Changes during storage in conventional and ecological wine: phenolic content and antioxidant activity

Polyphenol content, free radical scavenging capacity, and changes during storage over 7 months in the dark were studied in ecological and conventional red and white wines. In red wines, the most changeable components during storage were the anthocyanins since during storage anthocyanins content decreased 88% in conventional wine and 91% in ecological wine. Initially, the total flavonol contents of the conventional and ecological red wines were 163.88 +/- 2.69 and 153.58 +/- 1.71 mg/L, respectively, and no significant variations occurred during storage. No differences in hydroxycinnamic acid derivatives content between conventional and ecological red and white wines were observed. The flavonol level in white wines was very low, as expected since these compounds are found in grape skin. The initial antioxidant activity was 5.37 +/- 0.14 and 5.82 +/- 0.31 mM equivalents Trolox for conventional and ecological red wines, respectively; no significant differences were observed (p = 0.2831), and these values were 7-8 times higher than the antioxidant activity observed in conventional and ecological white wine. In contrast with other studies, the total concentrations of phenolic compounds in conventional and ecological red and white wines were not related to antioxidant activity (p > 0.05). In red wines, no significant differences were observed in the antioxidant activity of ecological and conventional red wine (p = 0.28), while in white wine significant differences were observed in the antioxidant activity between conventional and ecological white wine (p = 0.006).     

Relationship between potentiometric measurements, sensorial analysis, and some substances responsible for aroma degradation of white wines

Oxidative degradation of white wines can be described sensorially as developing from a loss at positive aroma characteristics, through the development of negative aromas to a linel stage of chromatic alterations. This work attempts to relate the oxidation "status" evaluate by potentiometric titrations, with sensorial degradation and the levels of substances responsible for "off-flavors", such as methional and phenylacetaldehyde. The potentiometric titration employed measures the most powerful antioxidants of white wines (e.g., those which more rapidly consume oxygen). Considering that aromatic precedes chromatic degradation, resistance to oxidation (ROX) constitutes a useful indicator of resistance to oxidation. Sensorial degradation (ID), potentiometric measures, and volatiles were determined both in samples submitted to a "forced aging" protocol and normal aged white wines. High correlation values were observed between ROX and the ID, in both sets (r > 0.87). ID is better explained by ROX values than by the indicated wine age or by the "degree of browning" (Abs = 420 nm). It was also observed that in samples with ROX values higher than 10, the concentration of methional and phenylacetaldehyde were above their respective odor threshold. Finally, it was observed that there is a relationship between oxygen consumption and the respective ROX. Although these results seem very promising, they needed to be further complemented in order to estimate the shelf life of a white wine using potentiometric titrations.     

Antioxidant capacities and phenolics levels of French wines from different varieties and vintages.

Phenolics from grapes and wines can play a role against oxidation and development of atherosclerosis. Levels of phenolics, major catechins [(+)-catechin, (-)-epicatechin, procyanidin dimers B1, B2, B3, and B4], phenolic acids (gallic acid and caffeic acid), caftaric acid, malvidin-3-glucoside, peonidin-3-glucoside, and cyanidin-3-glucoside were quantified by HPLC with UV detection for 54 French varietal commercial wines taken from southern France to study the antioxidant capacity and the daily dietary intake of these compounds for the French population. The highest antioxidant capacity was obtained with red wines and ranged from 12.8 mmol/L (Grenache) to 25.2 mmol/L (Pinot Noir). For white wines, Chardonnay enriched in phenolics by special wine-making was found to have an antioxidant capacity of 13.8 mmol/L, comparable to red wine values. For red wines classified by vintages (1996-1999) antioxidant capacities were approximately 20 mmol/L and then decreased to 13.4 mmol/L for vintages 1995-1991. Sweet white wines have 1.7 times more antioxidant capacity (3.2 mmol/L) than dry white wines (1.91 mmol/L). On the basis of a still significant French wine consumption of 180 mL/day/person, the current daily intake of catechins (monomers and dimers B1, B2, B3, and B4) averaged 5 (dry white wine), 4.36 (sweet white wines), 7.70 (rosé wines), 31.98 (red wines), and 66.94 (dry white wine enriched in phenolic) mg/day/resident for the French population. Red wine, and particularly Pinot Noir, Egiodola, Syrah, Cabernet Sauvignon, and Merlot varieties, or Chardonnay enriched in phenolics during wine-making for white varieties contribute to a very significant catechin dietary intake.     

