Voltammetric determination of the antioxidant capacity in wine samples using a carbon nanotube modified electrode

A direct determination of gallic acid was achieved at a carbon paste electrode modified with carbon nanotubes under differential pulse voltammetry conditions. The values obtained for gallic acid were used to estimate the antioxidant properties of the wine sample based on gallic acid oxidation. The proposed method is based on the gallic acid oxidation process at a modified carbon paste electrode (MCPE) containing 30% (m/m) of carbon nanotubes monitored at 0.35 V versus Ag/AgCl (KCl 3 mol L(-1)). Using the optimized experimental conditions, the calibration curve for gallic acid was linear in the concentration range from 5.0 × 10(-7) to 1.5 × 10(-5) mol L(-1) with a detection limit of 3.0 × 10(-7) mol L(-1). The MCPE was successfully applied for the determination of the antioxidant capacity for red and white wine samples without interference of glucose and ascorbic acid, and the obtained results were compared with the standard spectrophotometric method.     

Total polyphenol content and antioxidant capacity of commercially available tea (Camellia sinensis) in Argentina

Tea, Camellia sinensis (L.) O. Kuntze (Theaceae) is cultivated in Argentina in the northeastern region (provinces of Misiones and Corrientes), between 26 degrees and 28 degrees south latitude, the southernmost area of the world where tea is cultivated. The objective of this work was to determine the total polyphenol content and the in vitro antioxidant capacity of green and black tea cultivated and industrialized in Argentina. Twelve samples of eight brands were analyzed. The total polyphenol content was determined according to the International Organization for Standardization method (ISO) 14502-1 for the determination of substances characteristic of green and black tea. The antioxidant capacity was determined by the ferric thiocyanate method (FTC) and the 1,1-diphenyl-2-picrylhydrazyl (DPPH) free-radical scavenging assay. Green tea showed a higher polyphenol content than black tea. The total polyphenol concentration in green tea was found to vary from 21.02 +/- 1.54 to 14.32 +/- 0.45% of gallic acid equivalents (GAE), whereas in black tea, the polyphenol content ranged from 17.62 +/- 0.42 to 8.42 +/- 0.55% of GAE (P < 0.05). A similar profile was observed for the antioxidant capacity determined by both methods. The antioxidant activities were well correlated with the total polyphenol content (r (2) = 0.9935 for the ferric thiocyanate method and r (2) = 0.9141 for the 1,1-diphenyl-2-picrylhydrazyl free-radical scavenging assay). This is the first systematic screening for the quantification of polyphenols and antioxidant activity in tea commercialized in Argentine markets. The results obtained herein allow one to conclude that Argentine tea is of very good quality when compared to teas from other sources.     

Determination of antioxidant activity of wine byproducts and its correlation with polyphenolic content

It has been demonstrated that wine and other products derived from the grape have a high antioxidant capability; as a possible consequence of this, they may have potential benefits for health. The byproducts of the winemaking process represent a source of antioxidant compounds that has been relatively unexploited to date, but that is now the subject of increasing industrial interest. This article describes an approach to the study of the antioxidant activity of grape marcs, stalks, and dregs of both white and red varieties. This activity is compared with the measurements of their content of total polyphenols and of individual polyphenolic compounds, identified and quantified by HPLC. From the results we have been able to establish a positive correlation between the antioxidant activity and the total polyphenolic content of samples, but not with specific compounds.     

