Antioxidant capacity, vitamin C, phenolics, and anthocyanins after fresh storage of small fruits.

Fresh strawberries (Fragaria x ananassa Duch.), raspberries (Rubus idaeus Michx.), highbush blueberries (Vaccinium corymbosum L.), and lowbush blueberries (Vaccinium angustifolium Aiton) were stored at 0, 10, 20, and 30 degrees C for up to 8 days to determine the effects of storage temperature on whole fruit antioxidant capacity (as measured by the oxygen radical absorbing capacity assay, Cao et al., Clin. Chem. 1995, 41, 1738-1744) and total phenolic, anthocyanin, and ascorbate content. The four fruit varied markedly in their total antioxidant capacity, and antioxidant capacity was strongly correlated with the content of total phenolics (0.83) and anthocyanins (0.90). The antioxidant capacity of the two blueberry species was about 3-fold higher than either strawberries or raspberries. However, there was an increase in the antioxidant capacity of strawberries and raspberries during storage at temperatures >0 degrees C, which was accompanied by increases in anthocyanins in strawberries and increases in anthocyanins and total phenolics in raspberries. Ascorbate content differed more than 5-fold among the four fruit species; on average, strawberries and raspberries had almost 4-times more ascorbate than highbush and lowbush blueberries. There were no ascorbate losses in strawberries or highbush blueberries during 8 days of storage at the various temperatures, but there were losses in the other two fruit species. Ascorbate made only a small contribution (0.4-9.4%) to the total antioxidant capacity of the fruit. The increase observed in antioxidant capacity through postharvest phenolic synthesis and metabolism suggested that commercially feasible technologies may be developed to enhance the health functionality of small fruit crops.     

Effect of ascorbic acid and dehydration on concentrations of total phenolics, antioxidant capacity, anthocyanins, and color in fruits

The purpose of this investigation was to report on the total phenolics, anthocyanins, and oxygen radical absorbance capacity (ORAC) of strawberry, peach, and apple, the influence of dehydration and ascorbic acid treatments on the levels of these compounds, and the effect of these treatments on fruit color. Results showed that fresh strawberry had the highest levels for total phenolics [5317.9 mg of chlorogenic acid equivalents (CAE)/kg], whereas lower levels were found in fresh apple and peach (3392.1 and 1973.1 mg of CAE/kg, respectively), and for anthocyanins (138.8 mg/kg), whereas lower levels were found in fresh apple and peaches (11.0 and 18.9 mg/kg, respectively; fresh strawberry had an ORAC value of 62.9 mM/kg Trolox equivalents. The fresh apple and peach were found to have ORAC values of 14.7 and 11.4 mM/kg of Trolox equivalents, respectively. The color values indicated that the addition of 0.1% ascorbic acid increased the lightness (L) and decreased the redness (a) and yellowness (b) color values of fresh strawberry, peach, and apple, sliced samples, and the puree made from them. Also, results showed that dehydration is a good method to keep the concentrations of total phenolics and anthocyanins and ORAC values at high levels.     

Effect of high-oxygen atmospheres on blueberry phenolics, anthocyanins, and antioxidant capacity

The influence of high oxygen concentrations on total phenolic, total anthocyanin, individual phenolic compounds, and antioxidant capacity (measured as oxygen radical absorbance capacity, ORAC) in highbush blueberry fruit (Vaccinium corymbosum L. cv. Duke) was investigated. Freshly harvested blueberries were placed in jars ventilated continuously with air or with 40, 60, 80, or 100% O(2) at 5 degrees C for up to 35 days. Samples were taken initially and at 7-day intervals during storage. Whereas the quality parameters of titratable acidity, total soluble solids, and surface color were only slightly affected by the superatmospheric O(2) treatments, the antioxidant levels were markedly increased by 60-100% O(2) treatments as compared with 40% O(2) treatment or air control during 35 days of storage. Elevated O(2) between 60 and 100% also promoted increases of total phenolics and total anthocyanins as well as the individual phenolic compounds analyzed by HPLC. Fruit treated with O(2) concentrations of >/=60% also exhibited significantly less decay. Data obtained in this study suggest that high-oxygen treatments may improve the antioxidant capacity of blueberry fruit. Furthermore, antioxidant capacity may be correlated with total phenolic and anthocyanin contents in blueberries.     