Ellagic acid and flavonoid antioxidant content of muscadine wine and juice

Antioxidant properties of flavonoids and ellagic acid were characterized in eight wines and juices produced by various processing methodologies from red and white muscadine grape cultivars (Vitis rotundifolia). Juices and wines were produced by hot- and cold-pressed techniques, and additional wine was produced following on-hull fermentation for 3, 5, and 7 days. Chromatographic conditions were developed to simultaneously separate anthocyanins, ellagic acid, and flavonols and correlated to a measurement of overall antioxidant capacity (AOX), and their changes were monitored after storage for 60 days at 20 and 37 degrees C. Regression coefficients between concentrations of individual polyphenolics and AOX ranged from 0.55 for ellagic acid to 0.90 for kaempferol. Both red and white wines had higher AOX values after storage than juices made from an identical grape press, despite lower concentrations of individual polyphenolic compounds. Red wines fermented on-hull had higher initial concentrations of antioxidant polyphenolics as compared to a corresponding hot-pressed juice, but changes in AOX during storage were more affected by time than by storage temperature despite lower concentrations of flavonoids and ellagic acid present at 37 degrees C as compared to 20 degrees C. Oxidative or polymerization reactions significantly decreased levels of monomeric anthocyanins during storage with the greatest losses observed for delphinidin and petunidin 3,5-diglucosides. Processing methods for muscadine wine and juice production were important factors influencing concentrations of antioxidant flavonoids and ellagic acid, while the role of fermentation and time had the greatest influence on retention of AOX properties during storage.     

Characterization and quantitation of low and high molecular weight phenolic compounds in apple seeds

The phenolic constituents of seeds of 12 different apple cultivars were fractionated by sequential extraction with aqueous acetone (30:70, v/v) and ethyl acetate after hexane extraction of the lipids. Low molecular weight phenolic compounds were individually quantitated by RP-HPLC-DAD. The contents of extractable and nonextractable procyanidins were determined by applying RP-HPLC following thiolysis and n-butanol/HCl hydrolysis, respectively. As expected, the results revealed marked differences of the ethyl acetate extracts, aqueous acetone extracts, and insoluble residues with regard to contents and mean degrees of polymerization of procyanidins. Total phenolic contents in the defatted apple seed residues ranged between 18.4 and 99.8 mg/g. Phloridzin was the most abundant phenolic compound, representing 79-92% of monomeric polyphenols. Yields of phenolic compounds significantly differed among the cultivars under study, with seeds of cider apples generally being richer in phloridzin and catechins than seeds of dessert apple cultivars. This is the first study presenting comprehensive data on the contents of phenolic compounds in apple seeds comprising extractable and nonextractable procyanidins. Furthermore, the present work points out a strategy for the sustainable and complete exploitation of apple seeds as valuable agro-industrial byproducts, in particular as a rich source of phloridzin and antioxidant flavanols.     

Antioxidant activity in common beans (Phaseolus vulgaris L.)

Beans were pearled to evaluate the feasibility of increasing antioxidant activity and phenolic antioxidants. Phenolics were concentrated mostly in the hull fraction at about 56 mg of catechin equivalents per gram of sample. The methanolic extracts of the pearled bean samples were screened for antioxidant potential using the beta-carotene-linoleate and the 1,1-diphenyl-2-picrylhydrazyl (DPPH) in vitro model systems. The pearled material, also referred to as milled samples, exhibited antioxidant activity that correlated with phenolic content and inhibited DPPH significantly in a dose-dependent manner. Phenolics and antioxidant activities were also examined in chromatographic fractions of methanolic extracts of manually obtained hulls that represented a model used previously to ascertain antimutagenic activity. Fractions extracted with ethyl acetate/acetone and acetone displayed antioxidant activity, which implies potent free radical scavenging activity with antimutagenic activity.     

