is determined by the raw wine substrate and the acetification process employed in its production. Attempts to characterise vinegars have been based on these two features, along with variables such as total extract, glycerol, organic acids, volatile compounds and phenolic composition. When the final products are analysed, it is difficult to evaluate to what extent quality differences are due to the raw material or to differences in production methods, so it is necessary to determine the influence of each feature separately. The present work focuses on monitoring physicochemical changes during the acetification of sherry wine by submerged culture. ANOVA showed significant differences for ethanol, acetic and lactic acids and some volatile compounds (methanol, 1‐propanol, 2‐methyl‐1‐propanol, 2‐methyl‐1‐butanol, 3‐methyl‐1‐butanol, acetoin, acetaldehyde, ethyl acetate and ethyl lactate). However, no statistical changes were found for phenolic compounds during acetification. The phenolic composition of the final product was determined by the substrate employed. In addition, the influence of cycle duration on the chemical composition was studied; the only compound affected by this factor was 2‐methyl‐1‐butanol.
© 2001 Society of Chemical Industry
Accelerated aging of vinegars using oak chips has been tested in this work as an alternative to traditional aging in wood barrels. A wine vinegar was submitted to different aging assays involving two oak chips pretreatments and three different levels of alcohol content (0.1, 1 and 2°). Total phenol index (TPI), dry extract, major volatile compounds determined by gas chromatography (GC), non-volatile phenolic compounds (by liquid chromatography) as well as volatile compounds from wood (by GC with previous solid phase extraction) were followed for 90 days. Sensory analysis was performed by triangle and descriptive tests. The TPI increased significantly after 15 days of aging whereas the dry extract remained practically constant. Oak chips pretreatments influenced the content of whisky lactones. Moreover, an alcohol content of at least 1% (v/v) produced higher concentrations of ethyl acetate. Panelists found significantly differences (P<0.1) between samples with different alcohol concentrations.
In part I of this series a mathematical model for acetic acid fermentation was reported. However, no kinetic model can be complete until its equation parameters are estimated. This inevitably entails a practical identifiability analysis intended to ascertain whether the parameters can be estimated in an unambiguous manner based not only on the sensitivity of the model to them, but also on the amount and quality of available experimental data for this purpose. Also, estimating the model parameters entails optimizing a specific objective function subject to the model equations as major constraints and to additional, minor constraints on variables and parameters. This approach usually leads to the formulation of a non-linear programming problem involving differential and algebraic constraints where the decision variables constitute the parameter set to be estimated. In the scope of modelling biotechnological processes, this problem is not usually dealt with in a proper way. This second paper reviews available models for practical identifiability assessment and parameter estimation with a view to their prospective application to the proposed model and its validation.
A comparative study of the antioxidant activity of wine phenolics has been performed. Standards of phenolic compounds, including benzoic and cinnamic acids, flavanols, flavonols and resveratrol, as well as some of their metabolites have been analysed for their antioxidant activity. Antioxidant assays included the 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) and the 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging methods and the Oxygen Radical Absorbance Capacity method (ORAC).We compared the reactivity of standard phenolic compounds under selected tests and obtained a ranking order for each one. Both ABTS and DPPH methods were well correlated. Several new structure–activity relationships were observed. As the number of phenoxyl groups increases, the antioxidant capacity, determined by DPPH and ABTS tests, improves. In the case of the ORAC assay, the ortho-position of phenoxyl groups clearly determines the activity. The metabolites of phenolic compounds present antioxidant activity and their values are similar to those of the phenolic compounds themselves.The choice of solvent, the effect of concentration and the information provided by the three tests under study are considered.
The influence of controlled oxygenation on the colour and phenolic composition of red wine was studied by UV–VIS spectrophotometry, liquid chromatography (LC) coupled to diode array detection (DAD) and electrospray ionisation mass spectrometry, and thiolysis. The comparison between the control and oxygenated wines demonstrated changes in colour characteristics along with a significant increase in concentrations of pyranoanthocyanins, ethyl-bridged compounds and derived pigments both with storage time and with oxidation. Principal component analysis was applied to wine analysis data measured throughout the conservation period. The effect of the storage time and oxygenation was clearly reflected in this analysis.Mass-spectrometric analysis of the wines demonstrated the presence of compounds which are markers of reactions involving acetaldehyde. Two types of mechanisms were observed. The first concerns acetaldehyde condensation reactions and the second, the cycloaddition process between anthocyanins and flavanols mediated by acetaldehyde, generating tannin-pyranoanthocyanins.The presence in wines of trimeric structures resulting from these mechanisms, as well as the results obtained after thiolysis of the fraction containing polymeric species obtained by Fractogel chromatography, confirm that proanthocyanidins react with acetaldehyde in the same way as flavanol monomers.