Phenolic content and antioxidant capacity of muscadine grapes

Fruits of 10 cultivars of muscadine grapes (five bronze skin and five purple skin) grown in southern Georgia were separated into skin, seed, and pulp. Each fruit part and the leaves from the corresponding varieties were extracted for HPLC analysis of major phenolics. Total phenolics were determined colorimetrically using Folin-Ciocalteu reagent. Total anthocyanins were determined according to a pH-differential method, using a UV-visible spectrophotometer. Antioxidant capacity was determined by the Trolox equivalent antioxidant capacity (TEAC) assay. Gallic acid, (+)-catechin, and epicatechin were the major phenolics in seeds, with average values of 6.9, 558.4, and 1299.4 mg/100 g of fresh weight (FW), respectively. In the skins, ellagic acid, myricetin, quercetin, kaempferol, and trans-resveratrol were the major phenolics, with respective average values of 16.5, 8.4, 1.8, 0.6, and 0.1 mg/100 g of FW. Contrary to previous results, ellagic acid and not resveratrol was the major phenolic in muscadine grapes. The HPLC solvent system used coupled with fluorescence detection allowed separation of ellagic acid from resveratrol and detection of resveratrol. Reported here for the first time are the phenolic content and antioxidant capacity of muscadine leaves. Major phenolics in muscadine leaves were myricetin, ellagic acid, kaempferol, quercetin, and gallic acid, with average concentrations of 157.6, 66.7, 8.9, 9.8, and 8.6, respectively. Average total phenolics were 2178.8, 374.6, 23.8, and 351.6 mg/g gallic acid equivalent in seed, skin, pulp, and leaves, respectively. Total anthocyanin contents were 2.1 and 132.1 mg/100 g of FW in the skins of bronze and purple grapes, respectively, and 4.3 and 4.6 mg/100 g of FW in seeds and pulps, in that order. Antioxidant capacity values were, on average, 2.4, 12.8, 281.3, and 236.1 microM TEAC/g of FW for pulps, skins, seeds, and leaves, respectively.     

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.     

HPLC method for the quantification of procyanidins in cocoa and chocolate samples and correlation to total antioxidant capacity.

Monomeric and oligomeric procyanidins present in cocoa liquors and chocolates were separated and quantified in four different laboratories using a normal-phase high-performance liquid chromatography (HPLC) method with fluorescence detection. Procyanidin standards through decamers were obtained by extraction from cocoa beans, enrichment by Sephadex LH-20 gel permeation chromatography, and final purification by preparative normal-phase HPLC. The purity of each oligomeric fraction was assessed using HPLC coupled to mass spectrometry. A composite standard was then prepared, and calibration curves were generated for each oligomeric class using a quadratic fit of area sum versus concentration. Results obtained by each of the laboratories were in close agreement, which suggests this method is reliable and reproducible for quantification of procyanidins. Furthermore, the procyanidin content of the samples was correlated to the antioxidant capacity measured using the ORAC assay as an indicator for potential biological activity.     

Determination of the grape invertase content (using PTA-ELISA) following various fining treatments versus changes in the total protein content of wine. relationships with wine foamability

Proteins have proven to play a major role in the stabilization of foam in Champagne wines despite their low concentration that ranges from 4 to 20 mg/L. The aim of this study was to evaluate the effect of fining on total protein and grape invertase contents of champenois base wines and their foaming properties. Data showed that fining and especially the use of bentonite at doses ranging from 10 to 50 g/hL leads to a significant decrease in the total protein content of wines together with that of the grape invertase content, with such a decrease being very detrimental to the foaming properties of the treated wines in terms of foam height (HM) and foam stability (HS). Only a slight decrease in the total protein content, in the grape invertase concentration, and in the foam quality of wines was observed when using casein (10 and 20 g/hL) or bentonite combined with casein (both at 20 g/hL). Our study thus clearly establishes the good correlation existing between the wine protein concentration and its foaming properties. A remarkable correlation was observed between the decrease in the grape invertase content and the total protein content of wines, following bentonite treatments, suggesting that the grape invertase (which represents at least 10-20% of the wine proteins) follows a similar behavior upon fining to other proteins of Champagne wines, despite the high molecular mass and the highly glycosylated structure of this particular protein. Moreover, the decrease in total protein and grape invertase contents of wine after fining with bentonite was found to be correlated with a decrease in the foaming properties of the corresponding wines (with respectively R(2) = 0.89 and 0.95).     

Electrochemical estimation of the polyphenol index in wines using a laccase biosensor

