Antioxidant/pro-oxidant properties of model phenolic compounds. Part II: Studies on mixtures of polyphenols at different molar ratios by chemiluminescence and LC–MS

The behaviour of four known antioxidants (quercetin, ascorbic acid, catechin and caffeic acid) and their mixtures at different molar ratios was studied in view of elaborating predictions over an eventual pro-oxidant or synergistic antioxidant activity. The Co(II)–EDTA luminol chemiluminescence showed that the mixture of quercetin and ascorbic acid at ratio 2:1 had the most pronounced antioxidant activity, while that of quercetin and caffeic acid at ratio 1:2 showed the least antioxidant activity, which may be interpreted as a strong propensity for pro-oxidant behaviour. The LC–MS analysis for the two mixtures revealed a significant amount of unoxidised quercetin in the case of quercetin with ascorbic acid, whereas in the case of quercetin with caffeic acid this amount was negligible. This observation supports the fact that the first combination was more antioxidant than the second, through efficient quercetin recycling (reduction of the quinone by ascorbic acid; redox cycling of quinones).     

Exposure or release of ferulic acid from wheat aleurone: Impact on its antioxidant capacity

The relationship between the aleurone cell integrity and the exposure or release of bioavailable ferulic acid (FA) with the antioxidant capacity of aleurone in in vitro and under simulated gastric conditions was explored. The antioxidant capacity of aleurone was increased by around 2-fold when its median particle size was reduced to under 50 μm. The opening of aleurone cells increased the physical exposure of FA bound to the insoluble polysaccharides, which seemed to be responsible of the increased antioxidant capacity. Synergistic combination of xylanase and feruloyl esterase was found to be the most efficient enzymatic treatment releasing up to 86% of total FA in bioaccessible forms. This enzymatic treatment significantly enhanced the radical scavenging activity of aleurone by up to 4-fold, which overlapped the overall antioxidant potential estimated from the total content of FA in aleurone. The improvement in the antioxidant capacity of aleurone was also observed in the simulated gastric digestion by inhibition of lipid oxidation.     

Effect of fermentation time on antioxidative activities of Ganoderma lucidum broth using leguminous plants as part of the liquid fermentation medium

Oxidative damage plays an important role in the pathology of human diseases. Ganoderma lucidum, a medicinal fungus, has been used for thousands of years in traditional Oriental medicine. It is reported to have antioxidant functions such as inhibition of lipid peroxidation. The objective of the present study was to investigate the effect of fermentation time on the antioxidative activities of G. lucidum broth filtrate using leguminous plants as part of the liquid fermentation medium. Inhibition of Cu²⁺-induced oxidation of human low-density lipoprotein (LDL), DPPH radical-scavenging activity, total phenolic compounds, isoflavones and protocatechuic acid were measured to evaluate the antioxidant activity of G. lucidum fermentation broth filtrate. Our results showed that black soybean and Astragalus membranaceus improved the antioxidant activity of the G. lucidum fermentation broth filtrate. Protocatechuic acid was identified by LC–MS as the antioxidant compounds whose relative potency of inhibiting LDL oxidation to Trolox is 1.55. Protocatechuic acid showed positive correlation with the antioxidant activity of the fermentation broth filtrate while isoflavones did not contribute to antioxidant activity.     

Antioxidant activity,polyphenols, caffeine and melanoidins in soluble coffee: The influence of processing conditions and raw material

The production of soluble coffee starts with the selection of beans and is followed by roasting, grinding, extraction and drying. Lyophilised soluble coffees extracted by various methods from light, medium and dark-roasted arabica and robusta beans were evaluated for antioxidant activity (AA) using ABTS, Folin, DPPH and FRAP techniques. Caffeine, chlorogenic acid (5-CQA) and melanoidin content was also quantified. The data were analysed by principal component analysis. The AA values derived from the various methods used were correlated. Roasting resulted in the degradation of 5-CQA and formation of melanoidins, while AA was largely unaffected by roasting. The extraction of soluble coffee more prominently affected the AA of light-roasted coffee, mainly because it favoured the extraction of 5-CQA. The larger caffeine content in robusta coffee resulted in greater AA. All of soluble coffee products studied possessed antioxidant potential, which was conferred by their concentrations of phenolic compounds, caffeine and melanoidins.     

