Chemometric studies of vinegars from different raw materials and processes of production

The phenolic composition, aroma compounds, and organic acid content of 83 vinegars have been determined. Multivariate analysis techniques have been used to classify these vinegar samples according to raw material (white wine, red wine, apple, honey, alcohol, balsamic, and malt) and production process (with and without aging in wood). Cluster analysis grouped the samples according to production process. Only apple and balsamic vinegars were separated from wine vinegars. Alcohol, honey, and malt vinegars were grouped with no aged wine vinegars. Linear discriminate analysis allowed a 88% differentiation according to raw material and 100% according to aging in wood. Besides, from the results obtained, a major role of the volatile compounds in the differentiation of the vinegar samples according to their aging period in wood can be seen.     

Effects of apple cider vinegars produced with different techniques on blood lipids in high-cholesterol-fed rats

Red delicious apples were used to produce natural apple cider with and without inclusion of maceration. Traditional surface and industrial submersion methods were then applied to make vinegar from apple ciders. Apple cider vinegar samples produced with inclusion of maceration in the surface method had the highest total phenolic content, chlorogenic acid, ORAC, and TEAC levels. Cholesterol and apple vinegar samples were administered using oral gavage to all groups of rats except the control group. Apple cider vinegars, regardless of the production method, decreased triglyceride and VLDL levels in all groups when compared to animals on high-cholesterol diets without vinegar supplementation. Apple cider vinegars increased total cholesterol and HDL and LDL cholesterol levels and decreased liver function tests when compared to animals on a high-cholesterol diet without vinegar supplementation. A high-cholesterol diet resulted in hepatic steatosis. VSBM and VSB groups significantly decreased steatosis.     

Determination of antioxidant activity and characterization of antioxidant phenolics in the plum vinegar extract of cherry blossom (Prunus lannesiana)

Sakura-cha (salted cherry blossom tea) is a Japanese tea that is traditionally served at celebrations such as wedding ceremonies. The production of Sakura-cha includes the immersion of cherry blossom flowers in Japanese plum vinegar, and through this process, the byproduct (plum vinegar extract of cherry blossom) is obtained. In this study, the antioxidant activity of the plum vinegar extract of cherry blossom was examined. The plum vinegar extract of cherry blossom had a greater superoxide anion scavenging activity compared with red wine, which is a well-known strong antioxidant. Liquid chromatography-mass spectrometry analysis showed that cyanidin-3-glucoside, cyanidin-3-rutinoside, and caffeic acid were the major components in the phenolic extract prepared from plum vinegar extract of cherry blossom, and they possessed superoxide anion scavenging activity. Caffeic acid is mainly responsible for the scavenging activity of phenolic extract; the contributions of cyanidin-3-glucoside and cyanidin-3-rutinoside were minor.     

Isotopic composition of carbon in vinegars

Measurements of delta 13C and 14C-activity were performed on vinegars from various known sources. Natural vinegar can be distinguished from petrochemical acetic acid by 14C-analysis: Natural vinegar currently gives values of greater than 112% of modern activity; petrochemical acetic acid yields values of 0% of modern activity. Apple cider vinegar can be distinguished from corn-derived vinegar by delta 13C-analysis: Cider vinegar gives delta 13C-values near -26%; corn-derived vinegars yield delta 13C-values near -10%. delta 13C-Analysis also can be applied, with some restrictions, to wine vinegars. These techniques are applied to a series of retail vinegars.     

Chemical and biochemical transformations during the industrial process of sherry vinegar aging

The work described here concerns a study of the chemical and biochemical transformations in sherry vinegar during the different aging stages. The main factors that contribute to the nature and special characteristics of sherry vinegar are the raw sherry wine, the traditional process of acetic acid fermentation in butts (the solera system), and the physicochemical activity during the aging process in the solera system. A number of chemical and biochemical changes that occur during sherry vinegar aging are similar to those that take place in sherry wine during its biological activity process (where the wine types obtained are fino and manzanilla) or physicochemical activity process (to give oloroso wines). Significant increase in acetic acid levels was observed during the biological activity phase. In addition, the concentrations of tartaric, gluconic, succinic, and citric acids increased during the aging, as did levels of amino acids and acetoin. A color change was also produced during this stage. Glycerol was not consumed by acetic acid bacteria, and levels of higher alcohols decreased because of the synthesis of acetates. On the other hand, in the physicochemical phase the microbiological activity was lower. Concentrations of some cations increased because of evaporation of water through the wood. A color change was also produced in this stage. Concentrations of different amino acids decreased because of reaction with carbonyl compounds. A precipitation of potassium with tartaric acid was also observed.     