Red wine making by immobilized cells and influence on volatile composition

Red wine making using yeast cells immobilized in two types of raisin berries, at various temperatures (6-30 degrees C), was studied. A modification of the batch bioreactor was used to separate the grape skins used for color extraction from the biocatalyst and the fermenting grape must. The evaluation of the immobilized biocatalysts was made on terms of productivity and organoleptic quality, including color intensity and formation of volatiles. The immobilized cells were found capable of low-temperature wine making, producing red wines containing more than 11% v/v alcohol in 8 days at 6 degrees C. The quality of wines was examined by gas chromatography (GC) and GC-MS analysis and sensory evaluation. Higher alcohol concentrations were decreased, and ethyl acetate concentrations increased by the drop of temperature. Many esters, alcohols, carbonyls, and miscellaneous compounds were identified in wines produced by immobilized cells, revealing no significant qualitative differences as compared to wines produced by free cells. The sensory evaluation showed that the best red wine was produced at 6 degrees C.     

Quantitative analysis, occurrence, and stability of (E)-1-(2,3,6-Trimethylphenyl)buta-1,3-diene in wine

A stable isotope dilution assay has been developed for quantification of (E)-1-(2,3,6-trimethylphenyl)buta-1,3-diene (4) in wine using a [(2)H(6)]-analogue. Using this method, 4 was found in 96 out of 97 white wines, but in none of 12 red wines analyzed. 4 was found to be most prevalent in Semillon wines, followed by Chardonnay, with Riesling showing the least amount of 4 among these three varieties. 4, like 1,1,6-trimethyldihydronaphthalene (TDN, 3), appears to be formed during the aging process. 4 was found to be unstable in model wine, and in both white and red wine, with the order of stability being model > white > red. In a PVPP-stripped red wine, the rate of degradation of 4 was substantially lessened, with the final concentrations very close to those observed in model wine. When treated with either grape or wine tannin extracts in model wine, the concentration of 4 was found to decrease to levels very close to those observed with an untreated red wine. When white wine was heated at 45 degrees C, 4 was formed, indicating the presence of precursor forms. The amounts formed were much higher than those found in a commercial white wine. 4 was also observed in red wine heated to 45 degrees C, but the concentration produced was much less than that with white wine.     

Flavanol content and antioxidant activity in winery byproducts

Proanthocyanidins, particularly those coming from wine and grape products, have became of interest to nutritionists. Particular attention is currently being paid to the exploitation of this kind of grape byproducts for obtaining bio-active phenolic compounds with potential application as food antioxidants and preventive agents against cancer and other diseases. In this work, the flavanol composition of various winery byproducts submitted to different degrees of industrial exploitation has been studied and their antioxidant activity determined using two different methods (TBARS and TEAC) to evaluate their interest as suitable sources for the preparation of flavanol-rich antioxidant extracts. All the byproducts studied were still good flavanol sources no matter their exploitation degree. An important conclusion was that dried grape seeds, obtained as an end byproduct after the color extraction and alcohol distillation of the wine pomace, still kept important flavanol concentrations and significant antioxidant activity, even if they were submitted to high temperatures. These byproducts can be considered a cheap source for the extraction of antioxidant flavanols, which can be used as dietary supplements or in the production of phytochemicals.     

Impact odorants of different young white wines from the Canary Islands

Five young monovarietal white wines from the Canary Islands made from Gual, Verdello, Marmajuelo, white Listán, and Malvasia grape cultivars were studied to determine the characteristics of their most important aromas and the differences among them. The study was carried out using gas chromatography-olfactometry (GC-O) to detect the potentially most important aroma compounds, which were then analyzed quantitatively by gas chromatography-flame ionization detection and gas chromatography-mass spectrometry. The strongest odorants in the GC-O experiments were similar in all cases, although significant differences in intensity between samples were noted. Calculation of the odor activity values (OAVs) showed that 3-mercaptohexyl acetate was the most active odorant in the Marmajuelo and Verdello wines, as were 3-methylbutyl acetate in the Gual wine, beta-damascenone in the Malvasia wine, and ethyl octanoate in the white Listán wine. However, the most important differences between varieties were caused by the three mercaptans (3-mercaptohexyl acetate, 3-mercaptohexanol, and 4-methyl-4-mercapto-2-pentanone) and the vinylphenols (4-vinylphenol and 2-methoxy-4-vinylphenol). The correlation between the olfactometric values and the OAVs was satisfactory in the cases when the compound eluted in the GC-O system was well isolated from other odorants and had aromatic importance and the OAVs for the different wines were sufficiently different.     