The purposes of this work comprise the assessment of the antioxidant activity of wine samples by different analytical methods. The relation between antioxidant values and phenolic composition is also considered as well as the insight of which red wine phenolic fraction is more effective towards quenching radicals.In vitro antioxidant activity of wines has been examined by a number of assays including: oxygen radical absorbance capacity (ORAC), 2,2′-azinobis-(3-ethylbenzothiazoline)-6 sulfonic acid (ABTS) and 1,1-diphenyl-2-picrylhydrazyl (DPPH). Forty-one wine samples were analysed (16 red, 17 white and 9 sherry wines). The total phenolic index was evaluated. In addition, red wines were fractionated using solid phase extraction to separate three main fractions (phenolic acids, flavan-3-ol and anthocyanins, flavonols).Antioxidant activity of red wines is higher than that of white or sherry wines with every method under study. Analysis of variance (ANOVA) demonstrated significative differences among red and white wines; and among red and sherry wines. However, ANOVA showed no statistical significative differences among antioxidant results for white and Sherry wines. Total phenolic content is related to antioxidant activity, the highest correlation coefficients being obtained for ORAC method. Concerning red wine’s fractions activity, larger values were obtained for Fraction 2 corresponding to flavanols and anthocyanins in every case analysed. Additionally, similar values were obtained for Fraction 1 and white wines’ ORAC results.
The different options MS detection are investigated in order to achieve the best conditions for detection and identification of anthocyanins by LC–MS. A method for separation of these compounds that enables the main molecules in wines to be identified by direct analysis, without any previous preparation, is proposed. The anthocyanin composition of different red grape skin extracts and commercial monovarietal wines were determined by this method. Some recently described anthocyanin derivatives that are supposed to be formed during wine maturation were also investigated. Results showed that some of these derivatives are present in grape and young wine. The combination of diode array detection and MS analysis has been demonstrated to be essential for identification of anthocyanin derivatives.
The presence of phenolic compounds has been extensively studied in Sherry and Balsamic vinegars due to their impact on quality but little work has been done on red wine vinegars. Phenolic compounds were monitored during the acetification of red wine vinegars produced by surface culture in different wood barrels (oak, chestnut, acacia and cherry). A total of 166 samples were analysed for phenolic compounds using LC-DAD, the total phenol index (TPI) and the total monomeric anthocyanins (TA). Twelve phenolic compounds were identified corresponding to phenolic acids, flavanols and stilbens. Most phenolic acids did not significantly change their concentrations in the different acetifications. (+)-Catechin and resveratrol glycoside underwent significant decreases during acetification while gallic acid and gallic ethyl ester increased substantially for those vinegars produced in chestnut wood. The concentrations of phenolic compounds were used to build the functions for discriminant analysis. Samples belonging to two wine substrates (groups F and T) were correctly classified with 98.6% (group F) and 100% (group T) for the four types of wood barrels. During acetification a decrease (∼50%) in the content of total monomeric anthocyanins was observed. According to the results of triangle difference test the panel was able to distinguish most of the vinegars according to the different woods they were made in. The results of descriptive sensory analysis show that oak and cherry gave the maximum scores for most of the descriptors.
Wine is an important source of dietary antioxidants because of its phenolic compound content. The antioxidant activity (AA) of pure monomer substances present in wines, such as phenolic acids, flavanols, and anthocyanins, has already been described, but the AA of polymeric phenols is still unknown. In this study, we have fractionated a red wine by countercurrent chromatography (CCC) into four fractions: fraction 1, made up of polymeric compounds; fraction 2, containing malvidin-3-glucoside; fraction 3, containing peonidin-3-glucoside; and fraction 4, containing vitisin A. The AA of these fractions was determined by oxygen radical absorbance capacity and ferric reducing ability assays. The weight of fraction 1 was the largest, so this was the largest contributor to the AA of the wine. However, the antioxidant powers (muM Trolox/g fraction) of fractions 2-4 were similar and higher than that of fraction 1. We also determined AA before and after in vitro gastric and intestinal digestions. After gastric digestion, the AA was 100-1000 times higher than the original fraction values. Gallic acid was determined in gastric and intestinal digested fractions. After intestinal digestion, the concentrations of simple phenols, such as caffeic acid, p-coumaric acid, and protocatechualdehyde, increased as they were released from the fractions under our conditions. Protocatechuic acid was determined in more intestinal digested fractions than in gastric digested fractions. These results partly explain the increase in AA after the digestion and indicate the relevance of polymeric polyphenolic compounds as precursors of smaller molecules with biological activity.
