Bioguided isolation and identification of the nonvolatile antioxidant compounds from fennel (Foeniculum vulgare Mill.) waste

A bioguided isolation of an aqueous extract of fennel waste led to the isolation of 12 major phenolic compounds. Liquid chromatography coupled to atmospheric pressure chemical ionization mass spectrometry (LC/UV/APCI-MS) combined with spectroscopic methods (NMR) was used for compound identification. Radical scavenging activity was tested using three methods: DPPH*, superoxide nitro-blue tetrazolium hypoxanthine/xanthine oxidase, and *OH/luminol chemiluminescence. In addition to products described in the literature, eight antioxidant compounds were isolated and identified for the first time in fennel: 3-caffeoylquinic acid, 4-caffeoylquinic acid, 1,5-O-dicaffeoylquinic acid, rosmarinic acid, eriodictyol-7-O-rutinoside, quercetin-3-O-galactoside, kaempferol-3-O-rutinoside, and kaempferol-3-O-glucoside. The structures of eriodictyol-7-O-rutinoside and quercetin-3-O-glucuronide were completely elucidated by two-dimensional NMR experiments. The isolated compounds exhibited a strong antiradical scavenging activity, which may contribute to the interpretation of the pharmacological effects of fennel.     

Changes in antioxidant effects and their relationship to phytonutrients in fruits of sea buckthorn (Hippophae rhamnoides L.) during maturation

Different fractions of sea buckthorn fruits were investigated for antioxidant activity and its relationship to different phytonutrients. Capacity to scavenge radicals of the crude extract, like the phenolic and ascorbate extracts, decreased significantly with increased maturation. The changes were strongly correlated with the content of total phenolics and ascorbic acid. Antioxidant capacity of the lipophilic extract increased significantly and corresponded to the increase in total carotenoids. The phenolic fractions made a major contribution to the total antioxidant capacity due to the high content of total phenolics. The lipophilic fractions were most effective if the comparison was based on the ratio between antioxidant capacity and content of antioxidants. The crude extract of fruits showed the highest inhibitory effect in both 2,2-azobis(2,4-dimethylvaleronitrile) (AMVN) and ascorbate-iron induced lipid peroxidations. The aqueous and ascorbate-free extracts showed higher inhibition in the AMVN assay, but lower inhibition in ascorbate-iron induced peroxidation, than the lipophilic extract.     

Effect of drying of figs (Ficus carica L.) on the contents of sugars, organic acids, and phenolic compounds

Fresh figs were subjected to two different drying processes: sun-drying and oven-drying. To assess their effect on the nutritional and health-related properties of figs, sugars, organic acids, single phenolics, total phenolics, and antioxidant activity were determined before and after processing. Samples were analyzed three times in a year, and phenolic compounds were determined using high-performance liquid chromatography coupled with mass spectrometry (HPLC-MS). In figs, monomer sugars predominate, which is important nutritional information, and the content of sugars as well as organic acids in fresh figs was lower than in dried fruits. However, the best sugar/organic acid ratio was measured after the sun-drying process. Analysis of individual phenolic compounds revealed a higher content of all phenolic groups determined after the oven-drying process, with the exception of cyanidin-3-O-rutinoside. Similarly, higher total phenolic content and antioxidant activity were detected after the drying process. With these results it can be concluded that the differences in analyzed compounds in fresh and dried figs are significant. The differences between the sun-dried and oven-dried fruits were determined in organic acids, sugars, chlorogenic acid, catechin, epicatechin, kaempferol-3-O-glucoside, luteolin-8-C-glucoside, and total phenolic contents. The results indicate that properly dried figs can be used as a good source of phenolic compounds.     

