Aromatic potential of Castanea sativa Mill. compared to Quercus species to be used in cooperage

The composition of volatile and semi-volatile compounds of chestnut (Castanea sativa Mill.) was studied and compared to oak wood species frequently used in cooperage (Quercus alba, Quercus petraea, Quercus robur and Quercus pyrenaica) to evaluate its aromatic potential. Chestnut was found to be a suitable wood for use in ageing processes, based on the large, diverse number of detected compounds (e.g., lactones, furanic compounds, terpenes, lignin derivatives and triterpenic compounds). Chestnut wood possessed high levels of volatile phenols and phenolic aldehydes, specifically vanillin and its derivatives. Each wood species exhibited a characteristic, quantifiable composition of volatile compounds, and therefore, the sensorial profile of each wood species is expected to be different. The levels of certain volatile compounds were also useful for discriminating among the studied wood species.     

Effects induced by the nodulation with Bradyrhizobium japonicum on Glycine max (soybean) metabolism and antioxidant potential

This study was conducted in order to assess the effect of the inoculation of Glycine max (soybean) with Bradyrhizobium japonicum on the metabolite profile and antioxidant potential of its aerial parts. Extracts containing phenolic compounds and organic acids were analysed by HPLC–DAD and HPLC–UV, respectively. Volatiles profile was determined by HS-SPME/GC–IT-MS. The antioxidant activity of acidic and methanolic extracts was assessed against DPPH. Nodulation caused by B. japonicum led to an increase in the contents of phenolic compounds and organic acids. The same was observed for volatile compounds, with compounds like linalyl acetate, menthyl acetate and α-farnesene being detected only in inoculated plants. The phenolic extracts showed stronger antioxidant capacity than the organic acid extracts. In addition, extracts from plants nodulated with B. japonicum exhibited significantly higher antioxidant activity than control samples. These findings suggest that the inoculation with nodulating B. japonicum strains may be employed to manipulate the content of interesting metabolites in G. max aerial parts.     

Flavonoids of Zizyphus jujuba L. and Zizyphus spina-christi (L.) Willd (Rhamnaceae) fruits

The ripe edible fruits of jujube, Zizyphus jujuba Miller (syn. Z. sativa Gaertner, Z. vulgaris Lam.) and Christ’s thorn jujube Zizyphus spina-christi (L.) Willd (Rhamnaceae family) were phytochemically investigated, comparing their quali-quantitative flavonoids profile. Twelve compounds from both methanol extracts have been recognized as quercetin, kaempferol, and phloretin derivatives by means of HPLC/ESI-MS analyses. Six major compounds have been purified by Sephadex LH-20 column chromatography followed by HPLC and were characterized using NMR spectroscopy. One C-glycoside, 3′,5′-di-C-β-d-glucosylphloretin, was detected in Z. spina-christi. The quantitative analysis of all compounds was also reported showing a higher content of flavonoids in Z. jujuba.     

Dracaena draco L. fruit: Phytochemical and antioxidant activity assessment

The present study reports for the first time the metabolite profile and antioxidant activity of aqueous extract obtained from Dracaena draco L. fruit. Volatiles profile was determined by HS-SPME/GC-IT-MS, with 9 compounds being identified, distributed by several distinct chemical classes: 1 alcohol, 3 aldehydes, 2 carotenoid derivatives, and 3 terpenic compounds. Aldehydes constituted the most abundant class in this exotic berry, representing 59% of total identified volatile compounds. Phenolics profile was determined by HPLC/DAD and 5 constituents were identified: 5-O-caffeoylquinic, 3,5-O-dicaffeoylquinic, ferulic and sinapic acids, and quercetin-3-O-rutinoside. The major phenolic compound is quercetin-3-O-rutinoside, comprising 42% of the total phenolic content. Organic acids composition was also characterized, by HPLC-UV, and oxalic, citric, l-ascorbic, malic, quinic and shikimic acids were determined. The most abundant is quinic acid, representing 39% of the total organic acid content. The antioxidant potential of this matrix was assessed by (i) reducing power of Fe³⁺/ferricyanide complex, (ii) scavenging effect on DPPH free radicals, and (iii) ability to inhibit the 2,2´-azobis(2-amidinopropane) dihydrochloride (AAPH)-induced oxidative hemolysis in human erythrocytes. Strawberry (Fragaria × ananassa Duch. cv. Camarosa) extract was used for comparison purposes. All assay models showed remarkable concentration dependent antioxidant activity, reducing power and radical scavenging efficiency for D. draco fruit, being invariably higher than that of strawberry extract. This is the first report showing that D. draco fruit is a promising new antioxidant agent.     

