Polysaccharide profile and content during the vinification and aging of Tempranillo red wines

Passing from must to wine produced a loss of low-molecular-weight grape structural glucosyl polysaccharides, and an important gain in yeast mannoproteins (MP) and grape-derived arabinogalactan proteins (AGP), and rhamnogalacturonans-II (RG-II). AGP were more easily extracted than RG-II, and small quantities of RG-II monomers and galacturonans were detected. Postmaceration produced a reduction in all grape polysaccharide families, particularly acute in AGP. The reduction of polysaccharides during malolactic fermentation only affected grape AGP, and MP were continuously liberated during the entire vinification process. Wine oak and bottle aging was associated with a relative stability of the polysaccharide families. AGP were thus the majority polysaccharides in young wines but, contrary to what may be thought, structural glucosyl oligosaccharides dominated in musts and MP in aged wines. Precipitation of polysaccharides was noticeable during vinification, and it mainly affected high-molecular-weight AGP and MP. Hydrolytic phenomena affected the balance of wine polysaccharides during late maceration-fermentation.     

Evolution of phenolic composition of red wine during vinification and storage and its contribution to wine sensory properties and antioxidant activity

The objective of this work was to study the evolution of the phenolic composition of red wine during vinification and storage and its relationship with some sensory properties (astringency and bitterness) and antioxidant activities. Thus, red wine was made by a classic vinification method with Castela?o and Tinta Miu?da grapes (Vitis vinifera L.) harvested at maturity (3:2; w/w). Samples were taken at 2 and 7 days of maceration, at second racking, at the time of bottling and at 6 and 14 months after bottling. The total polyphenols extract (TPx) in each sample was isolated by column chromatography. The phenolic composition (anthocyanins and proanthocyanidins), in vitro antioxidant activity, and sensory property (astringency, bitterness) of the isolated TPx from different winemaking stages were evaluated through high-performance liquid chromatography-diode array detection, 1,1-diphenyl-2-picrylhidrazyl radical test, ferric reducing antioxidant power assay, total phenolic index, MWI (polyphenol molecular weight index), TSA (tannin specific activity), and sensory panel tasting. The results showed that the phenolic composition of red wine varied significantly during winemaking. The intensity of astringency (IA) and the intensity bitterness (IB) of the isolated TPx from different winemaking stages increased from 2 days of maceration until second racking and then decreased. Furthermore, MWI and TSA are positively correlated with IA and IB. The in vitro antioxidant activity of the isolated TPx from different winemaking stages maintained unchanged after alcoholic fermentation, which was independent of the variation of phenolic composition and sensory properties.     

Berry phenolics and their antioxidant activity

Phenolic profiles of a total of 26 berry samples, together with 2 apple samples, were analyzed without hydrolysis of glycosides with HPLC. The phenolic contents among different berry genera varied considerably. Anthocyanins were the main phenolic constituents in bilberry, bog-whortleberry, and cranberry, but in cowberries, belonging also to the family Ericaceae genus Vaccinium, flavanols and procyanidins predominated. In the family Rosaceae genus Rubus (cloudberry and red raspberry), the main phenolics found were ellagitannins, and in genus Fragaria (strawberry), ellagitannins were the second largest group after anthocyanins. However, phenolic acids were dominant in rowanberries (genus Sorbus) and anthocyanins in chokeberry (genus Aronia). In the family Grossulariaceae genus Ribes (currants and gooseberry), anthocyanins predominated, as well as in crowberries (family Empetraceae genus Empetrum). In apples, hydroxycinnamic acids were the main phenolic subgroup. Extraction methods for berries and apples were studied to produce phenolic extracts with high antioxidant activity. Evaluation of antioxidant activity was performed by autoxidazing methyl linoleate (40 degrees C, in the dark). The extraction method affected remarkably both the phenolic composition and the antioxidant activity, but with statistical analysis the observed activity could not be well explained with the contents of individual phenolic subgroups.     