Antioxidant capacity of oat (Avena sativa L.) extracts. 2. In vitro antioxidant activity and contents of phenolic and tocol antioxidants

Oat milling fractions were examined for concentrations of total phenolics, tocols, and phenolic acids and in vitro antioxidant activity to determine their potential as dietary antioxidants. Methanolic extracts of pearling fractions, flour and aspirations from flaking, and trichomes had high, intermediate, and low antioxidant activities, respectively, evaluated by the beta-carotene bleaching method. Pearling fractions were also highest in total phenolics and tocols. p-Hydroxybenzoic acid, vanillic acid, caffeic acid, vanillin, p-coumaric acid, and ferulic acid were identified and quantified by HPLC. Three avenanthramides and an unidentified ferulate derivative were also detected. Total phenolic content was significantly correlated with antioxidant activity, and regression equations that predicted antioxidant activity from phenolic and tocol concentrations were calculated. Antioxidant activity, evaluated by beta-carotene bleaching, was correlated with measures of oxygen radical absorbance capacity and low-density lipoprotein oxidation. These data indicate a potential for oat products, especially those enriched in outer layers of the groat, to contribute to dietary intakes of antioxidant phytonutrients.     

In vitro gastrointestinal digestion study of broccoli inflorescence phenolic compounds, glucosinolates, and vitamin C

Broccoli (Brassica oleracea L. var. italica cv. Marathon) inflorescences are a good source of bioactive compounds, such as phenolics (flavonoids and hydroxycinnamoyl derivatives), glucosinolates, and vitamin C. In this work, these health-promoting compounds were submitted to digestion under in vitro gastrointestinal conditions (pH, temperature, enzyme, and chemical conditions). This technique differentiated among the compounds associated with macromolecules in soluble and insoluble form and those that are freely soluble. In addition, it evaluates the chemical stability of the broccoli compounds under simulated physiological conditions. The gastric digestion of broccoli caused high losses in glucosinolates (69% loss), whereas phenolics and vitamin C presented higher stability under these conditions. Thus, there were no losses in flavonoids, a 7% loss of vitamin C, and a variable rate of loss (6-25%) in hydroxycinnamic acid derivatives. The stability of all of the compounds was affected by the in vitro intestinal conditions. Under the in vitro conditions, flavonoids and hydroxycinnamoyl acid derivatives were of low availability, due to their significant losses under these conditions, at the end of the experiment (84 and 80% loss, respectively). Vitamin C was the metabolite that showed the greater decrease after intestinal digestion (91% loss). Regarding the remaining glucosinolates, these compounds presented higher stability under intestinal conditions, rendering an availability similar to that found for phenolics (75% loss). Therefore, broccoli components were affected by gastric and/or intestinal conditions depending on the type of compound. Thus, glucosinolates were mainly degraded by gastric conditions, whereas phenolic compounds and vitamin C were degraded by intestinal conditions.     

Characterization of cyanidin- and quercetin-derived flavonoids and other phenolics in mature saskatoon fruits (Amelanchier alnifolia Nutt.)

In order to further characterize the anthocyanins, flavonols, and other phenolics present in mature saskatoon ( Amelanchier alnifolia Nutt.) fruit, extracts were characterized using high-performance liquid chromatography, gas chromatography, and liquid chromatography-mass spectrometry. Cyanidin 3-O-galactoside, cyanidin 3-O-glucoside, cyanidin 3-O-arabinoside, and cyanidin 3-O-xyloside were identified as the four major anthocyanins in the mature fruit. The quercetin-derived flavonols, quercetin 3-O-glucoside, quercetin 3-O-galactoside, quercetin 3-O-arabinoside, quercetin 3-O-xyloside, quercetin 3-O-arabinoglucoside, quercetin 3-O-robinobioside, and quercetin 3-O-rutinoside were also identified in mature fruit extracts. In addition, two chlorogenic acid isomers (hydroxycinnamates), 3-O-caffeoylquinic acid and 5-O-caffeoylquinic acid were detected. The total content of the anthocyanin-, flavonol-, and hydroxycinnamate-type phenolics detected in mature 'Smoky' saskatoon fruit was 140, 25, and 96 mg/100 g fresh weight, respectively. These data further our knowledge of the phenolic composition of mature saskatoon fruit, and as anthocyanins, flavonols, and hydroxycinnamates exhibit antioxidant activities, the presence and levels of these classes of phenolics will aid in the understanding of the potential health-beneficial effects of saskatoon fruits in the human diet.     

