Evaluation of free radical scavenging activities of antioxidants with an H(2)O(2)/NaOH/DMSO system by electron spin resonance.

An H(2)O(2)/NaOH/DMSO system has been developed for the formation of three free radicals, and the application of the system was examined with the antioxidants ascorbic acid and tocopherol. Superoxide anion, hydroxyl radical,and methyl radical are simultaneously generated in this system. The scavenging activity of ascorbic acid and tocopherol for these radicals was estimated by 5, 5'-dimethyl-1-pyrroline-N-oxide spin trapping electron spin resonance. Both water-soluble and oil-soluble antioxidants could be evaluated by using this system. Ascorbic acid specifically inhibited the superoxide anion and hydroxyl radical, whereas tocopherol suppressed the methyl radical.     

Free radical scavenging activity of chitooligosaccharides by electron spin resonance spectrometry

The radical scavenging effects of chitooligosaccharides (COSs) on hydroxyl radical, superoxide radical, alkyl radical, and 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical were investigated using a spin-trapping electron spin resonance (ESR) method and compared with the ESR signal intensity. COSs exhibited strong scavenging activity on hydroxyl radical and superoxide radical and weak scavenging activity on alkyl radical and DPPH radical. The radical scavenging activity of COSs increased with increment of concentration, and it was also dependent on molecular weight. These results suggest that the scavenging activity of COSs is dependent on their molecular weights and tested radicals.     

Free radical scavenging activity and antiulcer activity of garcinol from Garcinia indica fruit rind

Garcinol, a polyisoprenylated benzophenone derivative, was purified from Garcinia indica fruit rind, and its free radical scavenging activity was studied using electron spin resonance (ESR) spectrometry. In the hypoxanthine/xanthine oxidase system, emulsified garcinol suppressed superoxide anion to almost the same extent as DL-alpha-tocopherol by weight. In the Fenton reaction system, garcinol also suppressed hydroxyl radical more strongly than DL-alpha-tocopherol. In the H(2)O(2)/NaOH/DMSO system, garcinol suppressed superoxide anion, hydroxyl radical, and methyl radical. It was thus confirmed that this derivative is a potent free radical scavenger and able to scavenge both hydrophilic and hydrophobic ones including reactive oxygen species. Orally administered garcinol prevented acute ulceration in rats induced by indomethacin and water immersion stress caused by radical formation. These results suggested garcinol might have potential as a free radical scavenger and clinical application as an antiulcer drug.     

Radical scavenging and singlet oxygen quenching activity of marine carotenoid fucoxanthin and its metabolites

Antioxidant activity of carotenoids is suggested to be one of the factors for their disease preventing effects. Marine carotenoids fucoxanthin and its two metabolites, fucoxanthinol and halocynthiaxanthin, have been shown to exhibit several biological effects. The antioxidant activities of these three carotenoids were assessed in vitro with respect to radical scavenging and singlet oxygen quenching abilities. The 1,1-diphenyl-2-picrylhydrazyl radical scavenging activity of fucoxanthin and fucoxanthinol was higher than that of halocynthiaxanthin, with the effective concentration for 50% scavenging (EC 50) being 164.60, 153.78, and 826.39 microM, respectively. 2,2'-Azinobis-3-ethylbenzo thizoline-6-sulphonate radical scavenging activity of fucoxanthinol (EC 50, 2.49 microM) was stronger than that of fucoxanthin (EC 50, 8.94 microM). Hydroxyl radical scavenging activity as measured by the chemiluminescence technique showed that the scavenging activity of fucoxanthin was 7.9 times higher than that by fucoxanthinol, 16.3 times higher than that by halocynthiaxanthin, and 13.5 times higher than that by alpha-tocopherol. A similar trend was observed when the hydroxyl radical scavenging was assessed by the electron spin resonance (ESR) technique. ESR analysis of the superoxide radical scavenging activity also showed the superiority of fucoxanthin over the other two carotenoids tested. Singlet oxygen quenching ability of the three carotenoids was lower than that of beta-carotene, with quenching rate constants ( k Q, x10 (10) M (-1) s (-1)) being 1.19, 1.81, 0.80, and 12.78 for fucoxanthin, fucoxanthinol, halocynthiaxanthin, and beta-carotene, respectively. The higher radical scavenging activity of fucoxanthin and fucoxanthinol compared with halocynthiaxanthin is assumed to be due to presence of the allenic bond.     

