Browning of white wines: correlation with antioxidant characteristics, total polyphenolic composition and flavanol content

Browning is a serious problem in relation to white wine quality, which mostly affects the sensory attributes. It is well known to be associated with polyphenol oxidation, and therefore it may be accompanied by changes in the antioxidant capacity. On the basis of this consideration, thirteen experimental white wines, vinified and stored under identical conditions, were subjected to accelerated browning, and efforts were made to distinguish compositional parameters that might be related to the extent of browning development. Further, the relation of browning with the reducing power and the antiradical activity were assessed. Regression analysis at 95% significance level indicated that the antiradical activity is likely to be exerted principally by the flavanol fraction (r² = 0.92) and to a lesser extent by total phenols (r² = 0.85), as opposed to reducing power, which is mainly affected by total phenols (r² = 0.78), suggesting that synergistic phenomena account for the overall antioxidant status of white wines. In addition, the total phenolic and flavanol concentration correlated significantly with the browning rate constants and provided strong evidence that browning development might be predominately associated with flavanol (r² = 0.84) and to a lesser extent with total phenolic (r² = 0.79) oxidation.     

Browning development in white wines: dependence on compositional parameters and impact on antioxidant characteristics

Browning is a serious problem in relation to white wine quality and mostly affects the sensory attributes, whereas its impact on the dietary value of wines has never been investigated. Browning, however, is well known to be associated with polyphenol oxidation, and therefore it may be accompanied by changes in the antioxidant capacity. On the basis of this consideration, experimental white wines vinified and stored under identical conditions were subjected to accelerated browning, and efforts were made to distinguish compositional parameters that might be related to the extent of browning development. Further, the consequences of browning on the reducing power and antiradical activity were assessed. It was shown that none of the parameters examined (titratable acidity, pH, total SO₂, total polyphenols and total flavanols) play an important role in browning onset, but SO₂ appeared to exert a statistically significant influence (r²=0.6394, P<0.05) on the percentage change in the antiradical activity. Evidence also suggested that browning development might be prominently associated with decreases in both antiradical activity (r²=0.7891, P<0.01) and reducing power (r²=0.6925, P<0.05).     

Free radical scavenging capacity of selected red,rosé and white wines

The free radical scavenging capacity of selected red, rosé and white Spanish wines from different grape varieties was determined by the 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH^·) method using a new methodology developed at our laboratory. The amount of sample necessary to decrease by 50% the initial DPPH^· concentration (EC₅₀), the time needed to reach the steady state at EC₅₀ concentration (T_EC50) and the antiradical efficiency (AE = 1/EC₅₀T_EC50) were determined in the wine samples. Some differences between rosé wines made with Garnacha and Tempranillo grape varieties were observed in the UV‐vis spectra and in the free radical scavenging parameters, those from Garnacha variety having the highest antioxidant activity. The antiradical efficiency of the wines followed a decreasing order: red wines (22.44 × 10⁻⁶) > rosé wines (4.90 × 10⁻⁶) > white wines (1.88 × 10⁻⁶). There was a correlation between antiradical efficiency and total polyphenol (TP): AE = −3.33135 + 0.0180535TP; the correlation coefficient was r = 0.951454. © 1999 Society of Chemical Industry     

Anthocyanin profiles of major red grape (Vitis vinifera L.) varieties cultivated in Greece and their relationship with in vitro antioxidant characteristics

A range of fourty‐six red grape (Vitis vinifera spp.) samples, originating from six widely cultivated varieties and covering major parts of the Hellenic vineyard, were assayed for their content in six principal anthocyanin pigments. Representative in vitro antioxidant parameters were also determined, including antiradical activity (A_AR), reducing power (P_R) and hydroxyl free radical scavenging activity (SA_HFR). Quantitative determination using high performance liquid chromatography showed that the prevalent pigment was malvidin 3‐O‐glucoside (average content 82.53 mg per 100 g fresh berry weight), followed by its coumarate derivative (29.26 mg per 100 g), paeonidin 3‐O‐glucoside (10.84 mg per 100 g), petunidin 3‐O‐glucoside (7.80 mg per 100 g) cyanidin 3‐O‐glucoside (5.67 mg per 100 g) and delphinidin 3‐O‐glucoside (1.28 mg per 100 g). The richest variety was Syrah, with total average anthocyanin content of 186.02 mg per 100 g, whereas the Hellenic native variety Xinomavro had the lowest average anthocyanin level (38.70 mg per 100 g). The establishment of correlations of individual and total anthocyanin contents with the values from the antioxidant test was accomplished with linear regression. The links of total anthocyanins were significant with all antioxidant parameters (P < 0.001), but more importantly with SA_HFR (R² = 0.740). Malvidin 3‐O‐glucoside content had the higher correlation with SA_HFR compared with all other anthocyanins (R² = 0.698, P < 0.001).     