Antioxidant and antiradical activities in extracts of hazelnut kernel (Corylus avellana L.) and hazelnut green leafy cover

Phenolic compounds in the aqueous systems were extracted, from hazelnut kernel (HK) and hazelnut green leafy cover (HGLC), with 80% (v/v) ethanol (HKe and HGLCe) or 80% (v/v) acetone (HKa and HGLCa). The extracts were examined for their phenolic and condensed tannin contents and phenolic acid profiles (free and esterified fractions) as well as antioxidant and antiradical activities by total antioxidant activity (TAA), antioxidant activity in a beta-carotene-linoleate model system, scavenging of DPPH (2,2-diphenyl-1-picrylhydrazyl) radical, and reducing power. Significant differences (p < 0.05) in the contents of total phenolics, condensed tannins, and TAA existed among the extracts that were examined. HGLCa extract had the highest content of total phenolics (201 mg of catechin equivalents/g of extract), condensed tannins (542 mg of catechin equivalents/g of extract), and TAA (1.29 mmol of Trolox equivalents/g of extract) followed by HGLCe, HKa, and HKe extracts, respectively. Five phenolic acids (gallic acid, caffeic acid, p-coumaric acid, ferulic acid, and sinapic acid) were tentatively identified and quantified, among which gallic acid was the most abundant in both free and esterified forms. The order of antioxidant activity in a beta-carotene-linoleate model system, the scavenging effect on DPPH radical, and the reducing power in all extracts were in the following order: HGLCa > HGLCe > HKa > HKe. These results suggest that both 80% ethanol and acetone are capable of extracting phenolics, but 80% acetone was a more effective solvent for the extraction process. HGLC exhibited stronger antioxidant and antiradical activities than HK itself in both extracts and could potentially be considered as an inexpensive source of natural antioxidants.     

Free and Bound Phenolic Acids and Total Phenolics in Black,Blue, and Yellow Barley and Their Contribution to Free Radical Scavenging Capacity

Barley is considered a healthy food because of its high content of β‐glucan and phenolic antioxidants. In the current study, 28 black, blue, and yellow barleys were investigated in terms of their composition of free and bound phenolic acids and 2,2‐diphenyl‐1‐picrylhydrazyl radical scavenging capacity. Free phenolics were based on aqueous methanol extraction, whereas bound phenolics were extracted following alkaline hydrolysis. Phenolics were then separated and quantified by liquid chromatography and the Folin–Ciocalteu method. Significant differences were observed between the three barley color groups, and within each color group a wide range of phenolics concentrations existed. Ferulic acid was the predominant phenolic acid in free and bound extracts, followed by p‐coumaric acid in all the barleys investigated. Total phenols content and individual phenolic acids strongly correlated with free radical scavenging capacity of barley. Black and blue barley were found to be related and distinct from yellow barley. The results showed significant variations in phenolics among barleys, with a potential for the development of barley grains with high content of phenolic compounds as antioxidant potential.     

Antioxidant Activity and Phenolic Contents of Oat Groats and Hulls

Research was initiated to measure antioxidant activity of extracts from oat (Avena sativa L.) groats and hulls and the concentrations of phenolic substances that may contribute to antioxidant activity. Antioxidant activity of ethanolic extracts of four cultivars was evaluated by an in vitro assay that measures the inhibition of coupled autoxidation of linoleic acid and β-carotene. Total phenolic content was determined using Folin and Ciocalteau's phenol reagent and was expressed as gallic acid equivalents. Phenolic compounds were separated by reversed-phase HPLC and detected at 290 nm. Peaks were identified by comparing retention times and spectra with known standards and verified with internal standards. Groats had significantly higher antioxidant activity than hulls. For two cultivars, total phenolic content was similar in groats and hulls, whereas one cultivar had higher and another lower total phenolic content in groats than hulls. Ten phenolic compounds were separated and identified in extracts, and one flavan-3-ol and three avenanthramides were tentatively identified. The concentrations of many of these compounds differed among cultivars and between fractions. In general, caffeic acid and the avenanthramides were predominantly found in groats, whereas many of the other phenolics were present in greater concentrations in hulls.     