Antioxidant functions of selected allium thiosulfinates and S-alk(en)yl-L-cysteine sulfoxides

Pure thiosulfinates, R-S(O)S-R (2), where R = Me (2a), Pr (2b), or All (2c), at levels up to 4 mM were not capable of scavenging hydrogen peroxide or superoxide anion. Relative to standard antioxidants (ascorbic acid, n-propyl gallate, butylated hydroxytoluene, Trolox, and reduced glutathione), these thiosulfinates were 1-3 orders of magnitude less efficient at reducing 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical, 0.5-2 orders of magnitude less efficient at quenching singlet oxygen, and about equally effective at scavenging hydroxyl radical. Generally, AllS(O)SAll (2c) was the most effective and PrS(O)SPr (2b) was the least effective thiosulfinate in these assays, except that MeS(O)SMe (2a) exhibited no quenching effect toward singlet oxygen. These thiosulfinates were also incapable at levels up to 0.1 mM (where they were toxic) of in vitro induction of quinone reductase (QR) in murine hepatoma (hepa 1c1c7) cells. However, S-1-propenyl-L-cysteine sulfoxide (isoalliin, 1a) and cycloalliin (3) induced QR in this system at 2 mM and 1 mM, respectively, although doubling of QR required levels of 10-15 mM.     

Levels of active oxygen species are controlled by ascorbic acid and anthocyanin in Arabidopsis

Stabilization of the levels of active oxygen species (AOS) is important to the survival of organisms. To clarify the system controlling levels of AOS in plants, this study used an electron spin resonance (ESR) method to directly measure superoxide radical (O(2)(.-)) scavenging activities in the wild-type Arabidopsis thaliana (Col and Ler ecotypes), two anthocyanin mutants (tt3 and ttg1), and an ascorbic acid mutant (vtc1). Under ordinary growth conditions, Arabidopsis contained superoxide-scavenging activity (SOSA) of approximately 300-500 SOD units/g of fresh weight. The ESR pattern indicated that most (40-50%) of this activity was due to ascorbic acid. For the analysis of SOSA under conditions of oxidative stress, synthesis of AOS was induced by gamma-irradiation. The radical scavenging activity in irradiated plants increased approximately 10-fold following an associated increase in the accumulation of ascorbic acid and anthocyanin. The accumulation of ascorbic acid and anthocyanin was suppressed by treatment with an antioxidant before irradiation and was induced by treatment with a radical-generating reagent. The contributions of ascorbic acid and anthocyanin to the total superoxide radical scavenging activity differed among ecotypes. In the Ler ecotype, ascorbic acid accumulated at twice the level of that in the Col ecotype, and induction of anthocyanin was half that in Col. To confirm the activity of ascorbic acid and anthocyanin against AOS stress, the viability of the wild type and mutants (tt2, tt3,tt5, ttg1, and vtc1) was examined after gamma-irradiation. Only the plants in which ascorbic acid and anthocyanin were induced had the ability to grow and flower.     

In vitro antioxidative effects and tyrosinase inhibitory activities of seven hydroxycinnamoyl derivatives in green coffee beans

Seven kinds of hydroxycinnamic acid derivatives identified as 3-caffeoylquinic acid (3-CQA), 4-caffeolyquinic acid (4-CQA), 5-caffeoylquinic acid (5-CQA), 5-feruloylquinic acid (5-FQA), 3,4-dicaffeoylquinic acid (3,4-diCQA), 3,5-dicaffeoylquinic acid (3,5-diCQA), and 4,5-dicaffoylquinic acid (4,5-diCQA) by MS, 1H NMR, and HPLC analyses were isolated from low-quality (immature) and commercial quality green coffee beans. The quantity of chlorogenic acid isomers (10.4 g/100 g), especially 5-CQA, in commercial green coffee beans [West Indische Bereiding (West India processing beans from Sumatra Island, Indonesia, WIB)] was higher than that in low-quality beans [9.1 g/100 g, Eerste Kwaliteit (Export low-quality beans from Java Island, Indonesia, EK-1, grade 4)], whereas little difference in diCQAs was detected between the two kinds of beans. The free radical scavenging activity of these isolates was evaluated in assay systems using DPPH free radicals and superoxide anion radicals generated by xanthine-XOD. The diCQAs showed strong (1.0-1.8-fold) free radical scavenging activity compared to commonly used antioxidants such as alpha-tocopherol and ascorbic acid. The potency order of superoxide anion radical scavenging activity was diCQAs > caffeic acid, CQAs > 5-FQA. The activities of the diCQAs were twice as effective as those of CQAs and 4 times as effective as that of 5-FQA. The diCQAs also exhibited more potent (2.0-2.2-fold) tyrosinase inhibitory activities compared to CQAs, arbutin, and ascorbic acid. The isolates exhibited antiproliferation activities in four cancer cell lines, U937, KB, MCF7, and WI38-VA. Among these, KB cells were most sensitive (IC50 = 0.10-0.56 mM).     