Profile of volatile compounds during papaya juice fermentation by a mixed culture of Saccharomyces cerevisiae and Williopsis saturnus

This study investigated the formation and utilization of volatile compounds during papaya juice fermentation by a mixed culture of Saccharomyces cerevisiae and Williopsis saturnus. Time-course papaya juice fermentations were carried out using pure cultures of S. cerevisiae var. bayanus R2 and W. saturnus var. mrakii NCYC2251 and a mixed culture of the two yeasts at a ratio of 1:1000 (R2:NCYC2251). Changes in S. cerevisiae cell population, Brix, sugar consumption and pH were similar in the mixed culture and in the S. cerevisiae monoculture. There was an early growth arrest of W. saturnus in the mixed culture fermentation. A range of volatile compounds were produced during fermentation including fatty acids, alcohols, aldehydes and esters and some volatile compounds including those initially present in the juice were utilized. The mixed culture fermentation of S. cerevisiae and W. saturnus benefited from the presence of both yeasts, with more esters being produced than the S. cerevisiae monoculture and more alcohols being formed than the W. saturnus monoculture. The study suggests that papaya juice fermentation with a mixed culture of S. cerevisiae and W. saturnus may be able to result in the formation of more complex aroma compounds and higher ethanol level than those using single yeasts.     

Phytochemical profiles and inhibitory effect on free radical-induced human erythrocyte damage of Dracaena draco leaf: A potential novel antioxidant agent

The present study reports for the first time the metabolite profile and antioxidant activity of aqueous extract obtained from Dracaena draco L. leaf. Volatiles profile was determined by HS-SPME/GC-IT-MS, with 34 compounds being identified, distributed by distinct chemical classes: 2 alcohols, 5 aldehydes, 16 carotenoid derivatives and 8 terpenic compounds. Carotenoid derivative compounds constituted the most abundant class in leaf (representing 45% of total identified compounds). Phenolics profile was determined by HPLC/DAD and 9 constituents were identified: 2 hydroxycinnamic acid derivatives – 5-O-caffeoylquinic and 3,5-O-dicaffeoylquinic acids; 4 hydroxycinnamic acids – caffeic, p-coumaric, ferulic and sinapic acids and 3 flavonol glycosides – quercetin-3-O-rutinoside, kaempferol-3-O-glucoside and kaempferol-3-O-rutinoside. The most abundant phenolic compound is quercetin-3-O-rutinoside (representing 50.2% of total polyphenols). Organic acids composition was also characterised, by HPLC–UV and oxalic, citric, malic and fumaric acids were determined. Oxalic and citric acids were present in higher amounts (representing 47%, each). The antioxidant potential of this material was assessed by the ability to protect against free radical-induced biomembrane damage, using human erythrocyte as in vitro model. Leaf extract strongly protected the erythrocyte membrane from haemolysis (IC₅₀ of 39 ± 11 μg/ml), in a time- and concentration-dependent manner. This is the first report showing that D. draco leaf is a promising antioxidant agent.     

Polyphenolic composition and content in the ripe berries of wild Vitis species

To explore wild genetic resources for improving fruit and processing quality of cultivated grape cultivars, the polyphenolic composition and content in the ripe berries of 147 grape accessions from 16 Vitis species for two consecutive years were characterised. A total of 48 polyphenolic compounds, including 28 anthocyanins, 6 flavonols, 6 flavanols, 6 hydroxycinnamic derivatives, and 2 hydroxybenzoic acids, were identified via HPLC-MS and quantified by HPLC-DAD. These wild grape species had unique presence of abundant di-glucoside derivatives of anthocyanins. In addition, anthocyanins in most wild species were predominantly nonacylated. The mean contents for anthocyanins, flavanols, flavonols, hydroxycinnamic derivatives, and hydroxybenzoic acids were 9.610, 0.769, 0.093, 0.441 and 0.027 mg g⁻¹ FW, respectively. They were about 2 to 10 folds higher than their respective counterparts in the most widely cultivated grape species Vitis vinifera. As expected, most of these groups of compounds were correlated negatively with berry weight, but positively with the content of total soluble solids.     