Polyphenol content and total antioxidant activity of vini novelli (young red wines)

Eight commercial Italian vini novelli (red wines prepared by carbonic maceration and supposed to be consumed within three months from their wine-making) were evaluated for their total antioxidant activity. The wines had an average total phenol content (1605.4 +/- 337.4 mg/L gallic acid equivalents) lower than that of wines prepared by traditional maceration and consumable after aging (2057. 3 +/- 524.0 mg/L gallic acid equivalents). The average flavanol content (424.7 +/- 121.3 mg/L catechin equivalents) and the total antioxidant activity (16.8 +/- 3.8 mmol/L Trolox equivalents) of vini novelli were higher than the corresponding values (382.7 +/- 174.5 mg/L catechin equivalents and 12.3 +/- 3.3 mmol/L Trolox equivalents) found for aged wines. Three couples of experimental wines were prepared from the same grapes by traditional or carbonic maceration. These wines showed a different phenolic pattern, anthocyanins being more abundant in vini novelli. However, the average total antioxidant activities of the wines were similar, suggesting that aging (and not the wine-making technique) is the main factor influencing the antioxidant activity of red wines.     

Relationship among antioxidant activity, vasodilation capacity, and phenolic content of red wines

The relationship among antioxidant activity, based on the electron-spin resonance determination of the reduction of Fremy's radical, vasodilation activity, and phenolic content was investigated in 16 red wines. The wines were selected to provide a range of origins, grape varieties, and vinification methods. Sensitive and selective HPLC methods were used for the analysis of the major phenolics in red wine: free and conjugated myricetin, quercetin, kaempferol, and isorhamnetin; (+)-catechin, (-)-epicatechin, gallic acid, p-coumaric acid, caffeic acid, caftaric acid, trans-resveratrol, cis-resveratrol, and trans-resveratrol glucoside. Total anthocyanins were measured using a colorimetric assay. The total phenolic content of the wines was determined according to the Folin-Ciocalteu colorimetric assay and also by the cumulative measurements obtained by HPLC. The 16 wines exhibited a wide range in the values of all parameters investigated. However, the total phenol contents, measured both by HPLC and colorimetrically, correlated very strongly with the antioxidant activity and vasodilation activity. In addition, the antioxidant activity was associated with gallic acid, total resveratrol, and total catechin. In contrast, only the total anthocyanins were correlated with vasodilation activity. The results demonstrate that the different phenolic profiles of wines can produce varying antioxidant and vasodilatant activities, which opens up the possibility that some red wines may provide enhanced health benefits for the consumer.     

Multivariate analysis of antioxidant power and polyphenolic composition in red wines

It has been demonstrated that the dietary intake of compounds having antioxidant activity is very important, and various chemical, biological, and electrochemical methods have been proposed to evaluate the antioxidant power of compounds such as polyphenols. Wine, although nonessential, has a high polyphenol content up to 2-3 g/L in red wines obtained by traditional maceration. The polyphenol content of wines is usually evaluated by the Folin reagent, which provides an appropriate response to the requirements of wine manufacturers. Because the presence of individual polyphenols may be evaluated by HPLC, more or less selective methods toward the various chemical classes of polyphenols have been developed. An HPLC method set up recently was applied to evaluate how individual polyphenols contributed to the overall antioxidant power (AOP) of 60 Italian red wines, trying to identify the effect that individual compounds may have on the total AOP. Application of the multivariate analysis allowed us to detect some determining compounds such as gallic acid and some flavonols. On the basis of the correlation between two traditional chemical methods, namely the total polyphenol determination by the Folin reagent and the flavanol determination by the condensation reaction with p-(dimethylamino)-cinnamaldehyde, it was shown that the use of these two merely chemical methods is well correlated (r = 0.83 and 0.87) to an AOP evaluation of red wines.     

Method for measuring antioxidant activity and its application to monitoring the antioxidant capacity of wines.

A novel method for measuring the antioxidant activity using N, N-dimethyl-p-phenylenediamine (DMPD) was developed. The radical cation of this compound gives a stable colored solution and a linear inhibition of color formation can be observed in the presence of 0. 2-11 microg of TROLOX. The experimental protocol, which is rapid and inexpensive, ensures sensitivity and reproducibility in the measure of antioxidant activity of hydrophilic compounds. The effectiveness of the DMPD method on real foods was verified by evaluating the antioxidant ability of wine samples coming from different areas of Campania, Italy. Antioxidant capacity of wines is strictly related to the amount of phenolic compounds. The results obtained by the DMPD method are very similar to those obtained on the same samples when the radical cation of 2, 2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) (Miller et al., 1996) was used.     