Synthesis of lipophilic clovamide derivatives and their antioxidative potential against lipid peroxidation

Some N-(hydroxycinnamoyl)-L-tyrosine and L-DOPA alkyl esters were synthesized and evaluated as a variation of the clovamide (N-caffeoyl-L-3,4-dihydroxyphenylalanine) structure, a known antioxidant found in red clover. The amides were prepared in good yields starting from methyl and dodecylesters of L-tyrosine and L-DOPA by reacting with the N-hydroxysuccinimidyl esters of ferulic, sinapic, and acetyl-protected caffeic acid, respectively. In the DPPH* (2,2-diphenyl-1-picrylhydrazyl) and superoxide radical quencher assays they showed radical scavenging activity equal to or higher than those of the standard antioxidants ascorbic acid and tocopherol. The antioxidative potentials of the clovamide derivatives against bulk lipid oxidation, as determined by the accelerated autoxidation of oils, were equal to or higher than those of the standard antioxidants; some of the compounds were able to protect an emulsion of linoleic acid/beta-carotene against oxidation. N-Caffeoyl L-tyrosine methyl ester and the N-cinnamoyl L-DOPA alkyl esters especially were potent antioxidants in bulk lipids and moderate protectants in emulsions.     

Isolation and characterization of antioxidant protein fractions from melinjo (Gnetum gnemon) seeds

The protein from the seeds of melinjo ( Gnetum gnemon ) was purified using a precipitation method and ion exchange chromatographic techniques to identify the potent antioxidant and free radical scavenging activities. Two antioxidant protein fractions were isolated from G. gnemon seed with molecular weights of approximately 30 kDa (Gg-AOPI) and 12 kDa (Gg-AOPII) by SDS-PAGE. The N-terminal amino acid sequence of Gg-AOPII is Gly-Asn-Gly-Lys-Ala-Thr-Val-Ala-Ile-Leu-Val-Lys-Glu-Lys-Val-Glu-Tyr-Gly-Glu-Glu, and the result of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) analysis showed that they were distinct from each other; no protein in database matching was found to both Gg-AOPI and Gg-AOPII. The antioxidant or free radical scavenging activities of Gg-AOPs were investigated by employing in vitro assay systems including the inhibition of linoleic acid autoxidation, scavenging effect on α,α-diphenyl-β-picrylhydrazyl free radical (DPPH), 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS), reducing power, chelating abilities of metal ions Cu(2+) and Fe(2+), and protections against hydroxyl radical-mediated DNA damages. The result showed that two protein fractions exhibited significant (p < 0.05) antioxidant activities against free radicals such as DPPH, ABTS, and superoxide anion and showed activities similar to those of glutathione (G-SH) and BHT in a linoleic acid emulsion assay system. Moreover, Gg-AOPI and Gg-AOPII also exhibited notable reducing power and strong chelating effect on Fe(2+) and protected hydroxyl radical induced oxidative DNA damage. The data obtained by the in vitro systems obviously established the antioxidant potency of Gg-AOPs.     

Identification and antiradical properties of anthocyanins in fruits of Viburnum dilatatum thunb

The fruit of Viburnum dilatatum Thunb., called gamazumi, has been shown to prevent oxidative injury in rats given gamazumi crude extract (GCE). Therefore, phenolic compounds in GCE were purified by Sephadex LH-20 column chromatography and preparative high-performance liquid chromatography. Two major anthocyanins were isolated, and their structures were determined by NMR, liquid chromatography/electrospray ionization mass spectrometry/MS and sugar analysis as cyanidin 3-O-(2-O-beta-D-xylopyranosyl)-beta-D-glucopyranoside, namely, cyanidin 3-sambubioside (I) and that of cyanidin 3-O-beta-D-glucopyranoside, namely, kuromanin (II). This is the first identification of these compounds in V. dilatatum fruits, which contain I and II at 141.3 and 4.5 microg/g of fresh fruit, respectively. By the electron spin resonance method, the superoxide anion radical scavenging activities (IC(50)) of I and II were 17.3 and 69.6 microM, and their activities on hydroxyl radicals were 4.3 and 53.2 mM. As a positive control, the activities of ascorbic acid were 74.2 microM on superoxide anion radicals and 3.0 mM on hydroxyl radicals. Our results suggest that these anthocyanins having radical scavenging properties may be key compounds contributing to the antioxidant activity and physiological effects of V. dilatatum fruits.     

