Dark-Chocolate-Coated BRS Clara Raisins: Phenolic Composition and Sensory Attributes.

Dark chocolate dragée confectionary was made with BRS Clara raisins pre-treated with extra virgin olive oil (EVOO). The evaluation of the changes in the phenolic composition (flavonols, hydrocinnamic acid derivatives (HCADs), stilbenes and flavan-3-ol monomers, dimers, and proanthocyanidins (PAs)) resulting from the covering process showed that the chocolate coating was responsible for an increase in the concentrations of flavan-3-ols and PAs when compared to just the raisins. For the flavonols and HCADs, a reduction in the total concentration of compounds was observed when comparing the dragées to the raisins. Furthermore, there was a strong influence of chocolate in the qualitative profile with the emergence of new compounds (quercetin-3-pentoside, kampfterol-3-rutinoside, p-coumaric acid, and caffeoyl-aspartate). The combination of these ingredients (raisins and chocolate) resulted in a dark chocolate coated raisin (DC) with good sensory acceptance and a more complex phenolic composition that may positively contribute to its functional quality.

Stability of Phenolic Compounds, Antioxidant Activity and Color Parameters in Colored-Flesh Potato Chips.

Potato (Solanum tuberosum) chips are the most consumed snacks worldwide today. Colored potato chips prepared from potato cultivars with red and purple flesh are a novel alternative to traditional potato chips because of their higher phenolic compound content, such as anthocyanins and hydroxycinnamic acid derivatives (HCADs), which might make these chips healthier compared with traditional chips. There is little information on the stability of these compounds. In this study, the nutritional value of these chips was evaluated by determining phenolic profiles, antioxidant activity and color parameters with liquid chromatography diode array and mass spectrometry detection (HPLC-DAD-ESI-MS/MS) and spectrophotometric methods during storage for four months. Five anthocyanins and three HCADs were detected, with the latter compounds being the most abundant, with concentrations on average between the first (97.82 mg kg-1) and the last (31.44 mg kg-1) week of storage. Similar trends were observed in antioxidant activity and stability, with the CUPRAC method showing the highest response among all the methods employed. The color indices were stable throughout the storage time. Based on these results, colored-flesh potato chips are an optimal alternative for consumption because of their high retention of phenolic compounds and antioxidant activity during storage, providing potential benefits to human health.

Characterization of polyphenols in the methanol leaf extract of Bathysa gymnocarpa (Rubiaceae) by HPLC-DAD-ESI-MS/MS.

The species Bathysa gymnocarpa K.Schum is a tree belonging to the Rubiaceae family, endemic in Brazil. So far, there are reports neither of phytochemical work nor of biological evaluation of it. The analysis by High Performance Liquid Chromatography coupled to a Diode Array Detector and a tandem Mass Spectrometer with an Electrospray Ionization source (HPLC-DAD-ESI-MS/MS) of its crude extract allowed to characterize in a complex mixture, without isolation, fourteen compounds, being two as cinnamic acid derivatives, and the others as mono-, di- and triglycosilated derivatives of the flavonols quercetin and kaempferol. These compounds are reported for the first time in Bathysa spp.

Phenolic composition of jussara (Euterpe edulisMartius) from Minas Gerais and Espírito Santo, Brazil, determined by high performance liquid chromatography coupled to diode array detection and electrospray ionization tandem mass spectrometry (HPLC-DAD-ESI-MS) / Composição fenólica de Jussara (Euterpe edulisMartius) de Minas Gerais e Espírito Santo, Brasil, determinada por cromatografia líquida de alta eficiência acoplada à detecção de arranjo de diodos e espectrometria de massa contendo sistema de ionização por eletrospray (HPLC-DAD-ESI MS/MS)

ABSTRACT: This research assessed the phenolic composition of Jussara pulp from the Brazilian states of Minas Gerais (MG) and Espírito Santo (ES) using HPLC-DAD-MS/MS. Seventeen anthocyanins were detected in fruits, derived from cyanidin, pelargonidin and peonidin. Among the non-anthocyanic phenolic compounds, flavonols (kaempferol, quercetin and isorhamnetin derivatives), flavan-3-ols (catechin, epicatechin, B-type procyanidins and unknown dimers) and resveratrol in its glycosylated form have been identified. Catechin (32.41-60.56 mg 100g-1) and epicatechin (18.86-40.92 mg 100g-1) were the main flavan-3-ols present in the fruits. The samples showed small concentrations of resveratrol glycosides (0.02-0.91 mg 100g-1). The analytical methodology used (HPLC-DAD-ESI-MS/MS) permitted the identification of newly reported compounds in this fruit.