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.     

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

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

Effect of freezing and storage on the phenolics,ellagitannins, flavonoids,and antioxidant capacity of red raspberries

Scottish-grown red raspberries are a rich source of vitamin C and phenolics, most notably, the anthocyanins cyanidin-3-sophoroside, cyanidin-3-(2(G)-glucosylrutinoside), and cyanidin-3-glucoside, and two ellagitannins, sanguiin H-6 and lambertianin C, which are present together with trace levels of flavonols, ellagic acid, and hydroxycinnamates. The antioxidant capacity of the fresh fruit and the levels of vitamin C and phenolics were not affected by freezing. When fruit were stored at 4 degrees C for 3 days and then at 18 degrees C for 24 h, mimicking the route fresh fruit takes after harvest to the supermarket and onto the consumer's table, anthocyanin levels were unaffected while vitamin C levels declined and those of elligitannins increased, and overall, there was no effect on the antioxidant capacity of the fruit. It is concluded, therefore, that freshly picked, fresh commercial, and frozen raspberries all contain similar levels of phytochemicals and antioxidants per serving.     

Standardized methods for the determination of antioxidant capacity and phenolics in foods and dietary supplements

Methods available for the measurement of antioxidant capacity are reviewed, presenting the general chemistry underlying the assays, the types of molecules detected, and the most important advantages and shortcomings of each method. This overview provides a basis and rationale for developing standardized antioxidant capacity methods for the food, nutraceutical, and dietary supplement industries. From evaluation of data presented at the First International Congress on Antioxidant Methods in 2004 and in the literature, as well as consideration of potential end uses of antioxidants, it is proposed that procedures and applications for three assays be considered for standardization: the oxygen radical absorbance capacity (ORAC) assay, the Folin-Ciocalteu method, and possibly the Trolox equivalent antioxidant capacity (TEAC) assay. ORAC represent a hydrogen atom transfer (HAT) reaction mechanism, which is most relevant to human biology. The Folin-Ciocalteu method is an electron transfer (ET) based assay and gives reducing capacity, which has normally been expressed as phenolic contents. The TEAC assay represents a second ET-based method. Other assays may need to be considered in the future as more is learned about some of the other radical sources and their importance to human biology.     

Evolution of antioxidant capacity during storage of selected fruits and vegetables

Interest in the consumption of fresh fruits and vegetables is, to a large extent, due to its content of bioactive nutrients and their importance as dietary antioxidants. Among all of the selected fruits and vegetables, strawberries and black grapes have relatively high antioxidant capacities associated with high contents of total phenolic compounds, ascorbic acid, and flavonols. More interesting, the results of this study indicated that in most fruits and vegetables storage did not affect negatively the antioxidant capacity. Better, in some cases, an increase of the antioxidant capacity was observed in the days following their purchase, accompanied by an increase in phenolic compounds. In general, fruits and vegetables visually spoil before any significant antioxidant capacity loss occurs except in banana and broccoli. When ascorbic acid or flavonoids (aglycons of flavonols and anthocyanins) were concerned, the conclusions were similar. Their content was generally stable during storage.     

Phenol antioxidant quantity and quality in foods: fruits.

The free and bound phenols have been measured in 20 fruits commonly consumed in the American diet. Phenols were measured colorimetrically using the Folin-Ciocalteu reagent with catechin as the standard after correction for ascorbic acid contribution. On a fresh weight basis, cranberry had the highest total phenols, and was distantly followed by red grape. Free and total phenol quality in the fruits was analyzed by using the inhibition of lower density lipoprotein oxidation promoted by cupric ion. Ascorbate had only a minor contribution to the antioxidants in fruits with the exception of melon, nectarine, orange, white grape, and strawberry. The fruit extracts' antioxidant quality was better than the vitamin antioxidants and most pure phenols, suggesting synergism among the antioxidants in the mixture. Using our assay, fruits had significantly better quantity and quality of phenol antioxidants than vegetables. Fruits, specifically apples and cranberries, have phenol antioxidants that can enrich lower density lipoproteins and protect them from oxidation. The average per capita consumption of fruit phenols in the U.S. is estimated to be 255 mg/day of catechin equivalents.     