Organic acids in two Portuguese chestnut (Castanea sativa Miller) varieties

The organic acids composition of two different chestnut (Castanea sativa Miller) varieties (Judia and Longal) were determined by HPLC/UV. In order to check the influence of the processing over these compounds, samples treated in three distinct manners (roasted, boiled and fried) were also analysed. The results showed that chestnut is characterized by the presence of seven organic acids: oxalic, cis-aconitic, citric, ascorbic, malic, quinic and fumaric acids. The organic acid quantitative profile allows the distinction of the two varieties. Longal variety samples presented higher organic acids contents than those from Judia variety. The contents of the pair malic plus quinic acids may be useful for the discrimination of the two varieties. Roasting, boiling and frying procedures lead to significant reduction of total organic acids contents.     

Antioxidative properties and phytochemical composition of Ballota nigra infusion

The ability of Ballota nigra (Lamiaceae) infusion to act as a scavenger of DPPH radical, reactive oxygen species (superoxide radical, hydroxyl radical, hypochlorous acid) and nitric oxide was investigated. The tested infusion mainly exhibited a potent scavenging effect on DPPH, nitric oxide and superoxide radicals. In hydroxyl radical assay a potent pro-oxidant activity was noticed. No effect was found against hypochlorous acid. A phytochemical study was also undertaken, and seven phenolic compounds (chlorogenic, caffeic and caffeoylmalic acids, ballotetroside, forsythoside B, verbascoside and allysonoside) and eight organic acids (oxalic, aconitic, citric, ascorbic, malic, quinic, shikimic and fumaric acids) were identified and quantified by HPLC/DAD and HPLC/UV, respectively. Forsythoside B and quinic acid were revealed to be the main compounds in this infusion.     

Flavonols, betacyanins content and antioxidant activity of cactus Opuntia macrorhiza fruits

Flavonols, betacyanins content and antioxidant activity of red-purple cactus Opuntia macrorhiza fruits, a promising cactus pear species, were evaluated in comparison to the well known cactus pear fruits of Opuntia ficus-indica. Flavonol profile was evaluated by HPLC-DAD prior to and after enzymatic hydrolysis (glycosides vs. aglycons). In addition betacyanins, responsible for the purple to red color of cactus pear fruits were also estimated and compared to Beta vulgaris ssp. (roots) and red O. ficus-indica fruits. In all cases, cactus fruit pulps showed no flavonols at all. While different derivatives of isorhamnetin glycosides were found in O. ficus-indica fruit's peel, isorhamnetin-3-O-rutinoside was the only compound in O. macrorhiza fruit. Correspondingly, antioxidant activity assays showed a high antioxidant activity of both, O. macrorhiza fruit's peel and pulp. With regard to betacyanins, O. macrorhiza fruit's peel and pulp provide a deep red-purple color, whose average impact is higher compared to red beet (B. vulgaris spp.) and about 8-fold higher than red fruits from O. ficus-indica. Supporting these results, estimation of color attributes (L*, a*, b*, C and H°) showed also a high color impact of both O. macrorhiza fruit's peel and pulp.     

Green processes based on the extraction with pressurized fluids to obtain potent antimicrobials from Haematococcus pluvialis microalgae

In the present work, the antimicrobial activity of different pressurized liquid extracts obtained from Haematococcus pluvialis microalga was tested against several microorganisms of importance for the food industry (Escherichia coli, Staphylococcus aureus, Candida albicans and Aspergillus niger). Extractions were performed with hexane and ethanol at four different temperatures (50, 100, 150 and 200 °C) for 20 min. The results showed that extracts obtained with both solvents (hexane and ethanol) from the green motile cells of the microalgae (green phase) presented a low antimicrobial activity against all the microorganisms tested. However, the antimicrobial activity of the extracts obtained from the red hematocysts without flagella (red phase) was totally different depending on the solvent used for the extraction. Hexane extracts showed an antimicrobial activity quite similar to that obtained with the green microalgae, while the antimicrobial activity of ethanol extracts was much higher. This fact seems to indicate that compounds related to antimicrobial activity of this microalga are found in higher quantities in the red phase of the microalgae and could be relatively polar compounds. Moreover, ethanol extracts from the red phase obtained at 100 °C presented the highest antimicrobial activity. In order to identify the compounds responsible for the antimicrobial activity, a GC-MS characterization of the extracts obtained with both hexane and ethanol at 100 °C, for Haematococcus pluvialis in the green and red phases was also performed. Therefore, the highest antimicrobial activity of the ethanol extract corresponding to red Haematococcus can be associated with the presence in this extract of short-chain fatty acids, which have been previously described to possess antimicrobial activity.     