Phenolic acid, tocopherol and carotenoid compositions, and antioxidant functions of hard red winter wheat bran

An electron spin resonance (ESR) spectrometry study was conducted to examine the free radical scavenging properties of bran extracts of Alliance and Wichita wheat using hydroxyl radical (HO*), 2,2-diphenyl-1-picryhydrazyl radical (DPPH*), and superoxide radical anion (O2*-) and their chelating capacities against Cu2+. Also reported is the radical cation 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS*+) scavenging activity, oxygen radical absorbing capacity (ORAC), and chelating property against Fe2+ of the bran extracts measured by the spectrophotometric methods. Significant radical scavenging and chelating capacities were detected in the bran extracts, along with significant levels of phenolic acids, tocopherols, and carotenoids. Ferulic acid, with a concentration range of 130.60-146.38 microg/g, was the predominant phenolic acid in all of the tested bran samples and accounted for approximately 53-67% of total phenolic acids on a weight basis. Total tocopherol concentration ranged from 1.87 to 2.95 micromol/100 g of bran, whereas total carotenoid level was 0.20-0.33 micromol/100 g of bran. In addition, both wheat variety and growing conditions might significantly alter antioxidant properties and concentrations of beneficial components in wheat bran.     

Effect of long-term dietary administration of oregano on the alleviation of carbon tetrachloride-induced oxidative stress in rats

This study aimed at evaluating the protective effect of long-term dietary oregano on the alleviation of carbon tetrachloride-induced oxidative stress in rats. Twenty-four female Wistar rats were allocated to four groups of six animals each. Groups 1 (control) and 2 (CCl 4) were fed a basal diet, while groups 3 (oregano) and 4 (oregano + CCl 4) were fed the basal diet supplemented further with ground oregano at 1% level. Following six-week feeding, the rats of groups 2 and 4 were given a single intraperitoneal injection of CCl 4 at a dose of 1 mL/kg bw. Six hours after the CCl 4 injection, all animals were sacrificed, and serum, liver, kidney, and heart tissue samples were collected. Analysis results showed that the addition of oregano significantly increased the total phenolic content and the Trolox equivalent antioxidant capacity of the basal diet but had no effect on its lipid peroxidation index. Treatment with CCl 4 of rats from the CCl 4 group caused a significant increase in aspartate transaminase (AST), alanine transaminase (ALT), and alkaline phosphatase (ALP) in serum, whereas it decreased cholesterol and triglyceride content as compared to the control. It also increased the lipid peroxidation index and decreased the scavenging activities of the 2,2-azinobis(3-ethylbenzothiazoline-6-sulfonic acid diammonium salt (ABTS) radical cation, the hydroxyl anion radical, the superoxide anion radical, and the hydrogen peroxide in all tested tissues, as compared to that of the control. Without CCl 4 treatment, diet supplementation with oregano had no effect on these biochemical parameters, excluding the hydroxyl radical scavenging activity, which was increased in all tested tissues as compared to that of the control. Feeding oregano before CCl 4 treatment resulted in a significant decline of the increase in AST, ALT, and ALP activities ( P < 0.05 vs CCl 4 group), but the recorded values could not attain those of the control group ( P < 0.05 vs control group). It significantly increased the reduced cholesterol and triglycerides ( P < 0.05 vs CCl 4 group) to values not differing from those of the control. It also resulted in a significant reduction of the increased malondialdehyde ( P < 0.05 vs CCl 4 group) to values that could not attain the levels of the control but had no significant effect ( P > 0.05) on the reduced ABTS radical cation scavenging activity. It increased significantly the reduced hydroxyl anion radical scavenging activity ( P < 0.05 vs CCl 4 group) to values that could not attain those of the control in all tested tissues except kidney. Additionally, it resulted in a significant elevation of the decreased superoxide anion radical scavenging activity in serum and liver but had no effect in kidney and heart, whereas it also resulted in a significant elevation of the decreased hydrogen peroxide scavenging activity in liver, kidney, and heart but had no effect in serum. These results suggest that dietary oregano may effectively improve the impaired antioxidant status in CCl 4-induced toxicity in rats.     

