Flavonoid constituents and their contribution to antioxidant activity in cultivars and hybrids of rabbiteye blueberry (Vaccinium ashei Reade)

Fruit from 42 blueberry (Vaccinium spp.) cultivars, including 36 rabbiteye cultivars (Vaccinium ashei Reade), three V. ashei hybrid derivatives, and three northern highbush (Vaccinium corymbosum L.) standards were evaluated for antioxidant capacity, individual flavonoid content, and the contribution of each identified phenolic compound to total antioxidant activity. Considerable variation was found in flavonoid content, antioxidant activity, and their contribution to total antioxidant activity among cultivars. Among 42 blueberry cultivars, the rabbiteye ‘Early May’ contained the highest amount of chlorogenic acid, myricetin 3-arabinoside, quercetin derivatives, and delphinidin-, cyanidin-, petunidin-, and malvidin-basis anthocyanins. ‘Early May’ cultivar also had the highest antioxidant activity (88.2 μmol TE/g fw). ‘Owen’, ‘Bluegem’, ‘Clara’, Climax’, and ‘Centurion’ were among the other rabbiteye cultivars that also had high levels of flavonoids and antioxidant activities. In contrast, the pink-fruited V. ashei hybrid, ‘Pink Lemonade’, had the lowest content of flavonoids and lowest antioxidant activity. The mean flavonoid content and antioxidant activity of rabbiteye cultivars was higher than those among northern highbush and V. ashei hybrids. The antioxidant activity of V. ashei hybrid derivatives was derived mainly from chlorogenic acid, myricetin, and quercetin, which contributed 62.5% of total antioxidant activity, whereas anthocyanins (malvidin, petunidin, delphinidin, and cyanidin) were the main contributors to the antioxidant activity of rabbiteye cultivars (76.2%) and northern highbush standards (76.8%). Blueberry cultivars identified to have high phenolic content and high antioxidant activity could be used as parents for future blueberry breeding programmes to develop new blueberry cultivars with higher antioxidant activity and further improve human health.     

Phenolic acids and flavonoids in leaf and floral stem of cultivated and wild Cynara cardunculus L. genotypes

Ten genotypes, cultivated and wild of Cynara cardunculus L. were evaluated for their content of phenolic acids, flavonoids and their antioxidant activity. The major compounds present in the leaf were luteolin derivatives in globe artichoke and apigenin derivatives in wild and cultivated cardoon. Apart from ‘Cimiciusa di Mazzarino’ (var. scolymus), caffeoylquinic acids represent the main phenolic compounds in the floral stem. In particular, ‘Sylvestris Creta’ (var. sylvestris) and ‘Violetto di Sicilia’ (var. scolymus) show the highest content of caffeoylquinic acid ∼95% of the total measured polyphenols. The antioxidant capacity, in both leaf and floral stem, was qualitatively and quantitatively dependent on the phenolic acid and flavonoid profile. The phenolic acids and flavonoids in normally uneaten parts of wild and cultivated artichoke could be exploited as sources of natural antioxidants.     

Effect of meteorological conditions on antioxidant flavonoids in Portuguese cultivars of white and red onions

Although onion (Allium cepa L.) bulbs are good sources of phenolic compounds, the levels of these secondary metabolites are highly variable, depending on the cultivar, production, metereological conditions and post-harvest practices. The aim of this study was to characterize the interannual variation of flavonoid content in two Portuguese landrace varieties of onion (‘Branca da Póvoa’, white, and ‘Vermelha da Póvoa’, red), grown in the Spring–Summer of 2004, 2005, 2006, 2007 and 2008. HPLC-DAD was used to determine flavonoid concentration.     