Anthocyanin and proanthocyanidin content in selected white and red wines. Oxygen radical absorbance capacity comparison with nontraditional wines obtained from highbush blueberry

Antioxidant capacity, as measured by oxygen radical absorbance capacity (ORAC(PE)), total phenolic, total and individual anthocyanins, and proanthocyanidin fraction contents were evaluated in red and white wines from grapes. A comparison in terms of antioxidant capacity is made with nontraditional wines made from highbush blueberry. Blueberries are among fruits that are best recognized for their potential health benefits. In red wines, total oligomeric proanthocyanidin content, including catechins, was substantially higher (177.18 +/- 96.06 mg/L) than that in white wines (8.75 +/- 4.53 mg/L). A relative high correlation in red wines was found between ORAC(PE) values and malvidin compounds (r = 0.75, P < 0.10), and proanthocyanidins (r = 0.87, P < 0.05). In white wines, a significant correlation was found between the trimeric proanthocyanidin fraction and peroxyl radical scavenging values (r = 0.86, P < 0.10). A moderate drink (1 drink per day, about 140 mL) of red wine, or white wine, or wine made from highbush blueberry corresponds to an intake of 2.04 +/- 0.81 mmol of TE, 0.47 +/- 0.15 mmol of TE, and 2.42 +/- 0.88 mmol of TE of ORAC(PE)/day, respectively.     

White wine with red wine-like properties: increased extraction of grape skin polyphenols improves the antioxidant capacity of the derived white wine.

Lower antioxidant activity in white wines in comparison to red wines lies in the low grape-skin-derived polyphenol content. This paper reports the analysis of the antioxidant capacities of white wine samples obtained along two different processing procedures directed to enrich the wine with polyphenols. White wine samples derived from whole squeezed grapes stored for increasing periods of time (up to 18 h) contained increasing concentrations of polyphenols (from 0.35 to 0.55 mmol/L) and, in parallel, exhibited increased capacity to scavenge free radicals and to inhibit copper ion-induced low-density lipoprotein (LDL) oxidation. However, addition of increasing concentrations of alcohol (up to 18%) to the whole squeezed grapes remarkably augmented the extraction of grape skin polyphenols into the wine up to 1.25 mmol/L, resulting in an increased capacity of the wine to scavenge free radicals and to inhibit LDL oxidation, to an extent similar to that of red wine. The extent of LDL oxidation inhibition was directly related to the wine polyphenolic content (r = 0.986). It is concluded that processing white wine by imposing a short period of grape skin contact in the presence of alcohol leads to extraction of grape skin polyphenols and produces polyphenol-rich white wine with antioxidant characteristics similar to those of red wine.     

Assays for hydrophilic and lipophilic antioxidant capacity (oxygen radical absorbance capacity (ORAC(FL))) of plasma and other biological and food samples

Methods are described for the extraction and analysis of hydrophilic and lipophilic antioxidants, using modifications of the oxygen radical absorbing capacity (ORAC(FL)) procedure. These methods provide, for the first time, the ability to obtain a measure of "total antioxidant capacity" in the protein free plasma, using the same peroxyl radical generator for both lipophilic and hydrophilic antioxidants. Separation of the lipophilic and hydrophilic antioxidant fractions from plasma was accomplished by extracting with hexane after adding water and ethanol to the plasma (hexane/plasma/ethanol/water, 4:1:2:1, v/v). Lipophilic and hydrophilic antioxidants were efficiently partitioned between hexane and aqueous solvents. Conditions for controlling temperature effects and decreasing assay variability using fluorescein as the fluorescent probe were validated in different laboratories. Incubation (37 degrees C for at least 30 min) of the buffer to which AAPH was dissolved was critical in decreasing assay variability. Lipophilic antioxidants represented 33.1 +/- 1.5 and 38.2 +/- 1.9% of the total antioxidant capacity of the protein free plasma in two independent studies of 6 and 10 subjects, respectively. Methods are described for application of the assay techniques to other types of biological and food samples.     