A simple, automated test measuring the ferric reducing ability of plasma, the FRAP assay, is presented as a novel method for assessing "antioxidant power." Ferric to ferrous ion reduction at low pH causes a colored ferrous-tripyridyltriazine complex to form. FRAP values are obtained by comparing the absorbance change at 593 nm in test reaction mixtures with those containing ferrous ions in known concentration. Absorbance changes are linear over a wide concentration range with antioxidant mixtures, including plasma, and with solutions containing one antioxidant in purified form. There is no apparent interaction between antioxidants. Measured stoichiometric factors of Trolox, alpha-tocopherol, ascorbic acid, and uric acid are all 2.0; that of bilirubin is 4.0. Activity of albumin is very low. Within- and between-run CVs are <1.0 and <3.0%, respectively, at 100-1000 micromol/liter. FRAP values of fresh plasma of healthy Chinese adults: 612-1634 micromol/liter (mean, 1017; SD, 206; n = 141). The FRAP assay is inexpensive, reagents are simple to prepare, results are highly reproducible, and the procedure is straightforward and speedy. The FRAP assay offers a putative index of antioxidant, or reducing, potential of biological fluids within the technological reach of every laboratory and researcher interested in oxidative stress and its effects.
Little is known about the change of phenolic compounds and total phenolic content by the acetification process. The aim of this study was to assess the contents of selected phenolic compounds of cider and red and white wines in comparison to phenolic profiles in corresponding vinegars by using a new HPLC method for the simultaneous separation and quantification of polar phenolic acids and less polar flavonoids. Identifications were made by retention times and by means of mass spectra. Additionally, total phenolic contents of wines and vinegars were determined photometrically. The decrease in total phenol content by the acetification process was highest for cider vinegars (40%) and lower for red and white wine vinegars (13 and 8%, respectively). A decrease in the contents of individual phenolic compounds of vinegars from white white and ciders was not observed. In contrast, the contents of individual phenolic compounds in red wine vinegar decreased approximately 50%.
An improved method of oxygen radical absorbance capacity (ORAC) assay has been developed and validated using fluorescein (3',6'-dihydroxyspiro[isobenzofuran-1[3H],9'[9H]-xanthen]-3-one) as the fluorescent probe. Our results demonstrate that fluorescein (FL) is superior to B-phycoerythrin. The oxidized FL products induced by peroxyl radical were identified by LC/MS, and the reaction mechanism was determined to follow a classic hydrogen atom transfer mechanism. In addition, methodological and mechanistic comparison of ORAC(FL) with other widely used methods was discussed. It is concluded that, unlike other popular methods, the improved ORAC(FL) assay provides a direct measure of hydrophilic chain-breaking antioxidant capacity against peroxyl radical.
Changes in the physicochemical composition of wine vinegars produced by submerged culture system and aged in wood were followed. Five Sherry wine vinegars and a model vinegar solution were aged in six new American oak butts of 16.6 L capacity. A total of 24 phenolic compounds were monitored during the maturation study (24 months), along with other physicochemical parameters (total extract, acidity, residual alcohol and total phenolic index). Multivariate statistical analysis was applied to the data. From the sixth month on, significant changes were produced in most of the phenolic compounds, mainly aromatic aldehydes and 5-(hydroxymethyl)-2-furaldehyde. When all the phenolic compounds were considered as variables, cluster analysis grouped samples according to the wine substrate employed in the elaboration of vinegars under study. Within each subcluster, samples are arranged according to their aging status when phenolic compounds accounting significative changes at 180 days of aging are considered. Discriminant functions were constructed from the phenolic compounds data set. The validity of these functions was tested using 13 samples of aged commercial Sherry wine vinegars and 25 unaged vinegars. A total of 97.4% of the test samples was correctly classified within its respective group.