Exploring the phytochemical content and the antioxidant potential of Citrus fruits grown in Cyprus

The physicochemical and phytochemical profile as well as the antioxidant properties of the most important Citrus fruits grown in Cyprus [orange (Citrus sinensis, cv. ‘Valencia’), grapefruit (Citrus paradisi, cvs. ‘White Marsh’, ‘Star Ruby’, ‘Rio Red’) and an interspecific hybrid (Citrus reticulata x Citrus sinensis, cv. ‘Mandora’)] were determined. ‘Valencia’ fruit exhibited the highest phenolic, flavonoid and ascorbic acid content, as well as a higher antioxidant potency, followed by ‘Mandora’ fruit and the three grapefruit cultivars. HPLC indicated significant diversity on flavanones among the examined fruits, while LC-MS analysis revealed the presence of hydroxycinnamic acid derivatives, polymethoxyflavones and a furocoumarin. Overall, this study provides supporting evidence for the superiority of ‘Valencia’ orange fruit as an excellent source of bioactive compounds. In addition, to the best of our knowledge, this is the first study thoroughly describing the phytochemical profile of ‘Mandora’ fruit, an interspecific hybrid cultivated in Cyprus.     

How much do cultivar and preparation time influence on phenolics content in walnut liqueur?

The influence of cultivar and picking date on the phenolic content of walnut liqueur was investigated using HPLC with a PDA detector. Ten phenolic compounds, namely gallic, protocatechuic, ellagic, chlorogenic (5-caffeoylquinic), syringic, p-coumaric and sinapic acids, as well as (+)-catechin, 1,4-naphthoquinone and juglone were detected. The walnut liqueur under analysis was made of the cultivars ‘Franquette’ and ‘Elit’, on two sampling dates (June 30th and July 7th). A close interaction between cultivar and sampling date was noticed for most of the phenolics analyzed. The content levels of the main phenolic compounds under investigation were highest in ‘Franquette’ at the end of June and lowest in ‘Elit’ on the second or both sampling dates, except for syringic acid. A strong influence of cultivar choice and picking date was observed. The content levels of most phenolics were higher in liqueur prepared from the cultivar ‘Franquette’, than in ‘Elit’.     

Direct characterisation of phenolic antioxidants in infusions from four Mapuche medicinal plants by liquid chromatography with diode array detection (HPLC-DAD) and electrospray ionisation tandem mass spectrometry (HPLC-ESI-MS)

A simple, fast and direct method was developed for the qualitative analysis of phenolic constituents from infusions of Mapuche medicinal plants. Teas made of Linum chamissonis Schiede, Quinchamalium chilensis Mol., Adesmia emarginata Clos. and Escallonia illinita K. Presl. were analysed by high-performance liquid chromatography with diode array detector (HPLC-DAD) and electrospray mass spectrometry (ESI-MS). This technique allowed for the first time the tentative identification of 16 phenolic compounds in E. illinita, 27 in Q. chilensis, 10 in L. chamissonis and 19 in A. emarginata. The compounds were mainly phenolic acids, flavonoid glycosides, anthocyanins and tannins. The total phenolic and flavonoid content of the infusions was assessed as well as the free radical scavenging capacity measured by the bleaching of a solution of the 2,2-diphenyl-1-picrylhydrazyl (DPPH⁻) radical. From the four species, Q. chilensis exhibited the strongest antioxidant activity with highest total phenolic and flavonoid content.     

Nutritional components and anti-oxidant capacity of ten cultivars and lines of cactus pear fruit (Opuntia spp.)

Cactus pear fruit (Opuntia) are harvested from various species of the genus Opuntia of the cactus family (Cactaceae), and are produced and consumed in several countries. We have characterized the nutritional content and antioxidant capacity (AC) of the fruit of ten cultivars/lines of distinct pulp colors. ‘Camuesa’ had the highest betalains, total carotenoids, ß-carotene, ascorbic acid, and was one of the highest in total phenolic compounds, but its AC did not demonstrate outstanding differences with some other cultivars/lines that were not as rich in these compounds. ‘Roja Pelota’ had high AC when measured with the DPPH assay, but had low total carotenoids, ß-carotene and total phenolic content. ‘Reyna’ had slightly low AC as measured by the FRAP assay, practically no betalains, and low vitamin C, tocopherols, ß-carotene, and total phenolic content.     