Valorization of cauliflower (Brassica oleracea L. var. botrytis) by-products as a source of antioxidant phenolics

The present study reports the development of two extraction protocols, with potential industrial applicability, to valorize cauliflower (Brassica oleracea L. var. botrytis) byproducts as a source of antioxidant phenolics. In addition, the nonionic polystyrene resin Amberlite XAD-2 was used to obtain purified extracts. The extract yield, phenolic content, phenolic yield, and correlation between the antioxidant activity and the phenolic content were studied. The water and ethanol protocols yield a phenolic content of 33.8 mg/g freeze-dried extract and 62.1 mg/g freeze-dried extract, respectively. This percentage increased considerably when the extracts were purified using Amberlite XAD-2 yielding a phenolic content of 186 mg/g freeze-dried extract (water extract) and 311.1 mg/g freeze-dried extract (ethanol extract). Cauliflower byproduct extracts showed significant free radical scavenging activity (vs both DPPH(*) and ABTS(*)(+) radicals), ferric reducing ability (FRAP assay), and capacity to inhibit lipid peroxidation (ferric thiocyanate assay). In addition, the antioxidant activity was linearly correlated with the phenolics content. The results obtained indicate that the cauliflower byproducts are a cheap source of antioxidant phenolics very interesting from both the industrial point of view and the possible usefulness as ingredients to functionalize foodstuffs.     

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.     

Phenolic profile, antioxidant property, and anti-influenza viral activity of Chinese quince (Pseudocydonia sinensis Schneid.), quince (Cydonia oblonga Mill.), and apple (Malus domestica Mill.) fruits

To evaluate the phenolic extracts of Chinese quince, quince, and apple fruits, their phenolic profiles, antioxidant properties, and anti-influenza viral activities were investigated. Chinese quince had the largest amount of phenolics consisting mainly of high polymeric procyanidins. Quince had considerable amounts of hydroxycinnamic derivatives mainly composed of 3-caffeoylquinic acid and 5-caffeoylquinic acid and polymeric procyanidins. Apple (cv. Fuji) had the lowest amount of phenolics, mainly 5-caffeoylquinic acid and monomeric and oligomeric procyanidins. The antioxidant functions of Chinese quince and quince phenolic extracts were superior to that of chlorogenic acid standard or ascorbic acid evaluated in both the linoleic acid peroxidation system and the DPPH radical scavenging system. However, those extracts were less effective than apple phenolics or (-)-epicatechin in linoleic acid peroxidation system. On the other hand, Chinese quince phenolics showed the strongest anti-influenza viral activity on the hemagglutination inhibition test.     

Multivariate analysis of tronchuda cabbage (Brassica oleracea L. var. costata DC) phenolics: influence of fertilizers

A field experiment was carried out to investigate the effect of fertilization level on the phenolic composition of tronchuda cabbage ( Brassica oleracea L. var. costata DC) external and internal leaves. Eight different plots were constituted: a control without fertilization, one with organic matter, and six experiments with conventional fertilizers (nitrogen, boron, and sulfur, two levels each). The phenolic compounds were analyzed by reversed-phase HPLC-DAD. External and internal leaves revealed distinct qualitative composition. In the internal leaves were found 15 phenolics (5 kaempferol and 10 cinnamic acid derivatives), whereas the external leaves presented 3- p-coumaroylquinic acid and 13 kaempferol derivatives. Principal component analysis (PCA) was applied to assess the relationships between phenolic compounds, agronomical practices, and harvesting time. Samples obtained with conventional practices were quite effectively separated from organic samples, for both types of leaves. In general, samples developed without any fertilization presented the highest phenolics amounts: external and internal leaves contained 1.4- and 4.6-fold more phenolic compounds than the ones that received conventional fertilizer, respectively, and the internal leaves presented 2.4 times more phenolics than the ones grown with organic amendment. Additionally, samples from organic production exhibited higher total phenolics content than those from conventional practices, collected at the same time. Samples harvested first were revealed to be distinct from the ones collected later. The results show that it is possible to grow tronchuda cabbage without excess fertilizers, with highest amounts of phenolics and reduced environment contamination.     