The antioxidant activity of the six common anthocyanidins, pelargonidin, cyanidin, delphinidin, peonidin, petunidin, and malvidin, and their glycosidic forms was evaluated in three lipid-containing models [human low-density lipoprotein (LDL) and bulk and emulsified methyl linoleate]. In addition, the radical scavenging activity of the compounds against the 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical was studied. Most anthocyanins and their aglycons acted as strong antioxidants in emulsion and LDL. Many compounds showed an activity comparable to the well-known antioxidants alpha-tocopherol, Trolox, catechin, and quercetin. In bulk methyl linoleate, anthocyanins and anthocyanidins possessed only a weak antioxidant activity or even oxidation-promoting activity. Depending on the anthocyanidin, different glycosylation patterns either enhanced or diminished the antioxidant power. For the most part, the activities of the glycosides and the aglycons did not differ remarkably in emulsion. In LDL the aglycons showed in general higher activities than the glycosides. In bulk oil, to the contrary, the glycosides were more effective than the aglycons.
On the basis of observations from Vitis vinifera cv. Pinotage wines and experiments performed in model wine medium, a new chemical pathway responsible for the formation of anthocyanin-vinylphenol adducts in red wines is described. Until now, these pigments have been considered to be reaction products of anthocyanins and vinylphenols, the latter being generated during fermentation by enzymatic decarboxylation of the respective cinnamic acids. The mechanism of the novel pathway, involving intact hydroxycinnamic acid and anthocyanin, is explained. Only cinnamic acids with electron-donating substituents on the aromatic ring, such as coumaric acid, ferulic acid, caffeic acid, and sinapic acid, undergo this conversion, as they stabilize an intermediately formed carbenium ion. Decarboxylation and oxidation of the pyran moieties are the final steps in the generation of the corresponding 4-vinylphenol, 4-vinylguaiacol, 4-vinylcatechol, and 4-vinylsyringol adducts of anthocyanins in red wine.
I.
Introduction
218
II.
Quality Improvement
219
III.
Grape and Wine Polyphenols
220
IV.
Mass Spectrometry in the Study of Polyphenols and Procyanidins
222
V.
Mass Spectrometry in the Study of Anthocyanins and their Derivatives
229
VI.
Mass Spectrometry in the Study of Structures Formed by Polymerization of Anthocyanins and Flavan‐3‐ols
234
VII.
Mass Spectrometry and Grape and Wine Resveratrol
240
VIII.
Application of MALDI in the Study of Polyphenols
243
IX.
Mass Spectrometry Applied to the Study of Wine Polyphenols from Cork Bottle Stoppers and Oak Barrels
245
X.
Conclusions
246
References
247
Mass spectrometry, had and still has, a very important role for research and quality control in the viticulture and enology field, and its analytical power is relevant for structural studies on aroma and polyphenolic compounds. Polyphenols are responsible for the taste and color of wine, and confer astringency and structure to the beverage. The knowledge of the anthocyanic structure is very important to predict the aging attitude of wine, and to attempt to resolve problems about color stability. Moreover, polyphenols are the main compounds related to the benefits of wine consumption in the diet, because of their properties in the treatment of circulatory disorders such as capillary fragility, peripheral chronic venous insufficiency, and microangiopathy of the retina. Liquid Chromatography‐Mass Spectrometry (LC‐MS) techniques are nowadays the best analytical approach to study polyphenols in grape extracts and wine, and are the most effective tool in the study of the structure of anthocyanins. The MS/MS approach is a very powerful tool that permits anthocyanin aglycone and sugar moiety characterization. LC‐MS allows the characterization of complex structures of grape polyphenols, such as procyanidins, proanthocyanidins, prodelphinidins, and tannins, and provides experimental evidence for structures that were previously only hypothesized. The matrix‐assisted‐laser‐desorption‐ionization‐time‐of‐flight (MALDI‐TOF) technique is suitable to determine the presence of molecules of higher molecular weight with high accuracy, and it has been applied with success to study procyanidin oligomers up to heptamers in the reflectron mode, and up to nonamers in the linear mode. The levels of resveratrol in wine, an important polyphenol well‐known for its beneficial effects, have been determined by SPME and LC‐MS, and the former approach led to the best results in terms of sensitivity. © 2003 Wiley Periodicals, Inc., Mass Spec Rev 22:218–250, 2003; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/mas.10052