Chicoric acid found in basil (Ocimum basilicum L.) leaves

This is the first report to identify the presence of chicoric acid (cichoric acid; also known as dicaffeoyltartaric acid, which is a caffeic acid derivatized with tartaric acid) in basil leaves. Rosmarinic acid, chicoric acid and caftaric acid (in the order of most abundant to least; all derivatives of caffeic acid) were identified in fresh basil leaves. Rosmarinic acid was the main phenolic compound found in both leaves and stems. Chicoric acid was not detected in sweet basil stems, although a small amount was present in Thai basil stems. Other cinnamic acid monomers, dimers and trimers were also found in minor quantities in both stems and leaves. Basil polyphenolic contents were determined by blanched methanol extraction, followed by HPLC/DAD analysis. The characterization of the polyphenolics found in the basil extracts were performed by HPLC/DAD/ESI–MS/MS and co-chromatographed with purchased standard. The influence of inoculation with an arbuscular mycorrhizal fungus (AMF), Glomus intraradices, on plant phenolic composition was studied on two basil cultivars,‘Genovese Italian’ and ‘Purple Petra’. Inoculation with AMF increased total anthocyanin concentration of ‘Purple Petra’ but did not alter polyphenolic content or profile of leaves and stems, of either cultivar, compared to non-inoculated plants. In the US diet, basil presents a more accessible source of chicoric acid than does Echinacea purpurea, in which it is the major phenolic compound.     

Organic acids,antioxidant capacity,phenolic content and lipid characterisation of Georgia-grown underutilized fruit crops

Four underutilized Georgia-grown fruit crops, namely loquat (Eriobotrya japonica), mayhaw (Crataegus sp.), fig (Ficus carica), and pawpaw (Asimina triloba), and their leaves were analysed for total polyphenols by Folin–Ciocalteau method, and antioxidant capacity by ferric-reducing antioxidant power (FRAP) and Trolox-equivalent antioxidant capacity (TEAC) assays. Organic acids and phenolic compounds were identified by RP-HPLC. For lipid profile, fruits were separated into two fractions – seed and fruit (i.e., without seed); lipid was extracted using the Folch method and analysed for fatty acids, phytosterols, tocopherols, and phospholipids. The major organic acid identified in all samples was malic acid (177–1918 mg/100 g FW). The predominant phenolic acids in all the fruits were gallic (1.5–6.4 mg/100 g FW) and ellagic (0.2–33.8 mg/100 g FW), and the most abundant flavonoid was catechin (12.2–37.8 mg/100 g FW). Total lipid content varied from 0.1% in mayhaw fruit to 21.5% in pawpaw seed. Linoleic acid was the predominant fatty acid in all of the samples (28.2–55.7%).     

Influence of genotype,harvest time and plant part on polyphenolic composition of globe artichoke [Cynara cardunculus L. var. scolymus (L.) Fiori]

Globe artichoke is an ancient herbaceous plant native to the Mediterranean Basin. The edible part of the plant (head) is particularly rich in polyphenols, whose therapeutic properties are well documented. A field experiment was conducted in Sicily (south Italy) to examine the influence of genotype and harvest time on the polyphenol content and profile of different head parts. The concentrations of 19 phenolic compounds were determined by HPLC-DAD-ESI/MSⁿ analysis. It was observed that individual phenolic substances were preferentially accumulated in specific head parts and genotypes. Apigenin 7-O-glucuronide was found to be the major flavonoid, with 6298 mg kg⁻¹ DM in ‘Romanesco clone C3’ receptacle, whereas chlorogenic acid represented the main caffeoylquinic acid, reaching 14841 mg kg⁻¹ DM in the inner bracts of ‘Violetto di Sicilia’. Our findings prove also the influence of climatic conditions on the phenolic profile and thus suggest giving specific consideration to harvest time.     