Comparison of the concentrations of phenolic constituents in cane sugar manufacturing products with their antioxidant activities

Polyphenol content and free radical scavenging capacity of seven kinds of sugar manufacturing products (A sugars, clear juices, syrups, massecuite, and A, B, and C molasses) were studied. Seventy-two samples were collected at different stages of the process during two sugar harvests from a local sugar factory (Bois-Rouge, La Réunion). The total phenolic content of sugar products was determined according to the Folin-Ciocalteu assay. Polyphenols of sugar products were extracted with ethyl acetate and quantified by LC-UV-ESI-MS during all of the process. ABTS and DPPH assays were applied to aqueous solution of sugar products, which exhibited interesting free radical scavenging activity. Comparatively, ethyl acetate extracts exhibited higher antioxidant activity. Multivariate analyses (principal component analysis and canonical discriminant analysis) demonstrated a significant correlation between polyphenols and antioxidant activity. Moreover, it was observed that the sugar process results in an increase of the phenolic content and the free radical scavenging capacity of the different products. These products and especially molasses proved to be a rich source of natural antioxidants and may represent an interesting alternative to synthetic food antioxidants.     

Total phenolic content, antioxidant activity, and cross-cultural consumer rejection threshold in white and red wines functionally enhanced with catechin-rich extracts

White and red wines spiked with catechin-rich green tea extract and grape seed extract were assessed for phenolic content, antioxidant activity, and cross-cultural consumer rejection thresholds in relation to wine as a functional food. Health functionality is an important factor in functional foods, and spiking pure compounds or plant extracts is an effective method to increase or control functionality. The total phenolic content and antioxidant activity were measured in wines spiked to different extract concentrations, namely, control and 50, 100, 200, 400, and 800 mg/L, to confirm the dose-response curves in both white and red wines. Consumer rejection thresholds (CRTs) were established for spiked wines in a Korean and in an Australian population. Our results showed that the green tea extract and grape seed extract increased the antioxidant activity dose dependently, and the CRTs varied considerably between the Korean and the Australian groups, with Koreans preferring wines spiked with green tea extract and Australians showing a preference for wines spiked with grape seed extract. These results have implications for producing wine products that are enhanced in phenolic compounds and targeted to different cultural groups.     

Antioxidant activity of extracts obtained from residues of different oilseeds

Residues of the oil-extracting process of oilseeds contain bioactive substances such as phenolic compounds, which could be used as natural antioxidants for the protection of fats and oils against oxidative deterioration. Thus, the extraction of such constituents from residual material can be considered to contribute to the added value of these residues, which could justify their isolation. In the present work the fat-free residues of eight different oilseeds whose oils are usable for nutritional applications, and also as renewable resources, were extracted with 70% methanol, 70% acetone, water, and ethyl acetate/water, respectively. The resulting extracts were investigated regarding their content of total phenolic compounds by the Folin-Ciocalteau assay, sinapine, flavanoids, and the UV-absorption spectra. Further, the antioxidant activity of the extracts was characterized by the DPPH method, the beta-carotene-linoleic acid assay, and ESR investigations. The fat-free residues of the different oilseeds contained considerable amounts of extractable substances. The yields decreased with decreasing polarity of the solvent in the order water, 70% methanol, 70% acetone, and ethyl acetate. The ratio of total phenolic compounds to the extractable compounds ranged from 3 to 19%. There was no significant correlation between the amount of total extractable compounds and the total phenolic compounds (p < 0.001). All extracts showed remarkable antioxidant activities determined with the different methods. The effects depended strongly on the solvent used for the extraction as well as on the extracted residue. A correlation between the methods used for the characterization of the antioxidant activity and the composition of the residues could not be shown.     