Epidemiologic studies have demonstrated an inverse association between consumption of fruits and vegetables and morbidity and mortality from degenerative diseases. The antioxidant content of fruits and vegetables may contribute to the protection they offer from disease. Because plant foods contain many different classes and types of antioxidants, knowledge of their total antioxidant capacity (TAC), which is the cumulative capacity of food components to scavenge free radicals, would be useful for epidemiologic purposes. To accomplish this, a variety of foods commonly consumed in Italy, including 34 vegetables, 30 fruits, 34 beverages and 6 vegetable oils, were analyzed using three different assays, i.e., Trolox equivalent antioxidant capacity (TEAC), total radical-trapping antioxidant parameter (TRAP) and ferric reducing-antioxidant power (FRAP). These assays, based on different chemical mechanisms, were selected to take into account the wide variety and range of action of antioxidant compounds present in actual foods. Among vegetables, spinach had the highest antioxidant capacity in the TEAC and FRAP assays followed by peppers, whereas asparagus had the greatest antioxidant capacity in the TRAP assay. Among fruits, the highest antioxidant activities were found in berries (i.e., blackberry, redcurrant and raspberry) regardless of the assay used. Among beverages, coffee had the greatest TAC, regardless of the method of preparation or analysis, followed by citrus juices, which exhibited the highest value among soft beverages. Finally, of the oils, soybean oil had the highest antioxidant capacity, followed by extra virgin olive oil, whereas peanut oil was less effective. Such data, coupled with an appropriate questionnaire to estimate antioxidant intake, will allow the investigation of the relation between dietary antioxidants and oxidative stress-induced diseases.
Vitisin A was prepared from malvidin 3-glucoside and pyruvic acid in model wine medium, isolated by countercurrent chromatography, and purified by preparative high-performance liquid chromatography (HPLC). The synthesized compound was used as a reference standard to quantify vitisin A in Chilean wines from Vitis vinifera cv. Cabernet Sauvignon, including a vertical row of wines from the same vineyard over 16 years. Maximum vitisin A content was reached within the first year of storage. Importantly, up to half of the initial amount of vitisin A in young wines was still present in 15 year old wines. Although vitisin A was found to be much more stable as compared to other monomeric C-4 underivatized anthocyanins, it also slowly degrades after reaching its peak concentration. The "color activity concept" was applied to vitisin A, malvidin 3-glucoside, malvidin 3-(6' '-acetylglucoside), and polymeric pigments isolated by countercurrent chromatography in order to estimate their contribution toward the overall color expression of wines. It was found that vitisin A is only a minor contributor to the visually perceived color of aged red wines (color contribution approximately 5%). The major contributor is the polymeric fraction (color contribution approximately 70-90%).
High-performance liquid chromatography coupled with a coulometric array detector was used to characterize the electrochemical behavior of 17 flavonoids and three cinnamic acid derivatives. The antioxidant activity of these phenolic compounds was evaluated by the ferric reducing activity power (FRAP), the oxygen radical absorbance capacity (ORAC), and the 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical assays. All flavonoids, except kaempferol-3-rutinoside, malvidin-3-glucoside, and peonidin-3-glucoside, had two oxidation potentials (100-300 and 700-800 mV). Quercetin and myricetin had an additional oxidation wave at 400 mV. The electrochemical responses at a relatively low oxidation potential (300 mV) and the cumulative responses at medium oxidation potentials (400 and 500 mV) had the highest correlations with antioxidant activities. The highest correlations between electrochemical characteristics and antioxidant activities were found between electrochemical responses and antioxidant activities obtained in the FRAP assay and in the DPPH assay after short reaction periods. Lower correlations were revealed between electrochemical responses and antioxidant activities obtained in the ORAC assay.
Anthocyanins from blood orange [Citrus sinensis (L.) Osbeck] juices were isolated and purified by means of high-speed countercurrent chromatography and preparative high-performance liquid chromatography. Structures of the pigments were then elucidated by electrospray ionization multiple mass spectrometry and nuclear magnetic resonance (NMR) spectroscopy. The major anthocyanins of the juice were characterized as cyanidin 3-glucoside and cyanidin 3-(6"-malonylglucoside). Furthermore, six minor anthocyanins were detected and identified as cyanidin 3,5-diglucoside, delphinidin 3-glucoside, cyanidin 3-sophoroside, delphinidin 3-(6"-malonylglucoside), peonidin 3-(6"-malonylglucoside), and cyanidin 3-(6"-dioxalylglucoside). The occurrence of the latter compound in blood oranges is reported here for the first time, together with full NMR spectroscopic data. Further investigations revealed the presence of four anthocyanin-derived pigments, which are formed through a direct reaction between anthocyanins and hydroxycinnamic acids during prolonged storage of the juice. These novel pyranoanthocyanins were identified as the 4-vinylphenol, 4-vinylcatechol, 4-vinylguaiacol, and 4-vinylsyringol adducts of cyanidin 3-glucoside through comparison of their mass spectrometric and chromatographic properties with those of synthesized reference compounds.