The use of a laccase biosensor, under both batch and flow injection (FI) conditions, for a rapid and reliable amperometric estimation of the total content of polyphenolic compounds in wines is reported. The enzyme was immobilized by cross-linking with glutaraldehyde onto a glassy carbon electrode. Caffeic acid and gallic acid were selected as standard compounds to carry out such estimation. Experimental variables such as the enzyme loading, the applied potential, and the pH value were optimized, and different aspects regarding the operational stability of the laccase biosensor were evaluated. Using batch amperometry at -200 mV, the detection limits obtained were 2.6 x 10(-3) and 7.2 x 10(-4) mg L(-1) gallic acid and caffeic acid, respectively, which compares advantageously with previous biosensor designs. An extremely simple sample treatment consisting only of an appropriate dilution of wine sample with the supporting electrolyte solution (0.1 mol L(-1) citrate buffer of pH 5.0) was needed for the amperometric analysis of red, rosé, and white wines. Good correlations were found when the polyphenol indices obtained with the biosensor (in both the batch and FI modes) for different wine samples were plotted versus the results achieved with the classic Folin-Ciocalteu method. Application of the calibration transfer chemometric model (multiplicative fitting) allowed that the confidence intervals (for a significance level of 0.05) for the slope and intercept values of the amperometric index versus Folin-Ciocalteu index plots (r = 0.997) included the unit and zero values, respectively. This indicates that the laccase biosensor can be successfully used for the estimation of the polyphenol index in wines when compared with the Folin-Ciocalteu reference method.     

Catechin and caffeine content of green tea dietary supplements and correlation with antioxidant capacity

The health benefits associated with tea consumption have resulted in the wide inclusion of green tea extracts in botanical dietary supplements, which are widely consumed as adjuvants for complementary and alternative medicines. Tea contains polyphenols such as catechins or flavan-3-ols including epicatechin, epigallocatechin, epicatechin gallate, and epigallocatechin gallate (EGCG), as well as the alkaloid, caffeine. Polyphenols are antioxidants, and EGCG, due to its high levels, is widely accepted as the major antioxidant in green tea. Therefore, commercial green tea dietary supplements (GTDS) may be chemically standardized to EGCG levels and/or biologically standardized to antioxidant capacity. However, label claims on GTDS may not correlate with actual phytochemical content or antioxidant capacity nor provide information about the presence and levels of caffeine. In the current study, 19 commonly available GTDS were evaluated for catechin and caffeine content (using high-performance liquid chromatography) and for antioxidative activity [using trolox equivalent antioxidant capacity (TEAC) and oxygen radical antioxidant capacity (ORAC) assays]. Product labels varied in the information provided and were inconsistent with actual phytochemical contents. Only seven of the GTDS studied made label claims of caffeine content, 11 made claims of EGCG content, and five specified total polyphenol content. Caffeine, EGCG, and total polyphenol contents in the GTDS varied from 28 to 183, 12-143, and 14-36% tablet or capsule weight, respectively. TEAC and ORAC values for GTDS ranged from 187 to 15340 and from 166 to 13690 mumol Trolox/g for tablet or capsule, respectively. The antioxidant activities for GTDS determined by TEAC and ORAC were well-correlated with each other and with the total polyphenol content. Reliable labeling information and standardized manufacturing practices, based on both chemical standardization and biological assays, are recommended for the quality control of botanical dietary supplements.     

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).     

茶花粉酶法破壁工艺提高提取物抗氧化活性及多酚含量

为了建立蜂花粉抗氧化活性物质的提取工艺并探索其抗氧化活性与多酚含量的关系,该文研究了破壁用酶、提取溶剂、超声波处理对茶花粉提取液多酚含量及其抗氧化活性的影响。结果表明,茶花粉经纤维素酶破壁后其上清液具有较高的还原力和DPPH自由基清除能力;与温水和酸处理相比,纤维素酶破壁沉淀物经乙醇提取后,溶液多酚含量较高、抗氧化活性较强;茶花粉不同提取方式多酚含量与2种抗氧化活性指标具有一定的相关性（r=0.8685及r=0.7600）（p＞0.05）;与乙醇提取和水提取相比,纤维素酶破壁处理结合乙醇提取将茶花粉的多酚含量、还原力及DPPH自由基清除能力分别提高1.82倍、2.17倍、1.4倍和1.56倍、1.38倍、11倍,且二者对混合物还原力、DPPH自由基清除能力及多酚含量的贡献比例分别为1.6：1、3：1、1.08：1。该研究结果可为花粉资源的开发利用提供参考。     