RESUMO: O objetivo desta pesquisa foi avaliar a composição fenólica da polpa de Jussara dos Estados brasileiros de Minas Gerais (MG) e Espírito Santo (ES) usando HPLC-DAD-MS / MS. Dezessete antocianinas foram detectadas, dentre elas, derivadas de cianidina, pelargonidina e peonidina. Dentre os compostos fenólicos não antociânicos, foram identificados flavonóis (derivados de caempferol, quercetina e isorhamnetina), flavan-3-ols (catequina, epicatequina, procianidinas do tipo B e dímeros desconhecidos) e resveratrol em sua forma glicosilada. Catequina (32,41-60,56 mg 100g-1) e epicatequina (18,86-40,92 mg 100g-1) foram os principais flavan-3-óis presentes nas frutas. As amostras apresentaram pequenas concentrações de glicosídeos resveratrol (0,02-0,91 mg 100g-1). A metodologia analítica utilizada (HPLC-DAD-ESI-MS / MS) permitiu a identificação de novos compostos relatados presentes na composição da polpa de Jussara.

Noticeable Quantities of Functional Compounds and Antioxidant Activities Remain after Cooking of Colored Fleshed Potatoes Native from Southern Chile.

The effect of cooking on the concentrations of phenolic compounds and antioxidant activities in 33 colored-fleshed potatoes genotypes was evaluated. The phenolic profiles, concentrations, and antioxidant activity were evaluated with a liquid chromatography diode array detector coupled to a mass spectrometer with an electrospray ionization interface (HPLC-DAD-ESI-MS/MS). Eleven anthocyanins were detected; in the case of red-fleshed genotypes, these were mainly acyl-glycosides derivatives of pelargonidin, whereas, in purple-fleshed genotypes, acyl-glycosides derivatives of petunidin were the most important. In the case of the purple-fleshed genotypes, the most important compound was petunidin-3-coumaroylrutinoside-5-glucoside. Concentrations of total anthocyanins varied between 1.21 g kg-1 in fresh and 1.05 g kg-1 in cooked potato and the decreases due to cooking ranged between 3% and 59%. The genotypes that showed the highest levels of total phenols also presented the highest levels of antioxidant activity. These results are of relevance because they suggest anthocyanins are important contributors to the antioxidant activity of these potato genotypes, which is significant even after the drastic process of cooking.

Rapid Characterization of Triterpene Saponins from Zornia brasiliensis by HPLC-ESI-MS/MS.

Zornia brasiliensis Vogel (Leguminosae) is a species popularly known in Brazil as "urinária", "urinana", and "carrapicho", it is popularly used as a diuretic and in the treatment of venereal diseases. A specific methodology to obtain a saponin-enriched fraction and high-performance liquid chromatography coupled with diode array detection, ion trap mass spectrometry, and TOF-MS (HPLC-DAD-ESI-MS/MS) was applied for the analysis of triterpene saponins. The MS and MS/MS experiments were carried out by ionization in negative mode. Molecular mass and fragmentation data were used to support the structural characterization of the saponins. Based on retention times, high-resolution mass determination and fragmentation, 35 oleanane-triterpene saponins were tentatively identified in Z. brasiliensis.

Changes in the content of anthocyanins, flavonols, and antioxidant activity in Fragaria ananassa var. Camarosa fruits under traditional and organic fertilization.

