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Strawberry tree honey is a high-value honey from the Mediterranean area and it is characterised by a typical bitter taste. To possibly identify the secondary metabolites responsible for the bitter taste, the honey was fractionated on a C18 column and the individual fractions were subjected to sensory analysis and then analysed by liquid chromatography coupled with high-resolution tandem mass spectrometry in negative ion mode, using a mass spectrometer with an electrospray source coupled to a hybrid high resolution mass analyser (LC-ESI/LTQ-Orbitrap-MS). A chemometric model obtained by preliminary principal component analysis (PCA) of LC-ESI/LTQ-Orbitrap-MS data allowed the identification of the fractions that caused the perception of bitterness. Subsequently, a partial least squares (PLS) regression model was built. The studies carried out with multivariate analysis showed that unedone (2-(1,2-dihydroxypropyl)-4,4,8-trimethyl-1-oxaspiro [2.5] oct-7-en-6-one) can be considered responsible for the bitter taste of strawberry tree honey. Confirmation of the bitter taste of unedone was obtained by sensory evaluation of a pure standard, allowing it to be added to the list of natural compounds responsible for giving the sensation of bitterness to humans.

Liquid preparations such as tinctures and infusion derived from Ribes nigrum L. (black currant) leaves are widely used in Europe. Despite the various uses reported for the infusion and hydroalcoholic extracts of the leaves of this species, their chemical profile has not yet been defined. In the present study, the infusion, hydroalcholic and methanolic extracts prepared from R. nigrum leaves were analyzed. LC–MS analyses of these extracts allowed the characterization of 31 phenolic compounds mainly belonging to organic acids, flavonoids, catechins and its oligomers. Quantitative results proved that these preparations are a rich source of polyphenols and flavonoids and among them the infusion presented the highest polyphenol levels. A metabolomics approach was also used for the comparison and evaluation of the chemical composition of the different extracts obtained from R. nigrum leaves.

Psoriasis is an inflammatory disease of the epidermis based on an immunological mechanism involving Langerhans cells and T lymphocytes that produce pro-inflammatory cytokines. Genetic factors, environmental factors, and improper nutrition are considered triggers of the disease. Numerous studies have reported that in a high number of patients, psoriasis is associated with obesity. Excess adipose tissue, typical of obesity, causes a systemic inflammatory status coming from the inflammatory active adipose tissue; therefore, weight reduction is a strategy to fight this pro-inflammatory state. This study aimed to evaluate how a nutritional regimen based on a ketogenic diet influenced the clinical parameters, metabolic profile, and inflammatory state of psoriasis patients. To this end, 30 psoriasis patients were subjected to a ketogenic nutritional regimen and monitored for 4 weeks by evaluating the clinical data, biochemical and clinical parameters, NMR metabolomic profile, and IL-2, IL-1β, TNF-α, IFN-γ, and IL-4 concentrations before and after the nutritional regimen. Our data show that a low-calorie ketogenic diet can be considered a successful strategy and therapeutic option to gain an improvement in psoriasis-related dysmetabolism, with significant correction of the full metabolic and inflammatory status.

The research aimed to evaluate the polyphenolic composition and the antioxidant capacity of edible extracts of feijoa (Acca sellowiana (O. Berg) Burret) flowers. Phenolic compounds of whole feijoa flower (FM), feijoa petals (PM) and feijoa petals juice (PJ) were identified by high-performance liquid chromatography coupled with electrospray mass spectrometry and quantified by liquid chromatography coupled with ultraviolet/visible detection. Moreover, the total polyphenol (TP) content was measured spectrophotometrically and the antioxidant capacities of the extracts were evaluated by FRAP, CUPRAC, DPPH(·), and ABTS(·+) assays. The FM showed TP content (395.14 ± 7.91 mg GAE/L) higher than PM and PJ, and exhibited better antioxidant capacities. FM extracts were characterized by the high content of anthocyanins (115.3 ± 3.6 mg/L), flavonols (42.9 ± 3.3 mg/L) and the presence of ellagic acid (7.9 ± 0.2 mg/L) and other galloyltannins. In addition, cyanidin-3-O-glucoside and apigenin were detected in all the three extracts. The present study provided an overview on particular bioactive compounds that characterise different parts of edible feijoa flowers. Among the latter, FM proved to be the most suitable for exploitation in the food and health manufactory. GRAPHIC ABSTRACT: [Image: see text]

A comparison between High-Performance Thin-Layer Chromatography (HPTLC) analysis and Liquid Chromatography High Resolution Mass Spectrometry (LC&ndash, HRMS), coupled with Principal Component Analysis (PCA) was carried out by performing a combined metabolomics study to discriminate Arbutus unedo (A. unedo) plants. For a rapid digital record of A. unedo extracts (leaves, yellow fruit, and red fruit collected in La Maddalena and Sassari, Sardinia), HPTLC was used. Data were then analysed by PCA with the results of the ability of this technique to discriminate samples. Similarly, extracts were acquired by non-targeted LC&ndash, HRMS followed by unsupervised PCA, and then by LC&ndash, HRMS (MS) to identify secondary metabolites involved in the differentiation of the samples. As a result, we demonstrated that HPTLC may be applied as a simple and reliable untargeted approach to rapidly discriminate extracts based on tissues and/or geographical origins, while LC&ndash, HRMS could be used to identify which metabolites are able to discriminate samples.