Ochratoxin A in wines,musts and grape juices from Spain

A survey on the occurrence of ochratoxin A (OTA) in 240 grape‐based beverages was carried out. Red and white wines from four different Spanish Designations of Origin (n = 160), musts (n = 20), grape juices (n = 10), ordinary wines (n = 20), special wines (Malaga, muscatel, sherry, vermouth, etc) (n = 20) and sparkling wines (n = 10) were assayed for OTA content using immunoaffinity column clean‐up and high‐performance liquid chromatography with fluorimetric detection (detection limit 0.05 µg l^?1). Forty‐three (17.9%) of the samples tested contained detectable levels of OTA. The overall mean OTA concentration in red and white wines of Designations of Origin was 0.30 and 0.18 µg l^?1 respectively (ranges 0.05–3.19 and 0.05–1.13 µg l^?1 respectively). The percentage of wine samples with detectable amounts of OTA was higher for red (18.3%) than for white (10%) wines. OTA was also found in two of 10 red ordinary wines (0.68 and 4.24 µg l^?1), whereas none of 10 white ordinary wines contained OTA. The mean OTA amount detected in sparkling wines was 0.44 µg l^?1 (range 0.14–0.71 µg l^?1). Two of 20 must samples contained OTA at low levels (0.08 and 0.18 µg l^?1), while none of 10 grape juice samples contained OTA. Highest amounts of OTA were found in special wines (45%), with a maximum of 15.25 µg l^?1 in a muscatel sample. Copyright © 2004 Society of Chemical Industry     

Antioxidant activity of predigested protein obtained from a range of farmed edible insects

This study investigated the antioxidant activities of peptides obtained by in vitro gastrointestinal digestion of edible insects. The antioxidant potential of edible insects' hydrolysates was determined as the free radical‐scavenging activity, ion chelating activity and reducing power. The highest antiradical activity against DPPH^˙, whose IC₅₀ value is the lowest, was noted for Amphiacusta annulipes (19.1 μg/mL) and that against ABTS^˙+ was the highest for Zophobas morio (4.6 μg/mL). The peptides obtained from A. annulipes also showed the highest Fe²⁺ chelation ability (58.82%) and reducing power (0.652). The highest ability to chelate Cu²⁺ was noted for Locusta migratoria (86.05%). The locust was characterised by the highest concentration of peptides before digestion and after digestion (3.13 and 5.88 mg/mL, respectively), and the DH was 36.29%.     

Phenolic content and antioxidant potential of macerated white wines

Influence of maceration on phenolic content and antiradical activity was analyzed in fourteen white wines from Italian region Friuli–Venezia Giulia and Croatian region Istria. Total phenols were determined by Folin–Ciocalteu reagent, twelve individual polyphenols were determined by high-performance liquid chromatography and antiradical activity was determined using 2,2-diphenyl-1-picrylhydrazyl free radical (DPPH^·). The experiments showed that the maceration process increases significantly the amount of total phenols and inhibition of DPPH^·. Furthermore, a high synergistic activity of individual phenols was observed. The strongest inhibition of DPPH^· and the highest amount of total phenols were obtained for 800 Bianco, a blending macerated wine made from 3 white wine varieties. Our study shows that the antioxidant potential of white grape phenols can be preserved during wine processing. The maceration step allows the extraction of phenolic compounds from grape skins, seeds and stalks, resulting in phenol-rich white wine with strong antioxidant properties.     