Contribution of individual polyphenolics to total antioxidant capacity of plums

To study the effect of polyphenolics on antioxidant capacities of plums, the amounts of total phenolics, total flavonoids and individual phenolic compounds, and vitamin C equivalent antioxidant capacity (VCEAC) of eleven plum cultivars was determined. There was a good linear relationship between the amount of total phenolics and total antioxidant capacity (r2 = 0.9887). The amount of total flavonoids and total antioxidant capacity also showed a good correlation (r2 = 0.9653). Although the summation of individual antioxidant capacity was lower than the total antioxidant capacity of plum samples, there was a positive correlation (r2 = 0.9299) of total antioxidant capacity of plum samples with the sum of the VCEACs calculated from individual phenolics. Chlorogenic acids and glycosides of cyanidin, peonidin, and quercetin were major phenolics among eleven plum cultivars. The antioxidant capacity of chlorogenic acids and anthocyanins showed higher correlation (r2) of 0.7751 and 0.6616 to total VCEAC, respectively, than that of quercetin glycosides (r2 = 0.0279). Chlorogenic acids were a major source of antioxidant activity in plums, and the consumption of one serving (100 g) of plums can provide antioxidants equivalent to 144.4-889.6 mg of vitamin C.     

Major phenolics in apple and their contribution to the total antioxidant capacity

The contribution of each phytochemical to the total antioxidant capacity of apples was determined. Major phenolic phytochemicals of six apple cultivars were identified and quantified, and their contributions to total antioxidant activity of apples were determined using a 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) radical scavenging assay and expressed as vitamin C equivalent antioxidant capacity (VCEAC). Average concentrations of major phenolics and vitamin C in six apple cultivars were as follows (mg/100 g of fresh weight of apples): quercetin glycosides, 13.20; procyanidin B(2), 9.35; chlorogenic acid, 9.02; epicatechin, 8.65; phloretin glycosides, 5.59; vitamin C, 12.80. A highly linear relationship (r (2) > 0.97) was attained between concentrations and total antioxidant capacity of phenolics and vitamin C. Relative VCEAC values of these compounds were in the order quercetin (3.06) > epicatechin (2.67) > procyanidin B(2) (2.36) > phloretin (1.63) > vitamin C (1.00) > chlorogenic acid (0.97). Therefore, the estimated contribution of major phenolics and vitamin C to the total antioxidant capacity of 100 g of fresh apples is as follows: quercetin (40.39 VCEAC) > epicatechin (23.10) > procyanidin B(2) (22.07) > vitamin C (12.80) > phloretin (9.11) > chlorogenic acid (8.75). These results indicate that flavonoids such as quercetin, epicatechin, and procyanidin B(2) rather than vitamin C contribute significantly to the total antioxidant activity of apples.     

New enzymatic method for the determination of total phenolic content in tea and wine

A new spectrophotometric enzymatic method for the determination of total phenol content in tea and wine has been developed. The method is based on the peroxidase-catalyzed oxidation, by hydrogen peroxide, of phenols to phenoxyl radicals, which can react with aromatic substrates to form intensely colored adducts. In comparison with the widely used Folin-Ciocalteu method, this method appears to be more specific and more rapid and as a whole is not affected by the common interfering substances such as ascorbate, citrate, and sulfite. Numerous samples of teas and wines were analyzed by using the new method, and the results compared with those obtained by using the Folin and scavenging of DPPH methods. The differences of the total phenols content found by applying the three methods are discussed in terms of the different specificities of the analytical basis.     

Nondestructive prediction of total phenolics, flavonoid contents, and antioxidant capacity of rice grain using near-infrared spectroscopy

Phytochemicals such as phenolics and flavonoids, which are present in rice grains, are associated with reduced risk of developing chronic diseases such as cardiovascular disease, type 2 diabetes, and some cancers. The phenolic and flavonoid compounds in rice grain also contribute to the antioxidant activity. Biofortification of rice grain by conventional breeding is a way to improve nutritional quality so as to combat nutritional deficiency. Since wet chemistry measurement of phenolic and flavonoid contents and antioxidant activity are time-consuming and expensive, a rapid and nondestructive predictive method based on near-infrared spectroscopy (NIRS) would be valuable to measure these nutritional quality parameters. In the present study, calibration models for measurement of phenolic and flavonoid contents and antioxidant capacity were developed using principal component analysis (PCA), partial least-squares regression (PLS), and modified partial least-squares regression (mPLS) methods with the spectra of the dehulled grain (brown rice). The results showed that NIRS could effectively predict the total phenolic contents and antioxidant capacity by PLS and mPLS methods. The standard errors of prediction (SEP) were 47.1 and 45.9 mg gallic acid equivalent (GAE) for phenolic content, and the coefficients of determination ( r (2)) were 0.849 and 0.864 by PLS and mPLS methods, respectively. Both PLS and mPLS methods gave similarly accurate performance for prediction of antioxidant capacity with SEP of 0.28 mM Trolox equivalent antioxidant capacity (TEAC) and r (2) of 0.82. However, the NIRS models were not successful for flavonoid content with the three methods ( r (2) < 0.4). The models reported here are usable for routine screening of a large number of samples in early generation screening in breeding programs.     