Determination of phenolic compounds of ‘Sikitita’ olive leaves by HPLC-DAD-TOF-MS. Comparison with its parents ‘Arbequina’ and ‘Picual’ olive leaves

‘Sikitita’ is a new olive cultivar developed in Spain by crossing the cultivars ‘Picual’ and ‘Arbequina’. The phenolic fraction of olive leaves (Olea europaea L.), is purported to have good anti-oxidative properties which help to prevent several health problems. To our knowledge, no studies are available on the phenolic fraction of ‘Sikitita’ olive leaves or any other new cultivar developed from breeding. Thus, the identification and quantification of the phenolic fraction of ‘Sikitita’ olive leaves by HPLC-DAD-MS were studied and compared with those of its parent cultivars. The three cultivars were grown under the same agronomic and environmental conditions in the same orchard. The quantification was performed using HPLC-DAD, whereas qualitative data were acquired using HPLC-MS. It was thus possible to identify 30 different compounds, two of which have been tentatively characterized for the first time in olive leaves of Spanish cultivars. Significant differences between cultivars were observed for almost all the compounds. Results for ‘Sikitita’ olive leaves presented a higher degree of similarity with respect to ‘Picual’ than to ‘Arbequina’. Further work will monitor the time course of phenolic compounds over the growth period.     

Investigation of bitterness in carrots (Daucus carota L.) based on quantitative chemical and sensory analyses

Bitterness is considered as an undesirable taste of carrots. Quantitative chemical analysis of potential bitter compounds of different carrot genotypes was combined with sensory analysis in order to identify key compounds likely to be responsible for the bitterness of carrots. Eight carrot genotypes (‘Bolero’, ‘Mello Yello’, ‘Nairobi’, ‘Tornado’, ‘Purple Haze’, ‘Line 1’, ‘Line 2’, and ‘Line 3’) representing extremes in sensory-perceived odour, flavour, and taste. Potential bitter compounds like polyacetylenes, isocoumarins and phenolic acids were quantified in the peel and the corresponding peeled carrot, and their contribution to bitterness in raw carrots was analysed by sensory profiling using multivariate data analysis. Falcarindiol and a di-caffeic acid derivative were highly related to bitterness in contrast to falcarinol and other potential bitter compounds. Falcarindiol and the di-caffeic acid derivative were primarily present in the peel whereas falcarinol was almost evenly distributed in the root. Investigation of bitterness revealed that high sugar content to some extent could mask the bitter perception of carrots. As falcarinol is the most bioactive of the carrot polyacetylenes the results of the present study indicate that there is a basis for improving the health effects of raw carrots without affecting sensory quality.     

Comparative study of primary and secondary metabolites in 11 cultivars of persimmon fruit (Diospyros kaki L.)

Primary metabolites (sugars, organic acids) and secondary metabolites (phenolics and carotenoids) were quantified by HPLC in fully ripe fruit of 11 kaki cultivars: ‘Amankaki’, ‘Cal Fuyu’, ‘Fuji’, ‘Hana Fuyu’, ‘Jiro’, ‘O’Gosho’, ‘Tenjin O’Gosho’, ‘Thiene’, ‘Tipo’, ‘Tone Wase’ and ‘Triumph’. Amongst the analysed cultivars, ‘Tone Wase’ stands out as the richest in sugars, particularly glucose, and cultivars ‘Tipo’ and ‘Triumph’ contained the highest amounts of organic acids. Cultivars ‘O’Gosho’, ‘Cal Fuyu’ and ‘Hana Fuyu’ contained the least sugars and cultivar ‘Jiro’ the least organic acids. Amongst the individual phenolic compounds catechin and gallic acid were present in highest concentrations. The predominant carotenoid in both skin and pulp of ripe persimmon fruit was β-carotene, the highest content was measured in skin of cultivar ‘Hana Fuyu’, which also contained the highest level of total carotenoids. In persimmon pulp, much lower values for carotenoids were obtained, particularly in fruit of cultivar ‘Cal Fuyu’.     

Free radical scavenging capacity and antioxidant enzyme activity in deerberry (Vaccinium stamineum L.)