Headspace solid-phase microextraction coupled to gas chromatography-tandem mass spectrometry for the determination of haloanisoles in sparkling (cava and cider) and non-sparkling (wine) alcoholic beverages

A highly sensitive analytical method was developed to determine 2,4,6-trichloroanisole (TCA), 2,3,4,6-tetrachloroanisole (TeCA), 2,4,6-tribromoanisole (TBA) and 2,3,4,5,6-pentachloroanisole (PCA) in sparkling alcoholic beverages. The method was based on the use of headspace solid-phase microextraction (HS-SPME) using a polydimethylsiloxane (PDMS) fibre. It was coupled to gas chromatography-triple quadrupole tandem mass spectrometry (GC-QqQ-MS/MS) for the detection and quantification of the target haloanisoles. The method was fully automated and no sample preparation was needed. The method was validated for alcoholic beverages. The influence of CO₂ on the extraction efficiency was also evaluated for the studied sparkling drinks (cava and cider). All the calibration curves showed good linearity (R² > 0.98) within the tested range (1–50 ng l^?1). Recoveries were evaluated at three different levels (1, 5 and 50 ng l^?1) and were always between 71% and 119%. Precision was expressed as relative standard deviation (RSD), and was evaluated as intra- and inter-day precisions, with values ≤ 22% in both cases. Limits of quantitation (LOQs) were ≤ 0.91 ng l^?1, which are below the sensory threshold levels for such compounds in humans. The validated method was applied to commercial samples, 10 cavas and 10 ciders, but it was also used for the analysis of nine red wines and four white wines, demonstrating the further applicability of the proposed method to non-sparkling beverages. TCA was detected in most samples at up to 0.45 ng l^?1.     

Factorial design optimisation of grape (<Emphasis Type="Italic">Vitis vinifera</Emphasis>) seed polyphenol extraction

A 2³-full factorial design and response surface methodology were deployed to assess some basic factors (time, % ethanol and pH) affecting profoundly the extractability of polyphenolic phytochemicals from grape (V. vinifera) seeds. In an effort to obtain a thorough insight into the applicability of the models established, seed extracts from three different varieties were tested, by determining several indices of the polyphenolic composition, such as total polyphenol (TP), total flavanol (TFl) and proanthocyanidin (PC) concentrations. It has been shown that the models generated can adequately predict the recovery levels for each polyphenol group, but the optimal conditions predicted for TP, TFl and PC recovery varied significantly. Notable differences were also seen among the different varieties. Correlation of the polyphenol indices with the antiradical activity and reducing power of the extracts indicated that there is no consistent pattern to associate specific polyphenol classes with the antioxidant potential, which might be an evidence of antagonism. Examination of the optimally obtained extracts using liquid chromatography-mass spectrometry revealed that the most prominent compounds were catechin, some flavanol dimers and galloylated derivatives thereof.     

Spectral evaluation of total phenolic components in Vitis vinifera: Grapes and wines

Whereas high levels of flavonoid extractives are responsible for the characteristic λ_Dmax at about 280 nm in the ultra-violet spectra of red wines, there is wide variability in the spectral features of natural white wines, in which the phenolic content is often minimal. For the latter, λ_Dmax may occur anywhere within the range 265–285nm, with relatively strong absorbance at 320 nm arising from the presence of hydroxycinnamate esters. Massive fining of many white wines and juices with polyvinylpyrrolidone (10% w/v) has shown residual non-phenolic u.v. absorbing constituents to be sufficiently uniform to enable direct spectral measurement of total hydroxycinnamates in white juices, white wines and rosés as (E₃₂₀-1.4) absorbance units. For white grape juices and white wines, total hydroxycinnamates are directly quantitated as mg litre^?1 ‘caffeic acid equivalents’ and total flavonoid extractives may also be estimated. Total phenolic components of red wines are accounted as (E₂₈₀-4) absorbance units. The spectral interpretations enable comparative estimation of flavonoid extractives in all natural wine types.     