Effect of principal polyphenolic components in relation to antioxidant characteristics of aged red wines.

Aged red wines possess significantly different polyphenolic composition compared with young ones, mainly due not only to formation of polymeric compounds but also because of oxidation, hydrolysis, and other transformations that may occur in native grape phenolics during aging. Representative Greek, single-variety, aged red wines were examined for total phenol, total flavanol, and total anthocyanin content using spectrophotometry, and attempts were made to establish correlations with the antiradical, reducing, and hydroxyl free radical scavenging activity. In addition, HPLC analyses were carried out, to ascertain whether individual polyphenols are actually responsible for the antioxidant effects of aged red wines. It was found that total flavanols are the class of polyphenols that account for hydroxyl free radical scavenging efficacy and to a lesser extent for antiradical and reducing ability, whereas there was a less significant link between the antioxidant properties and the total phenolics and only a weak relationship to total anthocyanin content. The correlation of the antioxidant properties with the principal polyphenols showed that individual compounds are weakly associated with all the antioxidant parameters, suggesting that the expression of antioxidant activity in aged red wines is rather a consequence of synergism between various phenolics, and it is not simply attributed to specific constituents.     

Analytical innovations in the detection of phenolics in wines

A liquid chromatographic method with online photometric and luminescent detection for the determination of 18 phenolic compounds in wines is reported. Photometric detection is performed at four wavelengths, namely, 256, 280, 320, and 365 nm, using a diode array detection system. The luminescent detection is achieved by means of a postcolumn derivatization reaction of 10 of these compounds with terbium(III) in the presence of synergistic agents, such as ethylenediaminetetraacetic acid (EDTA) and n-octyltriphosphine oxide (TOPO). A micellar medium provided by the surfactants sodium dodecyl sulfate and Triton X-100 was used for the determination of the luminescent chelates at lambdaex 317 and lambdaem 545 nm. The long wavelength emission of lanthanide chelates can minimize interferences from background sample matrix, which usually emit at shorter wavelengths. The analytical features of the photometric and fluorometric methods, such as dynamic ranges of the calibration graphs, detection limits, and precision data, have been obtained. The practical usefulness of the developed methods is demonstrated by the analysis of Spanish and Italian wine samples (red, rosé, oloroso, and white), which were diluted and directly injected into the chromatographic system. The accuracy of both methods was checked by assaying a recovery study, which was performed at three different analyte levels for each type of sample.     

Antioxidant profile of red wines evaluated by total antioxidant capacity, scavenger activity, and biomarkers of oxidative stress methodologies

The study of the antioxidant capacity of foodstuffs requires the use of diverse determination methods to gain a wider picture of their multiple effects. The aim of this work was to evaluate the "antioxidant profile" of red wines applying TAC (total antioxidant capacity) methods: 2,2'-azinobis(3-ethyl-benzthiazoline-6-sulfonic acid) (ABTS), 2,2-diphenyl-1-picrylhydrazyl, N,N-dimethyl-p-phenylenediamine dihydrochloride, oxygen radical absorbance capacity, ferric reducing/antioxidant power, hydroxyl and superoxide radical scavenger activities, and biomarkers of oxidative stress methods such as lipid peroxidation inhibition and inhibition of damage to DNA. Furthermore, levels of total polyphenols (TPP) of wines were also evaluated. Three bottles of 107 different Spanish red wines (total samples 321), made from different grape varieties, aging processes, and vintages, were analyzed. The validation of TAC methods, the first step in this work, provided a good linearity, proportionality, and low detection limits. Among these methods, the ABTS was the most satisfactory for its rapidity, cost, and precision. All wines showed an important capacity to scavenge hydroxyl radicals and were capable of blocking superoxide radicals but with 10 times lower intensity. Wines also showed important protective action on biomarkers of oxidative stress; they were much more active to inhibit lipid peroxidation than DNA oxidation. Few statistically significant correlations among levels of TPP and antioxidant properties of wines were detected. Furthermore, values of these correlations were very low.     