BACKGROUND: Strawberries are consumed worldwide. In Chile, strawberry production has been established in Andisols, were phosphorus is scarce. Traditional fertilization (TF) and organic fertilization (OF) have both been established there. This study examined their impact on the polyphenolic content of strawberries. RESULTS: Two anthocyanins were identified by high performance liquid chromatography with diode array detection coupled to mass spectrometry (HPLC-DAD-ESI-MS/MS). The average total anthocyanin concentrations were found to be 651 mg kg-1 fresh weight in 100% OF, which represents a 56% increase compared to fruits that were not fertilized. In the case of flavonols, only quercetin-rhamnoside was identified, and its concentration reached 14.6 mg kg-1 with 100% OF. The ascorbic acid concentration reached 0.54 g kg-1 in 50% TF (a 20% increase over fruits without fertilization, WF). The antioxidant activities slightly increased in the fruits subjected to TF and OF in comparison with WF treatment. CONCLUSION: These results support a management strategy for obtaining the best quality and potential beneficial effects in health by increasing anthocyanins and other polyphenols under OF. © 2018 Society of Chemical Industry.

Comprehensive characterisation of polyphenols in leaves and stems of three anti-dengue virus type-2 active Brazilian Faramea species (Rubiaceae) by HPLC-DAD-ESI-MS/MS.

INTRODUCTION: The methanol (MeOH) leaf extracts of the species Faramea bahiensis, F. hyacinthina and F. truncata (Rubiaceae) have previously shown in vitro non-cytotoxic and anti-dengue virus serotype 2 (DENV2) activities in human hepatocarcinoma cell lineage (HepG2). Chemical studies have led to the isolation of major flavonoids, but quite complex fractions of phenolic compounds still remain. OBJECTIVE: To complete the study of phenolic compounds in the leaves and to access the presence of these compounds in the stems of these Faramea spp. by online high-performance liquid chromatography-diode array detector-electrospray ionisation tandem mass spectrometry (HPLC-DAD-ESI-MS/MS), as well as to evaluate the in vitro cytotoxic and anti-DENV2 activities of their MeOH stem extracts. METHODOLOGY: The identification was performed by comparing retention times, UV and mass spectra with those of available standards and by using the mechanisms and fragmentation patterns established in previous studies. The effects of the extracts in DENV2 infected HepG2 cell viability was determined by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. The virus titer was quantified by plaque assay. RESULTS: The study led to the characterisation of 31 phenolic compounds including flavonoid O- and C-glycosides, phenolic acids and one coumarin. The stem extracts from F. hyacinthina and F. bahiensis presented a similar bioactivity to those of their leaves but a loss of cytoprotective activity of F. bahiensis and a higher cytotoxicity of F. truncata were observed. CONCLUSIONS: This research allowed a detailed phenolic composition of three bioactive Faramea species to be achieved, thus contributing to the study of this genus and providing valuable information for further phytotherapeutic applications.

Effect of fertilization and arbuscular mycorrhizal fungal inoculation on antioxidant profiles and activities in Fragaria ananassa fruit.

BACKGROUND: The main methods used to increase the yield and quality of strawberry fruit produced in acidic soils with low P availability include root colonization by arbuscular mycorrhizal (AM) fungi and adjusting the type of P supplementation by means of traditional (TF) or organic (OF) fertilization, and adjusting nutrient doses. In this study, the antioxidant properties of strawberry fruit were evaluated under different treatments of fertilization (TF or OF) and different doses of P supplied at planting (0, 50 or 100% of the agronomic recommendation) and in the presence or absence of AM fungus as a bioinoculant. RESULTS: Fruits without fertilization treatments and with TF presented with higher anthocyanin concentrations. In general, higher values were obtained without AM colonization. However, spectrophotometric tests showed the highest activity and concentration in the AM-inoculated treatments. It is likely that phenolic compounds other than anthocyanins are present in the extracts. These other compounds could not be identified by the method used but could be detected by the Folin-Ciocalteu method. CONCLUSION: This study provides information that allows for improvements in strawberry fruit quality by agronomic management, with a potential beneficial effect on the health of consumers. © 2018 Society of Chemical Industry.

Dereplication by HPLC-DAD-ESI-MS/MS and Screening for Biological Activities of Byrsonima Species (Malpighiaceae).