Antioxidant and antimelanogenic activities of polyamine conjugates from corn bran and related hydroxycinnamic acids

The antioxidant activity of three major polyamine conjugates, N,N'-dicoumaroyl-putrescine (DCP), N-p-coumaroyl-N'-feruloylputrescine (CFP), and N,N'-diferuloyl-putrescine (DFP) isolated from corn bran, and their related hydroxycinnamic acids, p-coumaric acid and ferulic acid, were evaluated by three antioxidant in vitro assay systems, including 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical and superoxide and hydroxyl radicals generated by enzymatic and nonenzymatic reactions. Additionally, five phenolic compounds were evaluated for melanogenesis inhibitory activity using mushroom tyrosinase and B16 melanoma cells. Most of the phenolic compounds significantly scavenged DPPH, superoxide, and hydroxyl radicals in a dose-dependent manner. Particularly, DFP showed potent DPPH (IC50 = 38.46 microM) and superoxide (IC50 = 291.62 microM) radical scavenging activities, while DCP exhibited the strongest hydroxyl radical scavenging activity (IC50 = 120.55 microM). CFP also exerted moderate DPPH, superoxide, and hydroxyl radical scavenging activities. Meanwhile, DCP (IC50 = 181.73 microM) showed potent tyrosinase inhibitory activity toward l-tyrosine as the substrate, whereas DFP (IC50 = 733.64 microM) significantly inhibited melanin synthesis in B16 melanoma cells. These current results indicate that these three polyamine conjugates from corn bran may be useful potential sources of natural antioxidants and skin-whitening agents.     

Study of the polyphenolic composition and antioxidant activity of new sherry vinegar-derived products by maceration with fruits

Several experiments of maceration of a sherry wine vinegar with different fruits (orange, lemon, strawberry, grapefruit, and lime) have been carried out. After optimization (only peel, no heating and seven days as maximum time of maceration), parameters such as polyphenolic content, superoxide anion scavenging ability (related to antioxidant activity) and ascorbic acid content were determined in sherry wine vinegars macerated with two amounts of peel and for two maceration times (3 and 7 days). The analysis of variance pointed to a clear relationship (p<0.01) between type of fruit and amount of peel and polyphenolic content. The factor "time" was practically not significant for any polyphenol. Sherry wine vinegars macerated with different fruits exhibited higher superoxide anion scavenger ability, with the maximum values found for the vinegar macerated with lemon peel. The correlation analysis showed that the superoxide anion scavenger ability of the vinegars macerated, and thus their antioxidant activity, was highly correlated (p<0.01) with several polyphenols, especially with naringin, hesperidin, neohesperidin and gentisic acid and not with the ascorbic acid content.     

Antioxidant activity of A-type proanthocyanidins from Geranium niveum (Geraniaceae)

Geranium niveum S. Watson (Geraniaceae) is a medicinal herb widely used by the Tarahumara Indians of Mexico. This species is rich in proanthocyanidins and other phenolics. Previous in vitro assays have demonstrated that proanthocyanidins exhibited antiinflammatory, antiviral, antibacterial, enzyme-inhibiting, antioxidant, and radical-scavenging properties. In view of its medicinal use and chemical composition, the aim of the present study was to determine the in vitro antioxidant activity of the extracts and two proanthocyanidins (geranins A and D) from the roots of G. niveum by using seven different assay systems, namely, 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS), 1,1-diphenyl-2-picrylhydrazyl (DPPH), superoxide anion (O2*-), hydrogen peroxide (H2O2), hydroxyl radical (OH*), hypochlorous acid (HOCl), and singlet oxygen ((1)O2). Two known antioxidants, resveratrol and ascorbic acid, were used as positive controls. The results showed that geranins A and D and the extracts were able to scavenge ABTS, DPPH, O2*-, OH*, and HOCl. The scavenging ability of geranins A and D was similar to that of resveratrol and ascorbic acid in the following assays: ABTS, O2*-, and HOCl. The scavenging capacity of ascorbic acid for DPPH was higher than that of both geranins and resveratrol. On the other hand, the OH* scavenging action of both geranins and resveratrol was similar. The methanol-CHCl3 (1:1) extract had a higher ability to scavenge ABTS, DPPH, and O2*- radicals than the chloroform extract. In turn, the latter was more potent than the methanol-CHCl3 (1:1) extract as OH* or HOCl scavenger agent. Neither geranins A and D nor the extracts were able to scavenge H2O2 and (1)O2. In conclusion, G. niveum roots have proanthocyanidins with powerful radical scavenging in vitro activity. This property may partially explain the wide use of this plant in the Tarahumara indigenous system of medicine for the treatment of gastrointestinal illnesses (other than spasms), pain, and fevers associated with oxidative stress.     