Stilbenes and tyrosol as target compounds in the assessment of antioxidant and hypolipidemic activity of Vitis vinifera red wines from southern Brazil

The contents of stilbene monomers, cis-resveratrol, trans-resveratrol, cis-piceid, trans-piceid, and tyrosol, were quantified in Vitis vinifera red wines, cvs. Cabernet Franc, Merlot, Sangiovese, and Syrah, 2006 and 2007 vintages, from the Sa?o Joaquim region, a new grape-growing region at southern Brazil. Moreover, the effect of chronic consumption of these wines on the antioxidant and hypolipidemic activities was monitored in C57BL6 LDL receptor knockout mice and treated with a hypercholesterolemic diet. Red wines from this region had substantial levels of resveratrols (the predominant forms were glycoside and trans) and tyrosol. Biomonitoring of antioxidant and hypolipidemic activities in vivo revealed that consumption of these wines increased the antioxidant capacity and reduced the hypercholesterolemia and hypertriglyceridemia promoted by the hypercholesterolemic diet. Significant correlations were found between the increase of antioxidant capacity markers, the decrease of lipid levels promoted by wine consumption, and the contents of stilbenes and tyrosol, supporting the important biological activity of these compounds.     

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 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.     

Impact of isolation method on the antioxidant activity of rapeseed meal phenolics

Rapeseed meal is the byproduct of the rapeseed deoiling process. Among oilseed plants, rapeseed contains the greatest amount of phenolic compounds. In this study, the rapeseed phenolics were isolated with aqueous methanol, aqueous ethanol, hot water, and enzymatically with ferulic acid esterase. These isolates were tested for radical scavenging and for liposome and low-density lipoprotein (LDL) model systems. The radical scavenging activities of all isolates were >60% at a concentration of 1.5 mg/mL. In the liposome model system the formation of hexanal was inhibited by all rapeseed meal isolates by >90% and the formation of conjugated diene hydroperoxides by >80% (8.4 microg/mL concentration). All rapeseed meal isolates also inhibited oxidation of LDL particles by >90% inhibition (4.2 microg/mL concentration). Isolation of rapeseed meal phenolics with either water or enzyme is a very suitable method devoid of organic solvents. Thus, rapeseed meal phenolics constitute an interesting source for food and cosmetic applications with antioxidant effect.     

Profiles of carotenoids, anthocyanins, phenolics, and antioxidant activity of selected color waxy corn grains during maturation

Waxy corns are becoming increasingly consumed as fresh foods or as raw materials for whole grain foods facilitating human consumption in China, so they are usually harvested before complete maturity. Unfortunately, information on functional properties of immature waxy corns is very limited. Therefore, we investigated the profiles of carotenoids, anthocyanins, phenolics, and the antioxidant activity in three types of waxy corn with different colors (white, yellow, and black) during maturation, as well as a normal corn (yellow) used as control. The results showed that black waxy corn had the highest quantity of anthocyanins, phenolics and the best antioxidant activity, yellow corn contained a relatively large amount of carotenoids, while white corn had the lowest amounts of carotenoids, anthocyanins, phenolics, and antioxidant capacity. For each type of waxy corn, the higher carotenoids were found at the M2 stage (no major difference between the M1 and M2 stages for yellow corn). The levels of anthocyanin and phenolics decreased for white and yellow corns, contrary to those for black corn during maturation. The antioxidant activity determined by scavenging 2,2-diphenyl-1-picrylhydrazyl (DPPH), the ferric reducing antioxidant power (FRAP), and the Trolox equivalent antioxidant capacity (TEAC) assays increased with ripening, but no difference was found between the M2 and maturity stages for yellow and black corns. For white corn, the DPPH radical scavenging activity first increased and then decreased, while the antioxidant activity determined by TEAC and FRAP assay decreased during maturation. Differences in these parameters indicate that types and harvesting time have significant influences on functional properties of waxy corns.     

Role of polyphenols in copper complexation in red wines.