Comprehensive analysis of Phyteuma orbiculare L., a wild Alpine food plant

Plants which have been traditionally eaten by the alpine population may provide new opportunities for agricultural development in mountain regions. In this context we have investigated the chemical composition of Phyteuma orbiculare (Campanulaceae), a perennial herb whose leaves have been eaten as salad by rural populations in Valais (Switzerland). Extracts of different polarities were subjected to comprehensive metabolite profiling using a dereplication platform combining HPLC–PDA-MS, and offline NMR analysis. Twenty-three compounds, including various phenolic glycosides, a new dimeric phenylpropanoid glucoside, saponins, and fatty acids were identified online, or after targeted isolation. Selected phenolic constituents were quantitatively assessed by HPLC–PDA analysis. In addition, substances relevant for nutrition, such as β-carotene, fatty acids, ascorbic acid and minerals were quantified in leaves and flowers. The antioxidant capacity was determined with an ORAC assay, and total phenolic compounds were quantified. Finally, the phytochemical profile was compared to that of the related species P. spicatum, P. hemisphaericum and P. ovatum.     

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.     

Phytochemical composition and thermal stability of two commercial açai species, Euterpe oleracea and Euterpe precatoria

Açai fruit are native to the Amazon region of South America and two predominant species are commercially exported as fruit pulps for use in food and beverage applications. Detailed characterisation of the polyphenolic compounds present in the de-seeded fruits of Euterpe oleracea and Euterpe precatoria species were conducted by HPLC–ESI–MSⁿ analyses and their thermal stability and overall influence on antioxidant capacity were determined. Anthocyanins were the predominant polyphenolics in both E. oleracea (2247 ± 23 mg/kg) and E. precatoria (3,458 ± 16 mg/kg) species, and accounted for nearly 90% of the trolox equivalent antioxidant capacity in both E. oleracea (87.4 ± 4.4 μmol TE/g) and E. precatoria (114 ± 6.9 μmol TE/g) fruits. Various flavones, including homoorientin, orientin, taxifolin deoxyhexose and isovitexin; various flavanol derivatives, including (+)-catechin, (−)-epicatechin, procyanidin dimers and trimers, and phenolic acids, including protocatechuic, p-hydroxybenzoic, vanillic, syringic and ferulic acids, were also present in both species. Thermal stability of these compounds was evaluated, following a thermal holding cycle (80 °C for up to 60 min) in the presence and absence of oxygen. Both species experienced only minor changes (<5%) in non-anthocyanin polyphenolic contents during all thermal processes whereas 34 ± 2.3% of anthocyanins in E. oleracea and 10.3 ± 1.1% of anthocyanins in E. precatoria were lost under these conditions, regardless of the presence of oxygen. Proportional decreases (10–25%) in antioxidant capacity accompanied the anthocyanin changes. Results suggest that both açai species are characterised by similar polyphenolic profiles, comparable antioxidant capacities, yet only moderate phytochemical stability during heating.     

Volatile composition of red clover (Trifolium pratense L.) forages in Portugal: The influence of ripening stage and ensilage

The volatile organic compounds (VOCs) of three different red clover (Trifolium pratense L.) forages, fresh plant, hay and silage, were analyzed using GC and GC/MS. Comparing the volatile composition of hay and silage forages of red clover with the corresponding green plant, the effects of ripening and postharvest secondary metabolism can be noticed in hay and in ensilage. In hay, reductions of the percentages of alcohols, such as 3-methylbutanol and 1-hexanol, of aldehydes and of low boiling point ketones are observed. A sesquiterpene (β-farnesene; ca. 10%) and a phytol degradation product (6,10,14-trimethyl-2-pentadecanone; ca. 12%) were the most abundant compounds detected in hay. In silage, as a result of the fermentation of fresh red clover, esters (ca. 46%) are a more representative class of compounds.     