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.     

Interactions between flavonoids and proteins: effect on the total antioxidant capacity

Flavonoids are potent antioxidants. It is also known that flavonoids bind to proteins. The effect of the interaction between tea flavonoids and proteins on the antioxidant capacity was examined. Their separate and combined antioxidant capacities were measured with the Trolox equivalent antioxidant capacity (TEAC) assay. It was observed that the antioxidant capacity of several components of green and black tea with alpha-, beta-, and kappa-casein or albumin is not additive; that is, a part of the total antioxidant capacity is masked by the interaction. This masking depends on both the protein and the flavonoid used. Components in green and black tea, which show the highest masking in combination with beta-casein, are epigallocatechin gallate and gallic acid. The results demonstrate that the matrix influences the efficacy of an antioxidant.     

Over-seasons analysis of quantitative trait loci affecting phenolic content and antioxidant capacity in raspberry

This study examined the total phenol content (TPC) and total anthocyanin content (TAC) in ripe fruit of progeny of a mapping population generated from a cross between the European red raspberry cv. Glen Moy ( Rubus ideaus var. idaeus) and the North American red raspberry cv. Latham ( Rubus ideaus var. strigosus) over five seasons in two different growing environments. Measurements of antioxidant capacity (FRAP and TEAC) were also carried out. TPC was highly correlated with TEAC and FRAP across the entire data set. The subset of anthocyanin content was genotype-dependent but also correlated with TPC, although the proportion of anthocyanin compounds varied between progeny. Quantitative trait locus (QTL) analysis was carried out, and key markers were tested for consistency of effects over sites and years. Four regions, on linkage groups 2, 3, 5, and 6, were identified. These agree with QTLs from a previous study over a single season and indicate that QTL effects were robust over seasons.     

Novel antioxidant reactions of cinnamates in wine

Plant-derived polyphenolic compounds have received much attention for their ability to sequester high-energy free radicals in a great variety of food-related and biological systems, protecting those systems from oxidative change. The ability of these compounds to scavenge free radicals has always been attributed to their phenolic functionality, from which a hydrogen atom can be easily abstracted. In this study, the cinnamates and the ubiquitous hydroxycinnamates were found to equally suppress the formation of oxidation products in wine exposed to the Fenton reaction (catalytic Fe(II) with hydrogen peroxide). Mechanistic investigations led to the unexpected discovery that the α,β-unsaturated side chain of cinnamic acids could efficiently trap 1-hydroxyethyl radicals, representing a newly discovered mode of antioxidant radical scavenging activity for these broadly occurring compounds in a food system. The proposed pathway is supported by prior fundamental studies with radiolytically generated radicals.     

牧草产量的遥感估算与载畜能力研究

为了切实保护草地生态环境,实现草畜平衡,以畜牧业大省青海省为例,利用经过GPS定位的青海省牧草地面观测资料,分析牧草产量与NOAA/AVHRR植被指数NDVI之间的关系,分类建立青海省牧草产量估算线形模型与指数模型.模型的拟合结果良好,相关系数平方(R2)超过0.67.大部分时次的地面实测值与遥感估算值所处的产量等级基本一致,模型精度可以应用于大范围的牧草产量预测.根据牧草遥感估测结果,计算分析青海天然草场的载畜能力.结果表明,青海省县级天然草地年最高载畜量基本呈南高北低的态势.南部大部分县以及北部的祁连县在100～200万只绵羊单位之间,海西州和海东大部分县在50万只绵羊单位以下.