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.     

Alterations of vitamin C, total phenolics, and antioxidant capacity as affected by processing tomatoes to different products

This study was conducted to investigate the antioxidant vitamin C, the polyphenol content, and the hydrophilic antioxidant capacity of tomato juice, baked tomatoes, tomato sauce, and tomato soup. During the production of tomato juice and during the preparation of the other tomato products, samples were taken after different times, respectively, after each particular production step. High-performance liquid chromatography was used to determine the content of vitamin C. The total phenolics content was analyzed spectrophotometrically by using the Folin-Ciocalteu method. The hydrophilic antioxidant capacity was measured by using three different methods: the Trolox equivalent antioxidant capacity assay, the ferric reducing antioxidant power test, and the photochemiluminescence assay. The vitamin C contents of the tomato products decreased during the thermal processing of tomatoes. In contrast, the total phenolics concentration and the water soluble antioxidant capacity increased.     

Anthocyanins, phenolics, and color of Cabernet Franc, Merlot, and Pinot Noir wines from British Columbia.

Changes in phenolics (anthocyanins, flavonols, tartaric esters, and total phenolics) during ripening of grapes and in phenolics and color during vinification and aging of Cabernet Franc, Merlot, and Pinot Noir wines were studied. Anthocyanins in grape skins showed variations in accumulation pattern, concentration, and distribution depending on variety and to a lesser extent on season. During vinification, colorless phenolics increased during alcoholic fermentation, reached maximum values at pressing, and remained stable during malolactic fermentation and subsequent storage. Anthocyanins and color density, on the other hand, increased during the early stages of alcoholic fermentation, reached maximum values 2-3 days after the start of fermentation, decreased during malolactic fermentation, and slowly declined during subsequent storage. Viticultural practices that increased cluster sun exposure generally led to higher phenolics and color density of wines, whereas changing yeasts used for fermentation had minimal effects.     

Peroxyl radical scavenging capacity, polyphenolics, and lipophilic antioxidant profiles of mulberry fruits cultivated in southern China

Twenty-seven cultivars of mulberry fruits ( Morus atropurpurea Roxb) were analyzed for their total phenolic content, total anthocyanin content, and peroxyl radical scavenging capacities. The proanthocyanidin contents of the fruit were also quantified using 4-dimethylamino-cinnamaldehyde assay, and characterization was attempted using electrospray ionization mass spectra. The phenolic compounds of mulberry fruits were characterized using HPLC with ESI-MS and diode array detection. Results showed that the content of mulberry fruits varied with different cultivars with total phenolic content, total anthocyanin content, total proanthocyanidin content, and peroxyl radical scavenging capacities ranging from 0.060-0.244, 0.001-0.056, 0.001-0.015, and 0.301-1.728, respectively. Good correlations were observed among the phenolic, anthocyanin, and proanthocyanidin contents and the radical scavenging capacities of mulberry fruits. Mulberry fruits were found to contain low amount of proanthocyanidins. The high total phenolic content of mulberry fruits were mainly contributed by anthocyanins, rutin, and chlorogenic acids. The lipid soluble antioxidants are profiled by an HPLC method developed in-house, and the results of selected mulberry fruits revealed significant amounts of lutein and delta- and gamma-tocopherols but low alpha-tocopherol. Our results provide useful antioxidant nutritional information of a mulberry cultivar that has potential for large scale plantations.     