Fruit from three genotypes (‘B-76’, ‘B-59’ and ‘SHF-3A’) of deerberry [Vaccinium stamineum L.] were evaluated for fruit quality, total anthocyanin and phenolic contents, antioxidants, antioxidant capacity, and antioxidant enzyme activity. The fruit soluble solids, titratable acids, total anthocyanins, and total phenolic contents varied with genotypes. Cyanidin 3-galactoside and cyanidin 3-arabinoside were the two predominant anthocyanins. Resveratrol was also found in deerberries. Among the three genotypes, ‘B-76’ had higher amount of anthocyanins, phenolic compounds and resveratrol than ‘B-59’ and ‘SHF-3A’. Deerberries contained potent free radical scavenging activities for 2,2-Di (4-tert-octylphenyl)-1-picrylhydrazyl (DPPH), 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS⁺), peroxyl radical (ROO), superoxide radicals (), hydrogen peroxide (H₂O₂), hydroxyl radicals (OH), and singlet oxygen (¹O₂) radicals and also had high activities of antioxidant enzymes including glutathione-peroxidase (GSH-POD), glutathione reductase (GR), superoxide dismutase (SOD), ascorbate peroxidase (AsA-POD), guaiacol peroxidase (G-POD), monodehydroascorbate radical reductase (MDAR), dehydroascorbate reductase (DHAR), glutathione reductase (GR)] and non-enzyme antioxidants [ascorbic acid (ASA) and reduced glutathione (GSH)]. Antioxidant capacities were highly correlated to antioxidant enzymes activities. Among the three genotypes, ‘B-76’ had the highest level of antioxidants and antioxidant enzyme activity.     

Antiradical activity of different parts of Walnut (Juglans regia L.) fruit as a function of genotype

The objective of this work was to analyse phenolic compounds and antiradical capacity of different parts of walnut fruit among six genotypes of Juglans regia L. Therefore, total phenolic and flavonoid content were determined and methanolic extracts of walnut genotypes were considered by the reducing power, DPPH (2,2-diphenyl-1-picrylhydrazyl), superoxide anion and nitric oxide radical scavenging. Significant differences were found in phenolic content and radical scavenging capacity of different parts of fruits and among various genotypes. High correlation coefficient (R² = 0.81) was observed between phenol content and radical scavenging activity, but this was not always true (R² = 0.01). These results demonstrated that walnut genotypes have different phenolic compounds and phenolic compounds have different radical scavenging power. The differences of phenolic compounds were confirmed by using high performance liquid chromatography (HPLC).     

Changes in chemical constituents during the maturation and ripening of two commercially important pomegranate accessions

Pomegranate juice is well known for its health beneficial compounds. This study was undertaken to investigate changes in the major chemical composition in arils and peels during fruit maturation in two Israeli commercial accessions, ‘Wonderful’ and ‘Rosh-Hapered.’ In both accessions, the levels of total phenolic, antioxidant activity and hydrolysable tannins were reduced in the peels during maturation, while the anthocyanin level increased. The results show that the sugar content in the aril juice increased in both accessions while the levels of acidity and of citric acid decreased. However, these two accessions differed in other parameters in the aril juice, i.e., while the antioxidant and total phenolic contents significantly decreased in ‘Rosh-Hapered’, these changes were not observed in ‘Wonderful’. The anthocyanin level, however, increased in ‘Wonderful’ but did not change in ‘Rosh-Hapered.’ This knowledge could help establish the optimum harvest date ensuring the maximum nutritional properties of pomegranates.     

Identification and quantification of major phenolic compounds from mango (Mangifera indica, cv. Ataulfo) fruit by HPLC–DAD–MS/MS-ESI and their individual contribution to the antioxidant activity during ripening

Mango (Mangifera indica L.) is an economically important fruit throughout the world. ‘Ataulfo’ mango, a leading cultivar in Mexico, has the highest content of phenolic compounds among several commercial varieties of mango. However, the individual identification and antioxidant contribution of these phenols during ripening of mango fruit is unknown. Qualitative and quantitative analysis of the major phenolic compounds found in ‘Ataulfo’ mango fruit pulp was conducted in four stages of ripeness, using high-performance liquid chromatography coupled to mass spectrometry. The antioxidant contribution of each of the major phenolic compounds was calculated. The major compounds identified were chlorogenic acid (28–301 mg/100 g DW), gallic acid (94.6–98.7 mg/100 g DW), vanillic acid (16.9–24.4 mg/100 g DW), and protocatechuic acid (0.48–1.1 mg/100 g DW). The antioxidant contribution of the four phenolic acids increased during ripening. Gallic acid accounted for the highest contribution (39% maximum value), followed by chlorogenic acid (21% maximum value). This could indicate that these phenolic compounds may have an important role in the antioxidant metabolism in ‘Ataulfo’ mango fruit during ripening, and promoting health benefits to consumers.     