Chemical characterization and biological effects of Sicilian Opuntia ficus indica (L.) mill. Fruit juice: antioxidant and antiulcerogenic activity

The juice of whole fruits of Sicilian cultivars of prickly pear (Opuntia ficus indica (L.) Mill.) was investigated, and the contents of ascorbic acid, total polyphenols, and flavonoids were determined. In the juice, ferulic acid was the chief derivative of hydroxycinnamic acid and the mean concentration of total phenolic compounds was 746 microg/mL. The flavonoid fraction, analyzed by high-performance liquid chromatography-diode array detection, consisted of rutin and isorhamnetin derivatives. The juice showed antioxidant activity in the DPPH(*) test, probably due to the phenolic compounds that are effective radical scavengers. The preventive administration of the juice inhibited the ulcerogenic activity of ethanol in rat. Light microscopy observations showed an increase in mucus production and the restoration of the normal mucosal architecture. The juice is nutritionally interesting, and its dietary intake could provide protection against oxidative damage.     

Separation, characterization, and quantitation of phenolic acids in a little-known blueberry (Vaccinium arctostaphylos L.) fruit by HPLC-MS

The aim of this study was the qualitative and quantitative determination of free, ester, glycoside, and ester-bound phenolic acids in the blueberry (Vaccinium arctostaphylos L.) fruit. A method for the determination of the profile of phenolic acids of four different phenolic fractions in the fruit was developed using high-performance liquid chromatography-mass spectrometry (HPLC-MS). Thirteen compounds (gallic, protocatechuic, p-hydroxybenzoic, m-hydroxybenzoic, gentisic, chlorogenic, p-coumaric, caffeic, ferulic, syringic, sinapic, salicylic, and trans-cinnamic acids) were identified and quantified in the berry. These experimental results showed that the predominant phenolic acid in the fruit of V. arctostaphylos is caffeic acid in free and insoluble ester-bound forms and p-coumaric acid in soluble ester and glycoside forms. Seven phenolic acids were identified as hydroxybenzoic acid derivatives (HBAs) and four as hydroxycinnamic acid derivatives (HCAs). Total content of HBAs and HCAs in the four phenolic fractions constituted 30.1 and 69.9% of the free, 27.9 and 72.1% of the ester, 24.7 and 75.3% of the glycoside, and 51.7 and 48.3% of the ester-bound forms, respectively. Total phenolics as the sum of individual phenolic acids identified is 698.5 ng/g of fresh weight (fw) for the free, 3399.2 ng/g of fw for the ester, 3522.1 ng/g of fw for the glycoside, and 3671.6 ng/g of fw for the ester-bound phenolic fractions. The present results were compared with reported levels of phenolic acids in the fruits of different Vaccinium species. These data suggest that the fruit can be considered as a potentially good dietary source of phenolic acids.     

Solid foodstuff supplemented with phenolics from grape: antioxidant properties and correlation with phenolic profiles

Osmotic dehydration was assessed as an operation for supplementing a solid foodstuff (a gel was used as the model food) with grape phenolics from a concentrated red grape must to increase its antioxidant properties. The model food was processed for up to 24 h, and the osmotic pressure was adjusted by diluting the concentrated red grape must. In all conditions tested, low molecular weight phenolics (相似文献   

Anti-inflammatory effects of caper (Capparis spinosa L.) fruit aqueous extract and the isolation of main phytochemicals

Caper (Capparis spinosa L.) fruits have been used as food as well as folk medicine in the treatment of inflammatory disorders, such as rheumatism. The present study was carried out to study the anti-inflammatory activities of C. spinosa L. fruit (CSF) aqueous extract and to isolate main phytochemicals from its bioactive fractions. The CSF aqueous extract were separated into three fractions (CSF1-CSF3) by macroporous adsorption resins. The fractions CSF2 and CSF3 effectively inhibited the carrageenan-induced paw edema in mice. Systematic fractionation and isolation from CSF2+3 led to the identification of 13 compounds (1-13). Their chemical structures were elucidated by spectroscopic analyses including nuclear magnetic resonance (NMR) and mass spectrometry (MS) and literature comparisons. Major compounds found in the bioactive fraction CSF2+3 are flavonoids, indoles, and phenolic acids. To our knowledge, 8 of these 13 compounds (1-4, 6-7, 10, and 13) were identified from caper fruits for the first time. The anti-inflammatory effects of these purified compounds are currently under investigation.     