Effect of pre‐harvest salicylic acid spray treatment on post‐harvest antioxidant in the pulp and peel of ‘Cara cara’ navel orange (Citrus sinenisis L. Osbeck)

BACKGROUND: Exogenous salicylic acid (SA) pretreatment could change the antioxidant system and maintain the nutritional value of fruits and vegetables, which have a higher ability to withstand oxidation injuries. However, the relationship between a pre‐harvest SA spray and post‐harvest antioxidant compounds in fruit remains unknown. RESULTS: The post‐harvest behaviour of antioxidant compounds in ‘Cara cara’ navel orange (Citrus sinenisis L. Osbeck) fruit was investigated in relation to the pre‐harvest SA applications. Pre‐harvest SA treatment significantly increased the content of carotenoids (lycopene and α‐carotene), ascorbic acid, glutathione, total phenolics, and total flavonoids in the pulp and peel during storage. Furthermore, the values of these antioxidant compounds were high in the fruit treated with high SA concentrations (1.0 and 2.0 mmol L^?1). High antioxidant activity was also observed in the SA pre‐harvest treated fruit when compared with the control. The positive relationships were found between the antioxidant activity and the content of these active compounds. CONCLUSION: These results indicated that SA could maintain fruit antioxidant activity and nutrition which was shown by the increase in content of antioxidant compounds and suggested that pre‐harvest treatment with SA promised a novel technology, which was a substitute for the perplexing programme control of post‐harvest nutrition in fruit. Copyright © 2007 Society of Chemical Industry     

Impact of lipid oxidation-derived aldehydes and ascorbic acid on the antioxidant activity of model melanoidins

As the heat-induced formation of antioxidants throughout the Maillard reaction is known, this study was undertaken to evaluate the impact of lipid oxidation-derived aldehydes and ascorbic acid in Maillard model systems on the resulting antioxidant activity. For this purpose, various fractions of melanoidin-like polycondensation products were obtained from mixtures of amino acids (glycine, lysine, arginine) and lipid oxidation-derived aldehydes (hexanal, (E)-2-hexenal), in the presence or absence of glucose or ascorbic acid. All fractions showed a significant radical scavenging capacity (DPPH assay) and ferric reducing power (FRAP assay). The activity varied according to the composition of the model system tested, although some similar trends were discovered in both assays applied. The presence of lipid oxidation products in the browning products augmented the antioxidant activity in specific cases. For instance, the combined presence of arginine, hexanal and glucose in heated model systems resulted in a significantly higher antioxidant capacity. With an exception of ascorbic acid-containing model systems, melanoidin-like polycondensation products possessed significantly stronger antioxidant activities than the corresponding unheated initial reactant mixtures. Water-soluble high molecular weight (>12kDa) and nonsoluble fractions comprised the major part of the antioxidants derived from amino acid/lipid oxidation product model systems, with or without glucose or ascorbic acid.     

Antioxidant activity of ethanolic extract of Cortex fraxini and use in peanut oil

Cortex fraxini was extracted with 95% ethanol to obtain a crude antioxidant extract. The antioxidant activity was evaluated using the linoleic acid peroxidation method and the free radical scavenging assays, namely 2,2′-diphenyl-1-picrylhydrazyl (DPPH) and hydroxyl radicals. Cortex fraxini extract (CFE) showed high inhibition of peroxidation of linoleic acid when compared with butylated hydroxytoluene (BHT). CFE also exhibited excellent scavenging activity on DPPH and hydroxyl radicals. Total antioxidant activity was measured by the reduction of Mo(VI) to Mo(V) by the extract, and subsequent formation of a green phosphate/Mo(V) complex at acid pH. CFE had significant total antioxidant activity and the effects were increased with increasing reaction time. The total phenolic content of the sample, analyzed by using Folin–Ciocalteu’s reagent, was 91.33 mg/g dry weight expressed as pyrocatechol equivalents. Then the suitability of CFE as an antioxidant was determined in peanut oil, and the decrease of lipid oxidation was monitored using thiobarbituric acid-reactive substances (TBARS) assay. CFE treatment significantly (P < 0.05) reduced lipid oxidation in peanut oil compared to the control. No significant differences (P = 0.05) in lipid oxidation were detected between CFE antioxidant and BHT antioxidant samples.     

Influence of thermal treatment on phenolic compounds and antioxidant properties of oak acorns from Serbia

The aim of the present work was to investigate and compare phenolic compounds and antioxidant activity of methanol extracts of Quercus robur and Quercus cerris acorn kernels obtained before and after thermal treatment. Content of total phenolics, tannins, non-tannin phenolics and flavonoids was determined spectrophotometrically and content of gallic acid with HPLC. Antioxidant activity of the samples was assayed through FRAP (Ferric Reducing Antioxidant Power), DPPH scavenging test and inhibition of Fe²⁺/ascorbate induced lipid peroxidation. Extracts of native and thermally treated kernels showed high antioxidant activity, with extracts of thermally treated kernels being more active than extracts of native ones. Hydrolysable tannins and gallic acid were identified in all samples. Non-tannin phenolics, including gallic acid, were present in significantly higher quantities in thermally treated samples, whilst tannin content decreased. This indicates that during thermal treatment hydrolysable tannins were degraded. As the result of this degradation and consequent increase of non-tannin phenolics content, and amongst them especially gallic acid, thermally treated samples possess higher antioxidant activity than do the native ones. The obtained results have provided further grounds for establishing Q. robur and Q. cerris acorn kernels as a source for functional food preparation.     