Antioxidant properties of domesticated and wild Rubus species

The antioxidative capacities of a number of Rubus species of varied pigmentation have been investigated. In addition, total phenol, anthocyanin and ascorbic acid contents have been determined. Two methods to assess the antioxidant potential of fruit juices have been used. The antioxidant capacities of the fruit ranged from 0 to 25.3 µmol Trolox equivalents g⁻¹ (TEAC) or from 190 to 66 000 µmol l⁻¹ ferric reducing antioxidant power (FRAP). Ascorbic acid contributes only minimally to the antioxidant potential of Rubus juices (<10%, TEAC). There are apparent linear relationships between antioxidant capacity (assessed as both TEAC and FRAP) and total phenols (r_xy = 0.6713 and 0.9646 respectively). Also, anthocyanin content has a minor influence on antioxidant capacity (r_xy = 0.3774, TEAC; r_xy = 0.5883, FRAP). The sample with the highest antioxidant capacity (Rubus caucasicus) had the highest phenol content, but only a low percentage was represented by anthocyanins. The present study demonstrates the potential of certain wild Rubus species, notably R caucasicus, for improvement of nutritional value through germplasm enhancement programmes. © 2000 Society of Chemical Industry     

Phenolic Compounds and Antioxidant Capacities of 10 Common Edible Flowers from China

The free and bound phenolic compounds in 10 common Chinese edible flowers were investigated using reversed phase high‐performance liquid chromatography. Their antioxidant capacities were evaluated using 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH) radical‐scavenging activity, 2,2'‐azino‐bis(3‐ethylbenzothiazoline‐6‐sulphonic acid) (ABTS) radical‐scavenging activity, oxygen radical absorption capacity (ORAC), ferric reducing antioxidant power (FRAP), and cellular antioxidant activity (CAA). Free factions were more prominent in phenolic content and antioxidant capacity than bound fractions. Paeonia suffruticosa and Flos lonicerae showed the highest total phenolic content (TPC) 235.5 mg chlorogenic acid equivalents/g of dry weight and total flavonoid content 89.38 mg rutin equivalents/g of dry weight. The major phenolic compounds identified were gallic acid, chlorogenic acid, and rutin. P. suffruticosa had the highest antioxidant capacity in the DPPH, ABTS, and ORAC assays, which were 1028, 2065, 990 μmol Trolox equivalents/g of dry weight, respectively, whereas Rosa chinensis had the highest FRAP value (2645 μmol Fe²⁺ equivalents /g of dry weight). The P. suffruticosa soluble phenolics had the highest CAA, with the median effective dose (EC₅₀) 26.7 and 153 μmol quercetin equivalents/100 g of dry weight in the phosphate buffered saline (PBS) and no PBS wash protocol, respectively. TPC was strongly correlated with antioxidant capacity (R = 0.8443 to 0.9978, P < 0.01), which indicated that phenolics were the major contributors to the antioxidant activity of the selected edible flowers.     

Antimutagenic and antioxidant activities of cascalote (Caesalpinia cacalaco) phenolics

There is an increasing awareness and interest in the antioxidant behaviour and potential health benefits of phenolic acids. The identification of novel sources of phenolic acids has been also of scientific interest. Cascalote (Caesalpinia cacalaco) pods are known to be a good source of ‘tannins’, the name by which industry in Mexico recognizes phenolic extract. Phenolics were determined as gallic acid equivalents g^?1. The antimutagenic activity against aflatoxin B₁ and the antioxidant activity, using two different methods, of the extract were also evaluated. Gallic acid accounts for almost 90% of the phenolic extract of cascalote, the remaining 10% was tannic acid. Antimutagenic activity of cascalote phenolics was dose‐dependent, showing an inhibition level of 64.42% at the highest dose assayed. Antioxidant and antiradical activities were also dose‐dependent. The highest antioxidant activity showed by cascalote phenolics was 73.5%, higher than that of Trolox. The highest antiradical activity of cascalote phenolics was 75.3%, higher than that of BHT and Trolox. Cascalote pods are an outstanding source of gallic and tannic acids. Copyright © 2004 Society of Chemical Industry     

Optimisation of the Amido Black assay for determination of the protein content of grape juices and wines