HPLC–MS identification of phenols in hazelnut (Corylus avellana L.) kernels

In whole hazelnut kernels, as the main product of hazelnut (Corylus avellana L.), phenols were analysed in 20 hazelnut cultivars by high-performance liquid chromatography–tandem mass spectrometry (HPLC–MS). Twenty-three compounds from different phenolic groups were detected, and 15 of them were identified. In hazelnut kernels, these substances were detected: nine flavan-3-ols, two benzoic acids (gallic and protocatechuic acid), three flavonols and phloretin glycoside. Total phenol concentrations ranged from 70 to 478 mg gallic acid equivalents per kg hazelnut kernels. A high content level of total phenols was observed in the ‘Tonda Gentile delle Langhe’ and ‘Lewis’ cultivars, which was followed by the ‘Corabel’, ‘Fertile de Coutard’, ‘Daria’ and ‘Tonda Gentile Romana’ cultivars. Similarly, the highest antioxidative activity, measured by employing DPPH-antiradical assay, was also found in the ‘Tonda Gentile delle Langhe’ cultivar, followed by the ‘Fertile de Coutard’.     

Effect of nitrogen starvation on the phenolic metabolism and antioxidant properties of yarrow (Achillea collina Becker ex Rchb.)

In this study, the effects of long-term nitrogen deficiency (N 0.1 mM for 4 months) on growth, phenolic content and activity of phenylalanine ammonia lyase (PAL; EC 4.3.1.5) were investigated in the leaves, inflorescences and roots of yarrow (Achillea collina Becker ex Rchb.) grown in hydroponics. The antioxidant capacity of methanol extracts was also evaluated. Nitrogen starvation decreased plant growth and the leaves’ total nitrogen, amino acids, proteins, chlorophylls and carotenoids contents indicating that the primary metabolism was severely limited by low nitrogen availability. The amount of total phenolics and the antioxidant capacity were higher in leaves and roots of nitrogen-starved compared to control plants. The most abundant phenolic acids identified in yarrow were 5-O-caffeoylquinic acid (chlorogenic acid), and 3,5 and 4,5-di-O-caffeoylquinic acids. Nitrogen starvation significantly increased the contents of all these compounds and the PAL activity in leaf and root tissues. Results suggest that hydroponics, with proper manipulation of nutritional factors, might be a suitable system for the production of compounds with health benefits, such as caffeic acid derivatives, in yarrow.     

Distribution of quercetin-3,4′-O-diglucoside,quercetin-4′-O-monoglucoside,and quercetin in different parts of the onion bulb (Allium cepa L.) influenced by genotype

Flavonoids have gained much attention because of their proposed positive effects for human health. Onions are a rich source of flavonoids, consisting mainly of the major flavonols quercetin-3,4′-O-diglucoside (QDG) and quercetin-4′-O-monoglucoside (QMG) in the bulb and the aglycone quercetin in the outer scales. In this study, distribution of these three flavonoids was determined in 16 onion cultivars (Allium cepa) using HPLC–DAD. Three different parts of the onion bulb, the inner layers, the middle layers and the outer scales were analysed. The analysis showed varietal differences in the selected onion cultivars. The cultivars with the highest total flavonoid content were the red skinned ‘Red Baron’ and the yellow skinned cultivars ‘Ailsa Craig’ and ‘Prilep’. The distribution of the total flavonoid content in the different parts of the onion bulb showed the following order: middle layers > outer scales > inner layers. In the inner layers QDG was the major flavonoid, while in the middle layers QDG and QMG were in equal amounts. In the outer scales quercetin was the major flavonoid prior to QMG.