Effects of Ascorbic Acid and α-Tocopherol on Antioxidant Activity of Polyphenolic Compounds

The effects of ascorbic acid and α‐tocopherol on the antioxidant activity of 15 phenolic compounds were compared with 2 in vitro assays. Combination of ascorbic acid or α‐tocopherol plus polyphenolic compounds resulted in an additive effect as shown with DPPH–HPLC method. With the liposome oxidation method, combination of quercetin or catechins plus α‐tocopherol showed synergistic effects.     

Influence of the interactions between tea (Camellia sinensis) extracts and ascorbic acid on their antioxidant activity: analysis with interaction indexes and isobolograms

Products containing natural additives, including antioxidants, are usually perceived by consumers as safer than those with synthetic ones. Natural antioxidants, besides having a preservative activity, may exert beneficial health effects. Interactions between antioxidants may significantly change their antioxidant activity, thus in designing functional foods or food/cosmetic ingredients knowledge about the type of interactions could be useful. In the present study, the interactions between ascorbic acid (AA; vitamin C) and different black and green tea extracts and the influence on their antioxidant activities were investigated. The antioxidant activities of tea extracts and their mixtures with AA prepared in several different weight ratios were measured using the trolox equivalent antioxidant capacity (TEAC), 1,1-diphenyl-2-picrylhydrazyl (DPPH), and ferric-reducing antioxidant power (FRAP) methods. The type of interaction was determined by interaction indexes and isobolograms. It was found that the weight ratio of extracts to AA significantly influenced the antioxidant activity of a mixture and the type of interaction between these components. The weight ratio of tea extract to AA can cause the change of interaction, e.g. from antagonism to additivism or from additivism to synergism. The observed differences in the type of interactions were probably also a result of different extracts’ polyphenol composition and content. The type of interaction may also be affected by the medium in which extracts and AA interact, especially its pH and the solvent used. To obtain the best antioxidant effect, all these factors should be taken into account during the design of a tea extract–AA mixture.     

Synergistic antioxidant and antibacterial activity of rosemary plus butylated derivatives

Antioxidant and antibacterial activity of a methanol rosemary extract (RE) containing 30% carnosic acid (CA), 16% carnosol (COH) and 5% rosmarinic acid (RA) was studied in vitro alone and in combination with the antioxidant food additives butylated hydroxytoluene (BHT) and butylated hydroxyanisole (BHA). The antioxidant efficiency of the extract, CA, and RA, was determined by a kinetic analysis of the 2,2-diphenyl-2-picrylhydrazyl hydrate radical (DPPH·) scavenging activity. RE showed two different rate slopes in the reduction of DPPH· vs. time curve, which correlated with the distinct behaviours of RA and CA; pure RA reached the plateau more rapidly than CA. A synergistic antioxidant effect between RE and BHT was demonstrated by isobolographic analysis and a synergistic interaction of RE with BHA to inhibit Escherichia coli and Staphylococcus aureus growth was observed. Therefore, rosemary not only enhances the antioxidant efficiency of BHA and BHT, but also the antibacterial effect of BHA; allowing a decrease from 4.4 to17 folds in the amounts of the synthetic compounds used.     

连翘叶中连翘苷和连翘酯苷A对食用油脂的抗氧化活性

针对连翘叶中提取、分离和纯化的连翘苷和连翘酯苷A进行研究,通过油脂抗氧化实验,分别以油脂的酸价值和过氧化值为参考指标,评价连翘苷和连翘酯苷A的抗氧化活性和VC、柠檬酸对连翘苷和连翘酯苷A的协同增效作用。结果表明：制备得到纯度为93%连翘苷和92%连翘酯苷A,连翘苷和连翘酯苷A对猪油氧化作用均有一定的抑制作用,且随着剂量的增加,抑制效果越明显;其中,连翘酯苷A对油脂氧化的抑制作用远优于连翘苷,效果与阳性对照2,6-二叔丁基-4-甲基苯酚接近;VC和柠檬酸对连翘苷和连翘酯苷A的抗氧化作用均表现出协调增效作用。     