INTRODUCTION: Byrsonima species have been used in the treatment of gastrointestinal and gynecological inflammations, skin infections and snakebites. Based on their biological activities, it is important to study other organisms from this genus and to identify their metabolites. OBJECTIVES: To determine the metabolic fingerprinting of methanol and ethyl acetate extracts of four Byrsonima species (B. intermedia, B. coccolobifolia, B. verbascifolia and B. sericea) by HPLC-DAD-ESI-MS/MS and evaluate their in vitro antioxidant, anti-glycation, anti-inflammatory and cytotoxic activities. MATERIALS AND METHODS: Antioxidant activity was determined by DPPH˙, ABTS˙+ and ROO˙ scavenging assays. Anti-glycation activity was evaluated by the ability to inhibit the formation of advanced glycation endproducts (AGEs). Anti-inflammatory activity was evaluated using a murine macrophage cell line (RAW 264-7) in the presence of lipopolysaccharide (LPS). Tumour necrosis factor alpha (TNF-α) and nitrite (NO2- ) production were measured by ELISA and the Griess reaction, respectively. The compounds present in the extracts were tentatively identified by HPLC-DAD-ESI-MS/MS. RESULTS: The evaluation of the biological activities showed the potential of the extracts. The activities were assigned to the presence of glycoside flavonoids mainly derived from quercetin, quinic acid derivatives, gallic acid derivatives, galloylquinic acids and proanthocyanidins. Two isomers of sinapic acid-O-hexoside were described for the first time in a Byrsonima species. CONCLUSION: This research contributes to the study of the genus, it is the first report of the chemical composition of B. sericea and demonstrates the importance of the dereplication process, allowing the identification of known compounds without time-consuming procedures. Copyright © 2017 John Wiley & Sons, Ltd.

Hydroxycinnamic acids and flavonols in native edible berries of South Patagonia.

Diverse edible berries are native to the Patagonian region of Southern Chile. These berries are underused because their nutritional properties are relatively unknown. In this work, the profiles and concentrations of hydroxycinnamic acid derivatives and flavonols, and the antioxidant capacity of the berry extracts, were studied using HPLC-DAD-ESI-MS/MS and CUPRAC assays, respectively. In total, 46 compounds were identified, including 17 hydroxycinnamic acid derivatives and 26 flavonols. Caffeoylquinic acid isomers were the most abundant compounds, and quercetin and myricetin derivatives were the main flavonols found. The berries from Ribes genera showed a high diversity and concentration of these 2 families of compounds and contained 3-caffeoylquinic acid and quercetin-3-rutinoside at the highest concentrations. The Patagonian berries, especially the berries of Rubus and Ribes genera, had high cupric reducing antioxidant capacity, comparable with that described for berries from the Northern hemisphere. These results contribute to promote the nutritional study of these fruits.

Flavonols, alkaloids, and antioxidant capacity of edible wild berberis species from patagonia.

There are 20 species of the Berberidaceae family described in Chile, whose fruits are edible and show high anthocyanin and hydroxycinnamic acid levels. Berberis microphylla G. Forst, commonly known as calafate, is the most extensively distributed. Flavonols and alkaloids in seed, pulp, skin, and whole calafate berry extracts and other Berberis were studied using HPLC-DAD-ESI-MS/MS and HPLC with fluorescence detector. Berry samples from different locations in Chilean Patagonia, including different phenological stages, were systematically addressed. Results were compared with other organs of the plant and with other Berberis species. Total flavonol concentration in calafate (n = 65) was 1.33 ± 0.54 µmol/g. Glycosyl metabolites of quercetin and isorhamnetin were the most abundant. Similar profiles were observed in calafate from distinct locations, but important differences were observed for the other edible Berberis species. Calafate pulp and skin have higher flavonol concentrations than seeds, and the maturation process reduced its levels. TEACCUPRAC and TEACABTS of whole calafate extracts and fractions are also explored. Finally, only berberine was detected in the fruit (0.001%), mainly in seeds. Results contribute to the promotion of this berry as a superfruit from Patagonia.