While the heat/chill stability of white wines cannot be predicted from the total protein concentration, this information is useful in assessing the effectiveness of fining treatments. We have adapted the Amido Black assay for use in grape juice and wine. The response of bovine serum albumin (BSA) was similar in water, model wine and model juice. The linear range of the assay (<100 mg l^?1) extends beyond protein concentrations typically found in grape juices and wines. The limit of quantification was 11.1 mg l^?1 for BSA in model wine and 7.6 mg l^?1 in model juice, while the limit of detection was found to be less than 3 mg l^?1 in either solution. In contrast to other methods of protein determination, this assay is not affected by common wine phenolic and pectic compounds or by glutathione. The mean response of BSA was similar in model juice and red and white grape juices. The mean response of BSA in red wine was lower than in white wine and model wine (p < 0.001), and there was considerable variation in response among wines. Protein concentrations determined using this method were reproducible (CV < 10%). This optimised assay can be used to monitor protein levels in grape juices and wines. © 2001 Society of Chemical Industry     

Kinetics of browning onset in white wines: influence of principal redox-active polyphenols and impact on the reducing capacity

The browning capacity of white wines was studied, employing an accelerated test and samples produced and stored under identical conditions. Browning was approached from a kinetic point of view and efforts were focussed on the investigation of plausible correlations with major redox-active polyphenols, including substances with an o-diphenol feature, such as gallic acid, caftaric acid, 2-S-glutathionylcaftaric acid (GRP), caffeic acid, catechin, and epicatechin. Over a period of ten days, browning development was shown to obey zero-order kinetics from the third day of the treatment, and browning rate constants (k) varied from 15.3 to 74.5 × 10⁻³ day⁻¹. Regression analysis between k values and concentration of individual phenolics provided strong evidence that epicatechin is the principal browning agent (r² = 0.8033, P < 0.01). Furthermore, the monitoring of the reducing power (P_R), throughout treatments, indicated that increases in browning are accompanied by a commensurate decline in the reducing ability, raising concerns about the impact of browning reactions on the in vitro antioxidant properties of white wines.     

Reduction kinetics of the free stable radical 2,2-diphenyl-1-picrylhydrazyl (DPPH•) for determination of the antiradical activity of citrus juices

There is vast epidemiological evidence for the beneficial effects that the consumption of citrus juices exerts on human health. These effects are attributed to their content in substances exhibiting free radical scavenging and antioxidant activities, mainly ascorbic acid, flavonoids, carotenoids and polyphenolic derivatives. This work describes an approximation to the reduction kinetics of the stable free radical 2,2-diphenyl-1-picrylhydrazyl (DPPH^•) by the free radical scavenging activity of juices from sweet orange (Citrus sinensis L.), clementine (Citrus reticulata Blanco) and satsuma (Citrus unshiu K. Marc), as well as the deduction of a kinetic equation to fit the experimental data. This equation contains two contributions. The first contribution accounts for the concentration of DPPH^• reduced by the cumulative antiradical activity of those citrus juice components that are capable of fast hydrogen atom transfer (fast-kinetics), mainly ascorbic acid and some polyphenolic derivatives; the second accounts for the concentration of DPPH^• reduced by the cumulative antiradical activity of those citrus juice components that are capable of slow hydrogen atom transfer (slow-kinetics), mainly flavanone-7-O-glycosides and some polyphenolic derivatives. This methodology thus permits the determination of the total antiradical activity of a citrus juice (expressed as molar equivalents of ascorbic acid), as well as the partial contributions of the cumulative antiradical activities (also expressed as molar equivalents of ascorbic acid) due to both fast-kinetics and slow-kinetics.     

Antioxidant and antimicrobial potentials of Serbian red wines produced from international Vitis vinifera grape varieties

BACKGROUND: Antioxidant and antimicrobial potentials of Serbian red wines produced from different international Vitis vinifera grape varieties and their correlation with contents of phenolic compounds were studied by spectrophotometric and chromatographic methods. The antioxidant activity of red wines was estimated through their ability to scavenge 2,2′‐diphenyl‐1‐picrylhydrazyl free radical (DPPH^?). The red wines, gallic acid, (+)‐catechin and quercetin were screened in vitro for antimicrobial activity against Gram‐positive and Gram‐negative strains using microdilution and disc diffusion techniques. RESULTS: Excellent correlations between the contents of quercetin‐3‐glucoside (R² = 0.9463) and quercetin (R² = 0.9337) and DPPH^?‐scavenging ability of the red wines were found. Serbian red wines exhibited significant activity against Staphylococcus aureus, Listeria inocua, Micrococcus flavus, Sarcina lutea, Bacillus subtilis, Escherichia coli, Pseudomonas aeruginosa, Salmonella enteritidis and Shigella sonnei strains, which was in correlation with their phenolic composition and antioxidant activity. The compounds gallic acid, quercetin and (+)‐catechin showed high activity against B. subtilis, S. aureus, S. lutea and M. flavus Gram‐positive and S. enteritidis and P. aeruginosa Gram‐negative strains. CONCLUSION: The results show that quercetin‐3‐glucoside and quercetin concentrations can be used as markers for the determination of antioxidant and antimicrobial potentials of red wines. Copyright © 2012 Society of Chemical Industry     