Chemical characterization of the medicinal mushroom Phellinus linteus (Berkeley & Curtis) Teng and contribution of different fractions to its bioactivity

Mushrooms are widely appreciated for their organoleptic qualities, being also recognized as good sources of bioactive compounds that provide antioxidant, antimicrobial and cytotoxic activities. Polysaccharides (including glucans) are often pointed out as the most bioactive compounds isolated from mushrooms, but other molecules such as triterpenoids, might also be highlighted for their bioactivity. In scientific research, when isolated compounds are used, potential synergistic effects might be lost. Accordingly, the bioactivity of Phellinus linteus was evaluated in selected fractions (polysaccharides, glucans and triterpenoids), as well as in the methanolic and ethanolic extracts. The best antioxidant and antibacterial activities were obtained with methanolic extract, while glucan and triterpenoid fractions gave the strongest antifungal activity. In contrast, ethanolic extract gave the best results in cytotoxic activity, indicating that the bioactive compounds present might act synergistically. The differentiated activity of P. linteus fractions and extracts could be useful to find antimicrobial, antioxidant and cytotoxic agents as alternatives to synthetic chemicals with application in agriculture, food industry or pharmacy.     

Effects of water-soluble natural antioxidants on photosensitized oxidation of conjugated linoleic acid in an oil-in-water emulsion system

ABSTRACT:  The effect of photosensitized oxidation of conjugated linoleic acid in an oil-in-water (o/w) emulsion system was studied. Water-soluble natural antioxidants, including apple polyphenols from apple extract, green tea extract, 4-hydroxy-2(or 5)-ethyl-5(or2)-methyl-3(2H)-furanone(HEMF), 4-hydroxy-2,5-dimethyl-3(2H)-furanone (HDMF), and ascorbic acid, were tested for antioxidant activity in this system. The green tea extract showed the highest antioxidant activity followed by ascorbic acid. Apple polyphenols did not give significant antioxidant activity. HEMF and HDMF exhibited a prooxidant effect. The antioxidant activity of tea catechins was also investigated. Of them, EGCG and ECG exhibited antioxidant activity at 50 ppm, but the antioxidant activity between them was not significantly different ( P < 0.05). Comparatively, EC, EGC, and GCG showed no significant antioxidative effect at 50 ppm. When the concentration increased to 100 ppm, the antioxidant activity of ECG and EGCG significantly increased compared with that at 50 ppm, and EGCG had higher antioxidant activity than ECG. GCG also showed significant antioxidant activity at 100 ppm. EGCG exhibited the highest antioxidant activity among the tea catechins in the emulsion system at 100 ppm.     

Characterization and antioxidant evaluation of phenolic compounds extracted from the protein concentrate and protein isolate produced from pawpaw (Carica papaya Linn.) seeds

In this study, the qualitative and quantitative analysis of the absolute (100%) and aqueous (80%) methanolic extract of Carica papaya Linn processed seed flour samples in terms of their antioxidant properties and their phenolic compounds was investigated. The antioxidant properties were determined by 2,2-diphenyl-1-picrylhydrazyl (DPPH), ferric reducing antioxidant power, and metal chelating assay methods. The protein isolate exhibited higher radical scavenging activity power as compared to other samples. Ferulic acid, caffeic acid, p-coumaric acid, kaempferol-3-glucoside, p-hydroxybenzoic acid, and quercetin-3-galactoside were phenolic compounds isolated with ferulic acid as high as 0.62 mg/DWg. Carica papaya seed isolates and concentrate demonstrated potent antioxidant activity and could be of nutraceutical importance in the pharmaceutical and food industry.     

Implementation of response surface methodology to assess the antiradical behaviour in mixtures of ascorbic acid and α-tocopherol with grape (Vitis vinifera) stem extracts

The efficiency of grape stem extracts to express antiradical activity was assessed using two different approaches and DPPH as the radical probe. In addition, the mixture effects when the extracts were combined with ascorbic acid (AA) and α-tocopherol (α-Tcp) were also evaluated. The approaches included a simple linear regression analysis between the response (antiradical activity) and concentration, but also a response surface methodology, which permitted the monitoring of the response upon simultaneous variation of both the concentration of the total polyphenols of the extracts and either of the antioxidants (AA and α-Tcp). The deployment of linear regression poses important constraints with regard to concentration ranges, whereas response surface methodology might be a valuable statistical tool for similar assessments and credible modelling of binary mixtures of antioxidants. In all combinations tested it was found that an antagonism was manifested, presumably as a result of AA and α-Tcp regeneration by the extract polyphenols, at the expense of the latter.     