Identification and antioxidant activity of novel chlorogenic acid derivatives from bamboo (Phyllostachys edulis)

One known and two novel antioxidant compounds have been isolated from bamboo (Phyllostachys edulis). The butanol-soluble extract of the bamboo leaves was found to have a significant antioxidant activity, as measured by scavenging the stable 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical and the superoxide anion radical (O(2)(-)) in the xanthine/xanthine oxidase assay system. Antioxidant activity-directed fractionation of the extract led to the isolation and characterization of three structural isomeric chlorogenic acid derivatives: 3-O-(3'-methylcaffeoyl)quinic acid (1), 5-O-caffeoyl-4-methylquinic acid (2), and 3-O-caffeoyl-1-methylquinic acid (3). Compounds 2 and 3 were isolated and characterized for the first time from the natural products. In the DPPH scavenging assay as well as in the iron-induced rat microsomal lipid peroxidation system, compounds 2 (IC(50) = 8.8 and 19.2 microM) and 3 (IC(50) = 6.9 and 14.6 microM) showed approximately 2-4 times higher antioxidant activity than did chlorogenic acid (IC(50) = 12.3 and 28.3 microM) and other related hydroxycinnamates such as caffeic acid (IC(50) =13.7 and 25.5 microM) and ferulic acid (IC(50) = 36.5 and 56.9 microM). Among the three compounds, compound 1 yielded the weakest antioxidant activity, and the DPPH scavenging and lipid peroxidation inhibitory activity (IC(50) = 16.0 and 29.8 microM) was lower than those of chlorogenic and caffeic acids. All three compounds exhibited both superoxide scavenging activities and inhibitory effects on xanthine oxidase. Their superoxide anion (O(2)(-)) scavenging activities (IC(50) = 1, 4.3 microM; 2, 2.8 microM; and 3, 1.2 microM) were markedly stronger than those of ascorbic acid (IC(50) = 56.0 microM), alpha-tocopherol (IC(50) > 100 microM), and other test compounds, although their inhibition effects on xanthine oxidase may contribute to the potent scavenging activity. alpha-Tocopherol exerted a significant inhibitory effect (65.5% of the control) on superoxide generation in 12-O-tetradecanoylphorbol-13-acetate-induced human promyelocytic leukemia HL-60 cells, and compound 3 showed moderate activity (36.0%). On the other hand, other compounds including 1, 2, chlorogenic acid, and other antioxidants were weakly active (24.8-10.1%) in the suppression of superoxide generation.     

Scavenging capacity of berry crops on superoxide radicals, hydrogen peroxide, hydroxyl radicals, and singlet oxygen

The antioxidant activities against superoxide radicals (O(2)(*)(-)), hydrogen peroxide (H(2)O(2)), hydroxyl radicals (OH(*)), and singlet oxygen ('O(2)) was evaluated in fruit juice from different cultivars of thornless blackberries (Rubus sp.), blueberries (Vaccinium spp.), cranberries (Vaccinium macrocarpon Aiton), raspberries (Rubus idaeus L. and Rubus occidentalis L.), and strawberries (Fragaria x ananassa Duch.). Among the different cultivars, juice of 'Hull Thornless' blackberry, 'Earliglow' strawberry, 'Early Black' cranberry, 'Jewel' raspberry, and 'Elliot' blueberry had the highest antioxidant capacity against superoxide radicals (O(2)(*)(-)), hydrogen peroxide (H(2)O(2)), hydroxyl radicals (OH(*)), and singlet oxygen ('O(2)). In general, blackberries had the highest antioxidant capacity inhibition of O(2)(*)(-), H(2)O(2), and OH(*). Strawberry was second best in the antioxidant capacity assay for these same free radicals. With regard to 'O(2) scavenging activity, strawberry had the highest value, while blackberry was second. Cranberries had the lowest inhibition of H(2)O(2) activity. Meanwhile, blueberries had the lowest antioxidant capacity against OH(*) and 'O(2). There were interesting and marked differences among the different antioxidants in their abilities to scavenge different reactive oxygen species. beta-Carotene had by far the highest scavenging activity against 'O(2) but had absolutely no effect on H(2)O(2). Ascorbic acid was the best at inhibiting H(2)O(2) free radical activity. For OH(*), there was a wide range of scavenging capacities from a high of 15.3% with alpha-tocopherol to a low of 0.88% with ascorbic acid. Glutathione had higher O(2)(*)(-) scavenging capacity compared to the other antioxidants.     