Formation pathways of ethyl esters of branched short-chain fatty acids during wine aging

The particular behavior during wine aging of fermentative branched fatty acid ethyl esters, related to yeast nitrogen metabolism, compared that of their straight-chain analogues, related to yeast lipid metabolism, was first checked in 1-5 year aged Muscadet wines. Quantitative SIDA measurements showed that the levels of the former increased, whereas those of the latter decreased. Then, three hypothetical pathways suggested in the literature to explain these variations of branched esters were investigated. Two Muscadet and Sylvaner wines were spiked with levels of deuterated isobutanoic acid and its ethyl ester, similar to those of their natural analogues, then they were submitted to model aging. Quantitative SIDA measurements on the formation of these natural and labeled ethyl esters from the corresponding acids revealed that the behavior of the natural and labeled compounds were similar. The acid levels were much higher than the ester levels in the initial young wine, and a significant upward trend of their esterification ratios to those of the acid-ester equilibrium was observed with aging. Thus, this equilibrium proved to be the most effective in generating the branched fatty acid ethyl esters during wine aging. In contrast, the formation of these acids by Strecker-type degradation of wine amino acids in the conditions of the model aging or by hydrolysis of their glycoconjugates proved to be ineffective.     

Rapid, fully automated flow injection antioxidant capacity assay

A flow injection method for antioxidant capacity assessment based on a low-cost laboratory-made analyzer is reported. A sample of 30 microL is injected in acetate buffer stream, pH 4.6, that converges with ABTS*(+) reagent stream. Detection is achieved by monitoring absorbance at 414 nm. The proposed method achieves a sample throughput of up to 120 samples h(-1), the detection limit being 1.3 microM trolox. Precision was better than 5% relative standard deviation (n = 4) and the linear range was 4-100 microM, expanded to 250 microM trolox utilizing concentration gradients formed along the injected sample bolus. Information on reaction kinetics is obtained through a single injection. The method was applied to pure compounds and wine and honey samples. Good correlation was found between antioxidant capacity assessed through the proposed method and phenolic content: r = 0.94 for red wines, r = 0.96 for white and rose wines, and r = 0.89 for honeys.     

Feasibility study on chemometric discrimination of roasted Arabica coffees by solvent extraction and Fourier transform infrared spectroscopy

In this feasibility study, Fourier transform infrared (FTIR) spectroscopy and chemometric analysis were adopted to discriminate coffees from different geographical origins and of different roasting degrees. Roasted coffee grounds were extracted using two methods: (1) solvent alone (dichloromethane, ethyl acetate, hexane, acetone, ethanol, or acetic acid) and (2) coextraction using a mixture of equal volume of the solvent and water. Experiment results showed that the coextraction method resulted in cleaner extract and provided a greater amount of spectral information, which was important for sample discrimination. Principal component analysis of infrared spectra of ethyl acetate extracts for dark and medium roast coffees showed separated clusters according to their geographical origins and roast degrees. Classification models based on soft independent modeling of class analogy analysis were used to classify different coffee samples. Coffees from four different countries, which were roasted to dark, were 100% correctly classified when ethyl acetate was used as a solvent. The FTIR-chemometric technique developed here may serve as a rapid tool for discriminating geographical origin of roasted coffees. Future studies involving green coffee beans and the use of larger sample size are needed to further validate the robustness of this technique.     

Wine production using yeast immobilized on apple pieces at low and room temperatures

A biocatalyst was prepared by immobilization of Saccharomyces cerevisiae strain AXAZ-1 on apple pieces. It was examined by electron microscope and studied during the fermentation of grape must for batch wine-making. The immobilized yeast showed an important operational stability without any decrease of its activity even at low temperatures (1-12 degrees C). Specifically, at 6 degrees C the biocatalyst favored wine production within 8 days, which is less time than is required for the natural fermentation of grape must. At 1 degrees C wine production was effected in 1 month. This speeding up of the fermentation could be accepted and adopted by the industry for scaling up the wine-making process. Total and volatile acidities were similar to those found in dry wines. The concentrations of higher alcohols (propanol-1 and isobutyl alcohol) were low. The presence of amyl alcohols proved to be temperature dependent and decreased with the temperature decrease. The values of ethyl acetate concentrations were relatively high, up to 154 mg/L. This probably contributes to the fruity aroma and excellent taste of the produced wines. There was no indication of vinegar odor in the product given that the volatile acidity was <0.47 g of acetic acid/L. From the GC-MS analysis it was concluded that cell immobilization did not create serious changes in the product (wine) with regard to the qualitative composition of the aroma compounds.