Volatile components of Negroamaro red wines produced in Apulian Salento area

Volatile composition of monovarietal young red wines made from Negroamaro cultivar, an autochthonous grape variety of Vitis vinifera grown exclusively in Salento area (southeast of Italy in Apulia region), was investigated. Volatile compounds were extracted following a solid phase extraction (SPE) method, and then analysed by gas chromatography–mass spectrometry (GC/MS). Results showed a complex aroma profile rich in alcohols, esters and fatty acids, with a minor contribute from aldehydes, lactones, volatile phenols and sulphur compounds. For the first time, aromatic patterns that characterise wines produced from Negroamaro autochthonous grape variety were established, starting a fundamental register of typicity and geographical identity of Apulians wines. Statistical data analysis techniques (Principal component analysis (PCA) and ANOVA) showed the structure of the experimental data and the significant differences for each compound in the different wines.     

Anthraquinone profiles, antioxidant and antimicrobial properties of Frangula rupestris (Scop.) Schur and Frangula alnus Mill. bark

Frangula rupestris and Frangula alnus are deciduous shrubs distributed in Balkan Peninsula. While the bark of F. alnus is medicinally widely used, little is known about chemical and biological properties of F. rupestris. In the present study, F. rupestris and F. alnus bark were evaluated for their reducing power, DPPH radical scavenging and chelating activity, as well as antioxidant activity in β-carotene-linoleic acid assay. In addition, phenolic content, anthraquinone profile and antimicrobial activity of F. rupestris and F. alnus bark were determined. The most represented anthraquinone derivatives in F. rupestris and F. alnus bark were physcion (0.11 mg/g) and emodin (2.03 mg/g), respectively. Both species demonstrated excellent antioxidant and antimicrobial activities with MIC values equal or lower than 2.5 mg/mL. The presented research indicates that both species may have health benefits as natural antioxidants and antimicrobial agents for use in functional foods or medicine.     

Study of the bioactive compounds variation during yerba mate (Ilex paraguariensis) processing

Ilex paraguariensis St. Hil. (Aquifoliaceae) (yerba mate) is one of the most used plant species in South America due to its nutritional and medicinal properties. The industrial processing involves different stages (green leaves, zapecado, drying, forced or natural aging) which can modify the qualitative and quantitative composition and the pharmacological activities. In this work, the main compounds, caffeoyl derivatives (caffeic acid, mono- and dicaffeoylquinic acids), methylxanthines (caffeine and theobromine) and flavonoids (rutin, quercetin and kaempferol) were studied by HPLC in extracts obtained by decoction of samples of a large amount of I. paraguariensis during its industrial process stages. The comparative quantitative analysis of all the samples indicated that those obtained after the zapecado, drying and aging stages possess higher content of biologically active principles when compared with green leaves. No differences were found between the natural and forced aging processes. This is the first complete report on the quantitative variation of the bioactive compounds of I. paraguariensis during each step of the industrial processing. The results obtained in this work provide a guideline for the obtention of extracts enriched in biological principles for the pharmaceutical, food and cosmeceutical industry.     

Chemical and biological variability of hot pepper fruits (Capsicum annuum var. acuminatum L.) in relation to maturity stage

The aim of the present work was to evaluate the chemical composition and the radical-scavenging and antioxidant activities of hot pepper fruits (Capsicum annuum L. var. acuminatum) at three maturity stages (small green, green and red). GC–MS analysis of n-hexane and chloroform fractions showed a different composition between the three stages of ripening. The first stage of maturation (small green) showed the highest radical-scavenging activity (IC₅₀ of 129 μg/ml). Using the bovine brain peroxidation assay, the methanolic extract of green pepper showed significant antioxidant activity (IC₅₀ of 522 μg/ml). Addition of methanolic extract of red and green pepper inhibited oxidation of linoleic acid. Methanolic extract of red pepper showed greater antioxidative potency than the others (IC₅₀ of 3 μg/ml). The different composition of lipophilic compounds and the various amount of phenolics, showed in the three stage of ripening of C. annuum var. acuminatum fruits, modifies the antioxidant activity.