Interactions between quercetin and catechin in a model matrix: Effects on the in vitro antioxidant behaviour

A hydroalcoholic medium at pH 3.5, containing Fe³⁺ and pyruvic acid, was used as the model matrix to study quercetin/catechin interactions and their possible influence on the antioxidant characteristics of the system. Incubation at 55 °C for a period of 20 days resulted in a complete disappearance of quercetin and a decrease of catechin concentration by almost 75%. Liquid chromatography–mass spectrometry analysis showed that the degradation products are mainly quercetin derivatives, but evidence also indicated that there may be the formation of a co-pigment-like, decarboxylated pyruvic acid-bridged quercetin/catechin adduct. The hydroxyl free radical scavenging activity (SA_HFR) exhibited significant negative correlation (P < 0.05) with both quercetin and catechin concentration whereas the antiradical activity (A_AR) was positively and significantly (P < 0.05) linked only with quercetin, stressing its importance as natural antioxidant agent with a key role in food systems.     

Antioxidant activity of effluents during the purification of hydroxytyrosol and 3,4-dihydroxyphenyl glycol from olive oil waste

Two different processes have been developed for the recovery of hydroxytyrosol (HT) and 3,4-dihydroxyphenyl glycol (DHPG) from olive oil mills waste. The antioxidant activity of several effluents has been characterised by four “in vitro” tests: antiradical capacity (ARC), ferric reducing power (P _R) and inhibition of primary and secondary oxidation in lipid systems. HT-containing effluents exhibited higher or similar activity in ARC and P _R than equimolecular quantities of vitamins E and C. In oxidative tests they were between both assayed vitamins. Except for commercial Hytolive^®2, activities correlated with HT concentration of each sample. DHPG-containing effluent had higher activities than a solution with the same concentration of the synthetic DL-DHPG. This effluent was the most active in ARC and P _R tests, its activity being similar to vitamin E in the inhibition of primary oxidation. Both phenolic compounds showed antagonist effect when they coeluted, except for P _R assay. These results suggested that due to the low-cost procedure and to the antioxidant activity of effluents, they could be valuable as natural additives for food, pharmaceutical and cosmetic industries.     

On-line HPLC-ABTS•+ evaluation and HPLC-MS n identification of bioactive compounds in hot pepper peel residues

In this study, bioactive compounds were extracted with aqueous ethanol from hot pepper peel residues, and the crude extract was divided into four fractions with ethyl ether, ethyl acetate and n-butanol in turn. The total phenolics (TP) and total flavonoids (TF) in the extract were analyzed, and the n-butanol fraction contained the highest TP and TF content, which was 13.45 mg gallic acid equivalents/g and 3.39 mg rutin equivalents/g, respectively. The antioxidant activity of the extract was evaluated by radical [2,2′-azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS), 1,1-diphenyl-2-picrylhydrazyl] scavenging assays. The results of the correlation analysis showed that the antioxidant activity was well correlated with the content of TP and TF (R ² > 0.890). The antioxidant activity of individual antioxidant compound in the extract was evaluated using on-line HPLC-ABTS^?+ assay, and seven antioxidant compounds were identified using HPLC-DAD-MS ⁿ analyses. The main antioxidants identified were naringenin-7-glucoside, procyanidin dimer type B, quercetin-3-O-rhamnoside dimer, kaempferol-3-O-glucoside, kaempferol-3-O-rutinoside, quercetin-3-rutinoside and caffeic acid glycoside dimer. The results showed that hot pepper peel residues contained a certain amount of antioxidant compounds and had a potential application in food products.