Processing strawberries to different products alters contents of vitamin C, total phenolics, total anthocyanins, and antioxidant capacity

Strawberries were processed to juice, nectar, wine, and puree. For investigation of the antioxidant capacity as well as the contents of ascorbic acid, total phenolics and total anthocyanins, samples were taken after different stages of production to determine the effects of processing. The content of vitamin C was measured spectrophotometrically. The total phenolic content was analyzed by using the Folin-Ciocalteu method, and the amount of total anthocyanins was determined by using the pH-differential method. Two different methods-the trolox equivalent antioxidant capacity assay and the ferric reducing antioxidant power test-were used to determine the hydrophilic antioxidant capacity. This study showed the decrease of all investigated parameters within processing strawberries to different products. The content of ascorbic acid decreased with production time and processing steps, especially during heat treatment. The investigations on total phenolics in strawberry products proved fining to be a mild method to clarify berry juices and wines without removing high amounts of total phenolics. Fermentation did not lead to heavy losses of total phenolics, probably due to polymerization and condensation of monomer phenolics such as anthocyanins. Total anthocyanins and the hydrophilic antioxidant capacity decreased while using high temperatures. Anthocyanins also decreased considerably during the processing of wines, mainly caused by fermentation and pasteurization.     

Catechins and procyanidins in berries of vaccinium species and their antioxidant activity

The fractions of monomeric catechins and the fractions of dimeric and trimeric procyanidins were extracted and concentrated from wild berries of Vaccinium species to study their antioxidant activities. The compositions of the fractions were analyzed using high-performance liquid chromatography combined with diode-array and electrospray ionization mass spectrometric detection. Rare A-type dimers and trimers were identified as the predominant procyanidins in wild lingonberry, cranberry, bilberry, and bog whortleberry. Lingonberry and cranberry catechin and procyanidin fractions as well as bog whortleberry catechin fraction were good scavengers of radicals in the 2,2-diphenyl-1-picrylhydrazyl (DPPH) test and more efficient than the respective bilberry fractions. Bog whortleberry procyanidin fraction was less active, this being mainly due to the lower content of these compounds. Fractions from lingonberry, cranberry, and bilberry were equally efficient in inhibiting the oxidation of methyl linoleate emulsion, but differences among the berries were found in their abilities to inhibit low-density lipoprotein (LDL) oxidation. Catechins, the monomers, exhibited comparable activity to the fractions containing dimers and trimers in inhibiting the oxidation of methyl linoleate emulsion and human LDL. Bog whortleberry catechins were excellent antioxidants toward the oxidation of human LDL. Radical scavenging and antioxidant activities of Vaccinium berry fractions were attributable to the their composition of catechins and procyanidins. In conclusion, Vaccinium catechins as well as dimeric and trimeric procyanidins provide substantial antioxidant protection.     

E-cinnamic acid derivatives and phenolics from Chilean strawberry fruits, Fragaria chiloensis ssp. chiloensis

Three E-cinnamic acid glycosides, tryptophan, and cyanidin-3-O-beta-D-glucopyranoside were isolated from ripe fruits of the Chilean strawberry Fragaria chiloensis ssp. chiloensis. 1-O-E-Cinnamoyl-beta-D-xylopyranoside, 1-O-E-cinnamoyl-beta-D-rhamnopyranoside, and 1-O-E-cinnamoyl-alpha-xylofuranosyl-(1-->6)-beta-D-glucopyranose are reported for the first time. The cinnamic acid glycosides and aromatic compound patterns in F. chiloensis fruits were determined by high-performance liquid chromatography (HPLC). HPLC analyses of extracts showed that cyanidin-3-O-beta-D-glucopyranoside and free ellagic acid are present in achenes while the E-cinnamoyl derivatives and tryptophan were identified only in the thalamus. The free radical scavenging effect of the fruit extract can be associated with the anthocyanin content.     

Phenolic constituents and antioxidant capacity of four underutilized fruits from the Amazon region

The Amazon region comprises a plethora of fruit-bearing species of which a large number are still agriculturally unimportant. Because fruit consumption has been attributed to an enhanced physical well-being, interest in the knowledge of the chemical composition of underexplored exotic fruits has increased during recent years. This paper provides a comprehensive identification of the polyphenolic constituents of four underutilized fruits from the Amazon region by HPLC/DAD-ESI-MS(n). Arac?a? ( Psidium guineense ), jambola?o ( Syzygium cumini ), muruci ( Byrsonima crassifolia ), and cutite ( Pouteria macrophylla ) turned out to be primarily good sources of hydrolyzable tannins and/or flavonols. Additionally, different flavanonols and proanthocyanidins were identified in some fruits. The antioxidant capacity was determined by using the total oxidant scavenging capacity (TOSC) assay. Cutite showed the highest antioxidant capacity followed by jambola?o, arac?a?, and muruci.     