In vitro antioxidant synergism and antagonism between food extracts can lead to similar activities in H2O2‐induced cell death,caspase‐3 and MMP‐2 activities in H9c2 cells

BACKGROUND: The cardio‐health‐promoting activity of some foods may be due to their specific antioxidant content. The antioxidant activity of a mixture of plant extracts has been shown to differ from the activity of the individual extracts. As a result, the activity of the mixture can be described as synergistic, antagonistic or additive. This in vitro study evaluated the relationship between the in vitro antioxidant capacity of mixtures and their bioactivity when cardiomyocytes (H9c2) were challenged with H₂O₂. RESULTS: A mixture of raspberry and adzuki bean extracts produced a synergistic response and a mixture of broccoli and soybean extracts produced an antagonistic response in chemical‐based antioxidant assays. When these extracts were tested in cell cultures, individually and in mixtures, the mixture of raspberry and adzuki bean protected the cardiomyocytes from H₂O₂‐induced cell damage significantly better than the individual extracts. Conversely, the mixture of broccoli and soybean extracts was less effective in protecting H9c2 cells. The synergistic and antagonistic effects of the mixtures in protecting cell damage were brought about by enhanced or reduced ability in attenuating caspase‐3 and matrix metalloproteinase‐2 activities elevated by H₂O₂. CONCLUSION: Food mixtures with synergistic antioxidant activity and protective property against reactive oxygen species‐induced cell death can potentially be incorporated into novel functional foods or beverages with optimum health benefit. The antagonistic effect of food mixtures can be a health concern and thus should be avoided. Copyright © 2012 Society of Chemical Industry     

Headspace-solid phase microextraction (HS-SPME) analysis of oxidized volatiles from free fatty acids (FFA) and application for measuring hydrogen donating antioxidant activity

Volatile compounds from thermally oxidized free fatty acids (FFA) at 93 °C for 200 min were analyzed by headspace-solid phase microextraction (HS-SPME)-gas chromatography (GC). Commercially available mixtures of FFA were used instead of selecting specific vegetable oils with various fatty acid compositions. As oxidation time increased, total volatiles and some individual volatiles including hexanal, 2-hexenal, 2-heptenal, 2,4-heptadienal, 2-octenal, and 2,4-decadienal increased linearly with 0.99 coefficient of determination (R²) at specific oxidation time against conjugated dienoic acid (CDA) or p-anisidine value (p-AV). Total volatiles showed the highest linearity (R²) of 0.99 and 2-heptenal showed the highest increasing slope in peak areas for 200 min oxidation. Not all oxidized volatiles increased linearly during oxidation. Availability of HS-SPME method for determining hydrogen donating antioxidant activity was tested using FFA containing serially diluted butylated hydroxytoluene (BHT) at 93 °C for 60 min. 2-Heptenal and total volatiles showed higher linearity against BHT concentration than hexanal. HS-SPME could be a useful method to determine the hydrogen donating antioxidant activity from FFA using total volatiles or 2-heptenal as oxidation markers.     

阿魏酸类似物对强的松诱导的小鼠氧化应激的影响

本实验研究阿魏酸及其类似物姜黄素、谷维素对小鼠体内氧化应激的影响.将90只雄性ICR小鼠随机分为6组:正常组、模型组、阿魏酸组、姜黄素组、谷维素组和阳性对照(辅酶Q10)组.每3d正常组肌肉注射生理盐水,其他组注射40 mg/kg mb强的松进行造模.正常组和模型组饲喂正常饲料,其他4组每千克饲料中分别添加40 mg的...     

Physicochemical and structural characterisation of protein isolate,globulin and albumin from soapnut seeds (Sapindus mukorossi Gaertn.)

The amino acid (AA) composition and physicochemical and conformational properties of protein isolate (SNPI), globulin (SNG) and albumin (SNA) fractions from soapnut seeds were evaluated. The essential AA of SNG, SNA and SNPI (except sulfur-containing AA) are sufficient for the FAO/WHO suggested requirements for 2–5 year old infants. SNG and SNPI showed similar electrophoresis patterns and AA compositions, the subunit of those proteins consisted of two polypeptides linked by disulfide bonds. In contrast, SNA showed a different AA compositions and SDS–PAGE pattern. Both SNG and SNPI presented a typical U-shape protein solubility (PS)–pH profile, SNA showed a completely different PS–pH profile, especially at pH 2.0–4.0. The near-UV circular dichroism (CD), differential scanning calorimetry (DSC) and tryptophan fluorescence spectra analyses indicated that the flexibility in tertiary conformations decreased in the order: SNA > SNPI > SNG, while soapnut proteins had a similar secondary conformation, with a highly ordered structure (the β-types), as evidenced by far-UV CD spectra.