Flavonol glycosides found in hydroethanolic extracts from Tilia cordata, a species utilized as anxiolytics / Flavonóides glicosídeos encontrados no extrato hidroalcoólico de Tilia cordata, espécie usada como ansiolítico

Tilia species, among which is Tilia cordata Mill. (Tiliaceae), have been used in folk medicine as anxiolytic. The hydroethanolic extract was analyzed by using liquid chromatography with mass spectrometry HPLC-DAD-ESI-MS/MS in negative ion mode, and its chemical composition was compared to flavonoids reported as anxiolytics. The major flavonoids found were: quercetin-3,7-di-O-rhamnoside, kaempferol-3,7-di-O-rhamnoside and kaempferol 3-O-(6"-p-coumaroyl glucoside) or tiliroside. The anxiolytic activity of the genus Tilia has been attributed to the presence of quercetin and kaempferol derivatives, while the anxiolytic activity of T. americana var. Mexicana was attributed to tiliroside, which was also found among the major constituents of this species.

As espécies de Tilia, entre elas, a Tilia cordata Mill. (Tiliaceae) são utilizadas como ansiolíticas na medicina popular. O extrato hidroalcoólico foi analisado usando cromatografia líquida acoplada à espectrometria de massas HPLC-DAD-ESI/MS/MS no modo negativo e a sua composição química foi comparada com os flavonóides já reportados como ansiolíticos. Os principais flavonóides encontrados foram: quercetina-3,7-di-O-rhamnosideo, canferol-3,7-di-O-rhamnosideo, e canferol 3-O-(6"-p-cumaroil glucosideo) ou tilirosideo. A atividade ansiolítica do gênero Tília tem sido atribuída à presença de derivados de canferol e quercetina, enquanto que a atividade ansiolítica da T. americana var. Mexicana foi atribuída ao tilirosideo, o qual também foi encontrado entre os principais constituintes desta espécie.

Chemical composition of hydroethanolic extracts from five species of the Passiflora genus

The diversified genus Passiflora is well distributed all over Brazil, and many species have been long used as medicinal plants, mainly against anxiety disturbances. This effect has been attributed to its rich flavonoid composition. Flavonoids’ main class, flavonoid glycosides, has presented central action, particularly as sedative-hypnotic, anxiolytic and analgesic. The objective of the present study was to make a phytochemical screening of five little studied Passiflora species, in order to evaluate their phenolic composition. For this aim, HPLC-DAD-ESI-MS/MS was used. After the preparation of the hydroalcoholic extracts, each species was evaluated by direct injection electrospray ionization (ESI) and tandem mass spectrometry. Although belonging to the same genus, the composition of each species presented particularities; this justifies the importance of studies aiming for the phenolic composition of different Passiflora species. Flavones C-glycosides were detected in all extracts, and are found as the main constituents in P. vitifolia, P. coccinea, P. bahiensis and P. sidifolia. In this last one, flavone-6,8-di-C-glycoside, apigenin-6-C-rhamnosyl-8-C-arabinoside are present in high content. Cyclopassiflosides were found in high content together with cyanogenic glycosides in P. quadrangularis, while in P. coccinea, besides flavones-C-glycosides were also found procyanidins.

Chemical composition of hydroethanolic extracts from Siparuna guianensis, medicinal plant used as anxiolytics in Amazon region

Siparuna guianensis Aubl., Siparunaceae, is used as anxiolytic plants in folk medicine by South-American indians, "caboclos" and river-dwellers. This work focused the evaluation of phenolic composition of hydroethanolic extract of S. guianensis through HPLC-DAD-ESI/MS/MS. The constituents exhibited protonated, deprotonated and sodiated molecules and the MS/MS fragmentation of protonated, deprotonated and sodiated molecules provided product ions with rich structural information. Vicenin-2 (apigenin-6,8-di-C-glucoside) was the main constituent found in S. guianensis together quercetin-3,7-di-O-rhamnoside and kaempferol-3,7di-O-rhamnoside. A commercial extract of Passiflora incarnata (Phytomedicine) was used as surrogate standard and also was analyzed through HPLC-DAD-ESI/ MS/MS, showing flavones C-glycosides as constituents, among them, vicenin-2 and vitexin. The main constituent was vitexin. Flavonols triglycosides was also found in low content in S. guianensis and were tentatively characterized as quercetin-3O-rutinoside-7-O-rhamnoside, quercetin-3-O-pentosyl-pentoside-7-O-rhamnoside and kaempferol-3-O-pentosyl-pentoside-7-O-rhamnoside. Apigenin and kaempferol derivatives had been reported as anxiolytic agents. Flavonoids present in this extract were correlated with flavonoids reported as anxiolytics.