Influence of cultivar, harvest time, storage conditions, and peeling on the antioxidant capacity and phenolic and ascorbic acid contents of apples and pears

Apple and pear fruits are important sources of secondary plant metabolites and one of the major sources of dietary phenolics consumed all year round. The aim of this work was to identify the main variables influencing phenolic content and antioxidant capacity in apples. Higher phenolic and antioxidant contents were observed in some varieties (such as the Delbar Estival apple and Durondeau pear). Storage conditions were important. Our results also showed that fruits should be consumed rapidly after purchase and with their peel. After one week of domestic storage, the ascorbic acid content was found to decrease by 75%. Peeling led to a more than 25% decrease in total phenolics and ascorbic acid. The harvest time (at normal ripeness) had only a limited impact, but significant year-to-year variations were observed. In conclusion, well-chosen and well-stored apples and pears may contribute to an antioxidant-rich diet if consumed rapidly and with their peel.     

Potent aroma compounds of two red wine vinegars

Gas chromatography olfactometry (GCO) was used to determine key aroma compounds of two red wine vinegars. Sensory analysis was performed to choose the best neutralization agent of acetic acid (NaOH or MgO) and to test representativeness of four extracts obtained by different methods (dichloromethane extraction, XAD-2, mixture of XAD-2 and XAD-7, and Extrelut resins extraction). Neutralization with NaOH followed by dichloromethane extraction was selected to extract volatile compounds of vinegars. Key odorant compounds were determined by GCO based on detection frequency with 13 people. In the two red wine vinegars, 13 odors were perceived by at least 70% of the panelists, and 8 compounds among the 13 were identified: acetic acid, 3-methylbutyric acid, 2-phenyl-1-ethanol, 2, 3-butanedione, butyric acid, 2-methylbutyric acid, mixture of 2- and 3-methyl-1-butanol, and two newly identified compounds in vinegar, 3-hydroxy-2-pentanone and 3-(methylthio)-1-propanal. Quantification of all the volatile compounds was performed by GC-FID, and 10 other compounds were identified for the first time in wine vinegar.     

Pulsed electric field-assisted vinification of aglianico and piedirosso grapes

Pulsed electric field (PEF) treatments were applied to increase the polyphenolic content of fresh red wines made from Aglianico and Piedirosso grapes. Prior to the fermentation/maceration step, the grape skins were treated at different PEF intensities (field strengths from 0.5 to 1.5 kV/cm and energy inputs from 1 to 50 kJ/kg), with their permeabilization being characterized by electrical impedance measurements. Furthermore, the release kinetics of the total polyphenols and anthocyanins were characterized during the maceration stage by spectroscopic and Folin-Ciocalteu colorimetric methods, respectively. Finally, the fresh wine, obtained after pressing, was characterized for total acidity, pH, reducing sugar, color intensity, total polyphenols, anthocyanins content, antioxidant activity, and volatile compound composition. PEF treatment on Aglianico grapes induced a significantly higher release of polyphenols (+20%) and anthocyanins (+75%), thus improving the color intensity (+20%) and the antioxidant activity of the wine (+20%) while preserving the other organoleptic characteristics. In contrast, there was only a minor impact on the polyphenolic release kinetics of Piedirosso grapes, despite the significant degree of cell membrane permeabilization.     

Influence of the acetification process on phenolic compounds

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%.     

Antioxidant content and free radical scavenging ability of fresh red pummelo [Citrus grandis (L.) Osbeck] juice and freeze-dried products

The antioxidative phytochemicals in various fruits and vegetables are widely recognized for their role in scavenging free radicals, which are involved in the etiology of many chronic diseases. Colored fruits are especially considered a quality trait that correlates with their nutritional values and health benefits. The specific aim of this study was to investigate the antioxidants in the juice and freeze-dried flesh and peel of red pummelo and their ability to scavenge free radicals and compare them with those in white pummelo juice. The total phenolic content of red pummelo juice extracted by methanol (8.3 mg/mL) was found to be significantly higher than that of white pummelo juice (5.6 mg/mL). The carotenoid content of red pummelo juice was also significantly higher than that in white pummelo juice. The contents of vitamin C and delta-tocopherol in red pummelo juice were 472 and 0.35 mug/mL, respectively. The ability of the antioxidants found in red pummelo juice to scavenge radicals were found by methanol extraction to approximate that of BHA and vitamin C with a rapid rate in a kinetic model. The ability of methanol extracts of freeze-dried peel and flesh from red pummelo to scavenge these radicals was 20-40% that of BHA and vitamin C effects. Fresh red pummelo juice is an excellent source of antioxidant compounds and exhibited great efficiency in scavenging different forms of free radicals including DPPH, superoxide anion, and hydrogen peroxide radicals.     