Pinotage red wines were found to contain a reaction product of malvidin 3-glucoside and caffeic acid, the so-called pinotin A. A total of 50 Pinotage wines from the vintages 1996-2002 were analyzed for the content of pinotin A, malvidin 3-glucoside, caffeic acid, and caftaric acid. Statistical analyses were performed to reveal variations in the content of these compounds and to determine the factors that influence pinotin A formation during wine aging. An exponential increase of the concentration of this aging product was observed with prolonged storage time. The most rapid synthesis of pinotin A was observed in 2.5-4 year old wines, although at this age malvidin 3-glucoside is already degraded to a large extent. This phenomenon is explained by the increased ratio of caffeic acid/malvidin 3-glucoside, which strongly favors the formation of pinotin A and makes side reactions less likely. Pinotin A formation proceeds as long as a certain level of malvidin 3-glucoside is maintained in the wines. In wines >5-6 years old degradation or polymerization of pinotin A finally exceeds the rate of its de novo synthesis.
The total antioxidant capacity (TAC) and phenolic composition of 139 Pinotage wines (2002 and 2003 vintages) were determined using the 2,2'-azino-di(3-ethylbenzo-thialozine-sulfonic acid) scavenging assay and high-performance liquid chromatography, respectively. The contribution of individually quantified phenolic compounds to the wine TAC was calculated using their concentrations and Trolox equivalent antioxidant capacity (TEAC) values. The TEAC values of quercetin-3-galactoside, isorhamnetin, and peonidin-3-glucoside are reported for the first time. Between 11 and 24% of the measured TAC of Pinotage wines was explained by the sum of the calculated contributions of their quantified phenolic compounds comprising monomeric phenolic compounds and procyanidin B1. Ultrafiltration was carried out to attempt separation of monomeric and polymeric phenolic compounds. Analysis of ultrafiltration permeates and retentates enabled estimation of the TAC contribution of large molecular weight (MW) unknown compounds (46%) (>50 kDa), including oligomeric and polymeric phenolic compounds and small MW unknown compounds (34%) (<50 kDa). Three mixtures, containing 12 phenolic compounds in typical concentrations expected in Pinotage wines, exhibited 16-23% synergistic antioxidant activity. This suggests that synergy between phenolic compounds does play a role in the wine TAC but that it does not explain the large discrepancy between measured and calculated TAC values.
Malvidin-3-glucoside (27%); acetyl vitisin B (14%); malvidin 3-(6-acetyl)-glucoside (14%); vitisin B (13%) Fraction
- B Vitisin
Vitisin B (17%) Malvidin-3-glucoside (27%); acetyl vitisin B (14%); malvidin 3-(6-acetyl)-glucoside (14%); vitisin B (13%) Fraction 2 2nd inj. Malvidin-3-glucoside (55%);
Malvidin-3-glucoside-ethyl-catechin (ethyl-linked compound) was observed in three different peaks of the wine and vinegar chromatograms corresponding to different stereo isomers, as reported by other authors for Cabernet Sauvignon
- José Pérez
- Schwarz
- Quast
- Baer
Pérez-Magariño & González-San José, 2004; Schwarz, Quast, von Baer, & Winterhalter, 2003a). Malvidin-3-glucoside-ethyl-catechin (ethyl-linked compound) was observed in three different peaks of the wine and vinegar chromatograms corresponding to different stereo isomers, as reported by other authors for Cabernet Sauvignon (Atanasova et al., 2002; Cano-López et al., 2006; Monagas et al., 2003).
STATISTICA for Windows (Computer program manual)
- Inc Statsoft
Statsoft, INC. (2001). STATISTICA for Windows (Computer program manual). Tulsa,
OK: Staftsoft, Inc., 2300 East 14th Street, Tulsa, OK, 74104-4442.
Microoxygenation: A review
- Parish