Interspecific variation in anthocyanins, phenolics, and antioxidant capacity among genotypes of highbush and lowbush blueberries (Vaccinium section cyanococcus spp.)

Recent interest in the possible protective effects of dietary antioxidant compounds against human degenerative disease has prompted investigation of foods such as blueberries (Vaccinium sp.), which have a high antioxidant capacity. Fruit obtained from genotypes of highbush blueberries (Vaccinium corymbosum L.) and lowbush blueberries (Vaccinium angustifolium Aiton) were analyzed for their antioxidant capacity, their content of anthocyanins, and total phenolic compounds, to evaluate the intraspecific and interspecific variation in these parameters. The method of extraction influenced the composition of fruit extracts; the highest anthocyanin and total phenolic contents and antioxidant capacity were found in extracts obtained using a solvent of acidified aqueous methanol. Regardless of the method, lowbush blueberries were consistently higher in anthocyanins, total phenolics, and antioxidant capacity, compared with highbush blueberries. There was no relationship between fruit size and anthocyanin content in either species.     

Resveratrol, pterostilbene, and piceatannol in vaccinium berries

A study was conducted to determine the presence of resveratrol, pterostilbene, and piceatannol in Vaccinium berries. Samples representing selections and cultivars of 10 species from Mississippi, North Carolina, Oregon, and Canada were analyzed by gas chromatography/mass spectrometry. Resveratrol was found in Vaccinium angustifolium (lowbush blueberry), Vaccinium arboretum (sparkleberry), Vaccinium ashei (rabbiteye blueberry), Vaccinium corymbosum (highbush blueberry), Vaccinium elliottii (Elliott's blueberry), Vaccinium macrocarpon (cranberry), Vaccinium myrtillus (bilberry), Vaccinium stamineum (deerberry), Vaccinium vitis-ideae var. vitis-ideae (lingonberry), and Vaccinium vitis-ideae var. minor (partridgeberry) at levels between 7 and 5884 ng/g dry sample. Lingonberry was found to have the highest content, 5884 ng/g dry sample, comparable to that found in grapes, 6471 ng/g dry sample. Pterostilbene was found in two cultivars of V. ashei and in V. stamineum at levels of 99-520 ng/g dry sample. Piceatannol was found in V. corymbosum and V. stamineum at levels of 138-422 ng/g dry sample. These naturally occurring stilbenes, known to be strong antioxidants and to have cancer chemopreventive activities, will add to the purported health benefits derived from the consumption of these small fruits.     

Antioxidant and antiulcerative properties of phenolics from Chinese quince, quince, and apple fruits

To evaluate the health benefits of Chinese quince and quince phenolics, their antioxidant properties and antiulcerative activity were investigated in comparison with apple phenolics as a reference. The strength of antioxidant activity and DPPH radical scavenging activity of these fruit phenolics varied according to different in vitro evaluation systems, whereas the antioxidative property of rat blood increased in all rats orally administered phenolics. Ferulic acid and isoferulic acid were detected as major metabolites in rats given apple phenolics, quince phenolics, and 5-caffeoylquinic acid standard. (-)-Epicatechin and its 3'-O-methyl ether could be detected in rats administered apple phenolics and (-)-epicatechin standard. In the ethanol-induced gastric ulcer, pre-administration of Chinese quince and quince phenolics suppressed the occurrence of gastric lesions in rats, whereas apple phenolics seemed to promote ulceration. The trend of myeloperoxidase activity was similar to that of the ulcer index. The results showed that Chinese quince and quince phenolics might have health benefits by acting both in blood vessels and on the gastrointestinal tract.