Spectrofluorometric determination of histamine in wines and other alcoholic beverages

The spectrofluorometric determination of histamine in wines, other alcoholic beverages, and vinegars is described. Histamine is extracted with n-butanol, transferred to hydrochloric acid, and subjected to a condensation reaction with o-phthalaldehyde (OPT). The method was tested for sensitivity (0.03 ppm limit of detection and 0.08 ppm limit of determination), precision (6.4% CV for a content of 1.25 ppm and 19.5% CV for a content of 0.25 ppm), accuracy (97.1%), recovery (90.6-96.9%), and lack of interference by histidine. The method can be applied to wine, must, beer, champagne, cider, vermouth, and vinegar with satisfactory results.     

Evolution of the aroma profile of sherry wine vinegars during an experimental aging in wood

Changes in the aroma profile of five Sherry wine vinegars submitted to an experimental static aging in wood were followed along 24 months. Eighteen volatile compounds were determined by GC-FID. The results were subjected to multivariate analyses: principal component analysis and linear discriminant analysis. The aroma profile of vinegar can be useful to discriminate vinegars produced from different substrates or with different aging times. During the experimental aging, volatile compounds such as methyl acetate, methanol, diacetyl, and gamma-butyrolactone underwent significant concentration increases. Moreover, the initial ethanol content of vinegars is a factor in the final aromatic richness. The formation of ethyl acetate stood out in samples with an initial ethanol content of approximately 2 alcoholic degrees.     

Effect of mash maceration on the polyphenolic content and visual quality attributes of cloudy apple juice

The effects of enzymatic mash treatments on yield, turbidity, color, and polyphenolic content of cloudy apple juice were studied. Using HPLC-ESI-MS, cryptochlorogenic acid was identified in cv. Brettacher cloudy apple juice for the first time. Commercial pectolytic enzyme preparations with different levels of secondary protease activity were tested under both oxidative and nonoxidative conditions. Without the addition of ascorbic acid, oxidation substantially decreased chlorogenic acid, epicatechin, and procyanidin B2 contents due to enzymatic browning. The content of chlorogenic acid as the major polyphenolic compound was also influenced by the composition of pectolytic enzyme preparations because the presence of secondary protease activity resulted in a rise of chlorogenic acid. The latter effect was probably due to the inhibited protein-polyphenol interactions, which prevented binding of polyphenolic compounds to the matrix, thus increasing their antioxidative potential. The results obtained clearly demonstrate the advantage of the nonoxidative mash maceration for the production of cloud-stable apple juice with a high polyphenolic content, particularly in a premature processing campaign.     

Determination of antioxidant power of red and white wines by a new electrochemical method and its correlation with polyphenolic content

A new method for measuring the antioxidant power of wine has been developed based on the accelerated electrochemical oxidation of 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS). The calibration (R = 0.9922) and repeatability study (RSD = 7%) have provided good statistical parameters. The method is easy and quick to apply and gives reliable results, requiring only the monitoring of time and absorbance. It has been applied to various red and white wines of different origins. The results have been compared with those obtained by the total antioxidant status (TAS) method. Both methods reveal that the more antioxidant wines are those with higher polyphenolic content. From the HPLC study of the polyphenolic content of the same samples, it is confirmed that there is a positive correlation between the resveratrol content of a wine and its antioxidant power.     

Evolution of phenolic compounds during an experimental aging in wood of Sherry vinegar

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.     

Use of an electrochemically etched platinum microelectrode for ascorbic acid mapping in oranges

A positionable platinum microelectrode fabricated by electrochemical etching was used to monitor the concentration of ascorbic acid in fruits and vegetables. Studies carried out with ascorbate oxidase confirmed the suitability of the amperometric sensor to measure selectively the ascorbic acid content. The results obtained with the proposed method for ascorbic acid determination in orange juices compared well with those found by iodimetry with coulometrically generated iodine. The standard deviation calculated by measuring limiting current values in voltammograms was found to be 3% (n = 150). The sensor allowed the evaluation of the spatial distribution of ascorbic acid concentration in oranges by in-situ measurements. Ascorbic acid concentration maps show that in a perpendicular cut the concentration is higher near the peel to the center of the fruit. In a parallel cut, the concentration increases with the distance to the stem. A correlation between the ripening stage and the ascorbic acid concentration was also observed from electrochemical measurements, the content being higher in mature fruits.     