Antioxidative and anti-glycation activity of garcinol from Garcinia indica fruit rind

Garcinol, a polyisoprenylated benzophenone derivative, was purified from Garcinia indica fruit rind, and its antioxidative activity, chelating activity, free radical scavenging activity, and anti-glycation activity were studied. Garcinol exhibited moderate antioxidative activity in the micellar linoleic acid peroxidation system and also exhibited chelating activity at almost the same level as citrate. It also showed nearly 3 times greater DPPH (1, 1-diphenyl-2-picrylhydrazyl) free radical scavenging activity than DL-alpha-tocopherol by weight in aqueous ethanol solution. In a phenazine methosulfate/NADH-nitroblue tetrazolium system, garcinol exhibited superoxide anion scavenging activity and suppressed protein glycation in a bovine serum albumin/fructose system. Thus, garcinol might be beneficial as a potent antioxidant and a glycation inhibitor under specified conditions.     

Antioxidant activity and radioprotective effects against chromosomal damage induced in vivo by X-rays of flavan-3-ols (Procyanidins) from grape seeds (Vitis vinifera): comparative study versus other phenolic and organic compounds

The quantitative distribution of several flavan-3-ols was determined using HPLC in a grape (Vitis vinifera) seed extract (GSE) of four cultivars grown in the region of Murcia. Polymer >/= C(4) units made up the largest group of procyanidins in the GSE (90.92%, expressed as HPLC % area). The antioxidant activity of GSE and other reference compounds was investigated by measuring their ability to scavenge the ABTS(*)(+) radical cation (TEAC). The most effective compounds were, in order: GSE > rutin > (+)-catechin > diosmin >/= ascorbic acid. The radioprotective effects of GSE and other reference compounds were determined by using the micronucleus test for anticlastogenic activity, any reduction of the frequency of micronucleated polychromatic erythrocytes (MnPCEs) being evaluated in the bone marrow of mouse exposed to X-rays. The most effective compounds were, in order: GSE > rutin > dimethyl sulfoxide (DMSO) > ascorbic acid > 6-n-propyl-2-thiouracil-6c (PTU) > diosmin. The higher ABTS(*)(+) scavenging capacity and anticlastogenic activity of GSE can be explained, structurally, by the high number of conjugated structures between the catechol groups in the B-rings and the 3-OH free groups of the polymeric polyphenolic skeleton and, in addition, by the stability of the aroxyl flavonoid radical generated in the above processes.     

Isolation and structure elucidation of antioxidant polyphenols from quince (Cydonia vulgaris) peels

Thirteen new compounds, as well as 16 already known, have been isolated from organic extracts of peels of Cydonia vulgaris, a fruit of a shrub belonging to the same tribe as the apple. All of the structures were elucidated by EI- or ESI-MS and (1)H and (13)C NMR after purification of individual compounds by HPLC. Thirteen fatty acid esters of cinnamyl alcohols, three fatty acid esters of hydroxybenzoic acid, three fatty acid esters of hydroxybenzaldehyde, three glucosides of aromatic acids, four chlorogenic acids, two flavonols, and a benzylamine have been identified. The fatty acid moieties have been identified by GC-MS analysis of the methanolysis products. All of the compounds were tested for their radical scavenging and antioxidant activities by measuring their capacity to scavenge the 2,2'-diphenyl-1-picrylhydrazyl (DPPH) radical and anion superoxide radical and to induce the reduction of Mo(VI) to Mo(V). The chlorogenic acids and the flavonols exhibited more antioxidant and radical scavenger capacity than the positive standards alpha-tocopherol and ascorbic acid. The results of the tests were analyzed by cluster analysis that grouped all of the compounds on the basis of the substituents on the aromatic ring.