Four monovarietal red wines, Tinta Roriz, Tinta Barroca, Touriga Nacional, and Touriga Francesa, were studied for their complexometric properties toward copper. For the purpose, ion selective electrode potentiometric titrations were carried out, and the data were treated by two methods suitable for heterogeneous ligands: the Scatchard plot, which provided the complexation capacity (CC(total) = maximum number of moles of sites per liter), and the differential equilibrium function (DEF), which provided the conditional stability constants of the sites effectively involved in the metal complexation (K(DEF)) at a given titration point. The different wines displayed similar properties: CC(total) ranged from 4.5x10(-3) (Tinta Barroca) to 4.9x10(-3) M (Touriga Francesa), and log K(DEF) values were between 4.2 and 6.5. The range of log(|Cu|(bound)/CC(total)) = log theta embraced in the titration was between -0.2 and -1.9. With regard to the natural levels of copper, from 4.4x10(-7) (Tinta Roriz) to 1.3x10(-6) M (Touriga Nacional), and ligands (CC(total)) in the wines, it can be expected that copper will be strongly complexed in the studied wines (log K(DEF) > 6). Studies carried out, in parallel, for solutions of isolated seed tannins and skin polyphenols (mainly anthocyans) showed that their contribution to the CC(total) of the wines was <40% for tannins and <2% for skin polyphenols. However, skin polyphenols were shown to be much stronger copper ligands (log K(DEF) = 6.7, log theta = -1.5) than tannins (log K(DEF) = 4.5, log theta = -1.5).     

Ellagitannins,flavonoids, and other phenolics in red raspberries and their contribution to antioxidant capacity and vasorelaxation properties

Analysis of extracts of Glen Ample raspberries (Rubus idaeus L.) by gradient, reverse phase HPLC with diode array and tandem mass spectrometry identified eleven anthocyanins, including cyanidin-3-sophoroside, cyanidin-3-(2(G)-glucosylrutinoside), cyanidin-3-glucoside, cyanidin-3-rutinoside, pelargonidin-3-sophoroside, pelargonidin-3-(2(G)-glucosylrutinoside), and pelargonidin-3-glucoside. Significant quantities of an ellagitannin, sanguiin H-6, with an M(r) of 1870 were detected along with lower levels of a second ellagitannin, lambertianin C, which has an M(r) of 2804. Other phenolic compounds that were detected included trace levels of ellagic acid and its sugar conjugates along with one kaempferol- and four quercetin-based flavonol conjugates. Fractionation by preparative HPLC revealed that sanguiin H-6 was a major contributor to the antioxidant capacity of raspberries together with vitamin C and the anthocyanins. Vasodilation activity was restricted to fractions containing lambertianin C and sanguiin H-6.     

Occurrence of anthocyanin-derived pigments in red wines

Several anthocyanin-derived pigments that showed UV-visible spectra different from those of the original grape anthocyanins were detected by HPLC-DAD analysis in 1-year-old bottled Port wines from the Douro region. Among these, three malvidin 3-glucoside derived pigments were detected in large amounts, representing approximately 60% of the total anthocyanidin monoglucosides content. These pigments were isolated, purified, and identified by LSI-MS and NMR ((1)H, DQF-COSY, ROESY, HSQC, and HMBC) techniques. The major pigment is malvidin 3-glucoside pyruvic adduct, previously characterized, and the other two corresponded to its respective acetyl and coumaroyl glucoside derivatives. The latter is reported for the first time in red wines.     

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.     

燕麦生物碱的提取及其抗氧化活性研究

采用正交试验设计对麸皮中燕麦生物碱（AV）的提取条件进行优化,提取物经大孔吸附树脂纯化,并利用活性氧和DPPH自由基的清除率研究其抗氧化活性。结果表明：最佳提取参数为温度60℃,提取时间2h,溶剂为乙醇/水/冰醋酸（80/19.9/0.1）,料液比1︰8,此条件下得率为5.29%,经树脂纯化后粗提物中生物碱纯度达19.2%,且纯化后的燕麦生物碱表现出较强的清除OH·,O2-·和有机自由基DPPH的体外抗氧化活性,其清除能力分别是α-生育酚的79.4%、82.2%和78.0%。