Influence of processing stages on antimutagenic and antioxidant potentials of rooibos tea

The antimutagenic and antioxidant potentials of rooibos (Aspalathus linearis) tea samples, collected from each of its major processing stages, were evaluated according to the Salmonella typhimurium mutagenicity test and the hydrogen donating ability and superoxide anion radical scavenging assays, respectively. Ten random samples were collected before and after fermentation, as well as after sun-drying, sieving, and steam pasteurization. Results indicated that the fermented tea had a significantly (P < 0.05) lower antimutagenic and antioxidant potential than the unfermented tea. Of the different processing stages, the most significant reduction in the antimutagenic and antioxidant property of the tea was found during the "fermentation" step. Sun-drying, sieving, and steam pasteurization also reduced the antimutagenic potential of the tea, although not to the same extent as the first processing step. The hydrogen donating ability was significantly increased after steam pasteurization in comparison to those of fermented and sun-dried tea. Pasteurization did not affect superoxide anion radical scavenging in comparison to fermented tea. Differences seem to exist in the antimutagenicity and antioxidant potencies of the tea sampled at the various stages during processing. A possible role of tea polyphenols in the antimutagenic and antioxdant activities of the tea is suggested as processing caused a significant reduction in the total polyphenolic content.     

Identification and antiradical properties of anthocyanins in fruits of Viburnum dilatatum thunb

The fruit of Viburnum dilatatum Thunb., called gamazumi, has been shown to prevent oxidative injury in rats given gamazumi crude extract (GCE). Therefore, phenolic compounds in GCE were purified by Sephadex LH-20 column chromatography and preparative high-performance liquid chromatography. Two major anthocyanins were isolated, and their structures were determined by NMR, liquid chromatography/electrospray ionization mass spectrometry/MS and sugar analysis as cyanidin 3-O-(2-O-beta-D-xylopyranosyl)-beta-D-glucopyranoside, namely, cyanidin 3-sambubioside (I) and that of cyanidin 3-O-beta-D-glucopyranoside, namely, kuromanin (II). This is the first identification of these compounds in V. dilatatum fruits, which contain I and II at 141.3 and 4.5 microg/g of fresh fruit, respectively. By the electron spin resonance method, the superoxide anion radical scavenging activities (IC(50)) of I and II were 17.3 and 69.6 microM, and their activities on hydroxyl radicals were 4.3 and 53.2 mM. As a positive control, the activities of ascorbic acid were 74.2 microM on superoxide anion radicals and 3.0 mM on hydroxyl radicals. Our results suggest that these anthocyanins having radical scavenging properties may be key compounds contributing to the antioxidant activity and physiological effects of V. dilatatum fruits.     

Effect of reddening-ripening on the antioxidant activity of polyphenol extracts from cv. 'Annurca' apple fruits

Apple is among the most consumed fruits worldwide, and several studies suggest that apple polyphenols could play a role in the prevention of degenerative diseases. 'Annurca' apple fruit undergoes, after harvest, a typical reddening treatment to turn the apples' skin red, and it is noted for its high firmness. This paper reports the effect of reddening-ripening treatment on polyphenol concentration and antioxidant activity of both peel and flesh extracts. The in vitro antioxidant properties have been compared with the protective effect against the cytotoxic effects of reactive oxygen species using Caco-2 cells as model system. Pretreatment of cells with different polyphenolic apple extracts provides a remarkable protection against oxidative damage. This effect seems to be associated with the antioxidant activity of 'Annurca' apple polyphenolic compounds. The flesh has antioxidant properties comparable to those possessed by the peel. Neither the reddening nor the fruit conservation causes changes in the antioxidant properties possessed by this apple variety. The data indicate that polyphenolic compounds in 'Annurca' apples are relatively stable in the peel and also in the flesh; therefore, the health benefits of polyphenols should be maintained during long-term storage. Finally, a diet rich in apple antioxidants could exert a beneficial effect in the prevention of intestinal pathologies related to the production of reactive oxygen species.