Antioxidant activity and phenolic composition of wild, edible, and medicinal fennel from different Mediterranean countries

Fennel (Foeniculum vulgare Mill.) is a typical aromatic plant of the Mediterranean area, long used as a medicinal and spice herb. Fennel is also well-known for its essential oil, which has been extensively studied for many years owing to its commercial importance. In this work, the antioxidant activity and the total phenolic and flavonoid contents, as well as the quantitative determination of individual flavonoids and phenolic acids of wild, edible, and medicinal fennel from different Mediterranean countries, have been determined. The antioxidant activity was measured as the free radical (DPPH), hydroxyl radical, and superoxide anion scavenging activities. Wild fennel was found to exhibit a radical scavenging activity, as well as a total phenolic and total flavonoid content, higher than those of both medicinal and edible fennels.     

Comparison of antioxidant activity, anthocyanins, carotenoids, and phenolics of three native fresh and sun-dried date (Phoenix dactylifera L.) varieties grown in Oman

Fresh and sun-dried dates of three native varieties from Oman, namely, Fard, Khasab, and Khalas, were examined for their antioxidant activity and total contents of anthocyanins, carotenoids, and phenolics, as well as free and bound phenolic acids. All results are expressed as mean value +/- standard deviation (n = 3) on a fresh weight basis. Fresh date varieties were found to be a good source of antioxidants (11687-20604 micromol of Trolox equiv/g), total contents of anthocyanins (0.24-1.52 mg of cyanidin 3-glucoside equiv/100 g), carotenoids (1.31-3.03 mg/100 g), phenolics (134-280 mg of ferulic acid equiv/100 g), free phenolic acids (2.61-12.27 mg/100 g), and bound phenolic acids (6.84-30.25 mg/100 g). A significant (p < 0.05) amount of antioxidants and carotenoids was lost after sun-drying of dates, whereas the total content of phenolics and free and bound phenolic acids increased significantly (p < 0.05). Anthocyanins were detected only in fresh dates. Date varieties had different levels and patterns of phenolic acids. Four free phenolic acids (protocatechuic acid, vanillic acid, syringic acid, and ferulic acid) and nine bound phenolic acids (gallic acid, protocatechuic acid, p-hydroxybenzoic acid, vanillic acid, caffeic acid, syringic acid, p-coumaric acid, ferulic acid, and o-coumaric acid) were tentatively identified. Of the date varieties studied, Khalas, which is considered to be premium quality, had higher antioxidant activity, total carotenoids, and bound phenolic acids than other varieties. These results suggest that all date varieties serve as a good source of natural antioxidants and could potentially be considered as a functional food or functional food ingredient, although some of their antioxidant constituents are lost during sun-drying.     

Plant phenolics affect oxidation of tryptophan

The effect of berry phenolics such as anthocyanins, ellagitannins, and proanthocyanidins from raspberry (Rubus idaeus), black currant (Ribes nigrum), and cranberry (Vaccinium oxycoccus) and byproducts of deoiling processes rich in phenolics such as rapeseed (Brassica rapa L.), camelina (Camelina sativa), and soy (Glycine max L.) as well as scots pine bark (Pinus sylvestris) was investigated in an H2O2-oxidized tryptophan (Trp) solution. The oxidation of Trp was analyzed with high-performance liquid chromatography using both fluorescence and diode array detection of Trp and its oxidation products. Mechanisms of antioxidative action of the phenolic compounds toward the oxidation of Trp were different as the pattern of Trp oxidation products varied with different phenolic compounds. The antioxidant protection toward oxidation of Trp was best provided with pine bark phenolics, black currant anthocyanins, and camelina meal phenolics as well as cranberry proanthocyanidins.