Ziziphus jujuba Mill. leaves are receiving a great attention for their ability to improve sleep, exerting beneficial effects for both the heart and the central nervous system. With the aim to obtain a comprehensive analysis of the specialised metabolites occurring in the leaves of Z. jujuba, a LC-ESI/(HR)Orbitrap/MS profile in negative ion mode of the methanol extract was carried out. The LC-MS profile guided the isolation of 42 compounds, of which the structures were elucidated by 1D and 2D-NMR experiments. Based on this approach, 2 previously unreported dammarane-type saponins have been characterized along with flavonoid derivatives, dammarane-type saponins and triterpenic acids. Dammarane-type saponins were tested for their cytotoxic activity against A549 and HeLa cancer cell lines. None of the tested compounds, in a range of concentrations between 12.5 and 100 μM, caused a significant reduction of the cell number. This work provides a deep insight on the chemistry of the leaves of Z. jujuba and could be useful for further biological studies aimed at identifying phytochemicals contributing to the health benefits attributed to this herbal drug.

Corylus avellana (hazelnut) is one of the most popular tree nuts on a worldwide basis. The main products of C. avellana are kernels, a nutritious food, with a high content of healthy lipids, contained in a hard shell. In recent years, along with the ongoing research carried out on hazelnut kernels, a growing interest has been addressed to the hazelnut byproducts including hazelnut skin, hazelnut hard shell, and hazelnut green leafy cover as well as hazelnut tree leaf. These byproducts deriving from the roasting, cracking, shelling/hulling, and harvesting processes have been found as a source of “phytochemicals” with biological activity. The aim of this review is to provide a comprehensive and critical update on the chemistry and biological activity of specialized metabolites occurring in hazelnut kernels and byproducts. Phenolics are the most abundant phytochemicals not only in the kernels, but also in other processing byproducts. Attention has been also devoted to taxane derivatives isolated from C. avellana leaves. An overview on the biological activity, mainly antioxidant, antiproliferative, and antimicrobial along with less common biological effects, has been provided, contributing to highlight C. avellana as a source of bioactive phytochemicals with the potential to exert beneficial effects on human health. Finally, analytical techniques for the quali-quantitative analysis of specialized metabolites occurring in the different parts of C. avellana have been reviewed.

The species Myrtus communis L. represents a significant economic resource in Sardinia region (Italy), in fact its tissues are used both for the preparation of myrtle liquor and for essential oils or extracts with important pharmacological activities. Identification and quantification of polyphenolic compounds in leaves of M. communis L. appears interesting from both a biological and ecophysiological point of view. In the present study the discrimination of phytochemical content of M. communis L. leaves from different geographic origin and cultivars, was explored by Liquid Chromatography coupled with high resolution mass spectrometry (LC-ESI/LTQOrbitrap/MS) followed by Multivariate Data Analysis and phytochemical characterization. A total of 47 compounds were detected and 35 of them were tentatively identified on the bases of their retention time, UV/Vis spectra, MS spectra and MS fragmentation patterns. Principal Component Analysis (PCA) and Partial Least Square – Discriminant Analysis (PLS-DA) projection methods were applied to compare fingerprints and to discriminate the different geographical areas of the seeds used for the cultivation.

Introduction Prunus dulcis Mill. is a plant cultivated for the production of its edible seeds, known as sweet almonds. In the last decades almond demand has highly increased due to their wide use in the industrial manufacturing of almond-based foods; this has led to a huge production of waste materials, mainly corresponding to shells and husks. Objective To achieve a deeper understanding of the chemical composition of almond husks with the aim of exploring these byproducts as a source of bioactives to be used in nutraceutical and cosmetic formulations. Methods Methanol, ethanol and ethanol-water extracts of the almond husks were analysed by high-resolution liquid chromatography electrospray ionisation Orbitrap mass spectrometry (HR-LC-ESI-Orbitrap-MS) in negative ion mode. Tandem mass spectrometry (MS/MS) data were acquired by using the Data-Dependent Scan experiment, allowing the precursor ion to be selected as the most intense peak during LC-MS analyses. Nuclear magnetic resonance (NMR) experiments were performed on a Bruker DRX-600 spectrometer. Folin-Ciocalteu, DPPH• (2,2-diphenyl-1-picrylhydrazyl) and TEAC (Trolox equivalent antioxidant capacity) assays were employed to determine the total phenolic content and the radical scavenging activity of the extracts. Results The LC-MS/MS analysis of the methanol extract guided the isolation of phloroglucinol derivatives, flavonoids and terpenes. Eco-friendly extraction methods showed to be selective in extracting flavonoids while the comparison of the LC-MS profiles of the Italian cultivars Toritto and Avola showed significant differences, confirming how different growing conditions may influence the metabolome of a plant species. Conclusion This study led to a deeper insight into the chemical constituents of almond husks and showed how the eco-friendly extraction resulted in an effective method to obtain extracts rich in antioxidant sources.

Wild strawberry (Fragaria vesca) is recognized as a traditional food of Campania region (Italy). The vegetative parts have a pharmaceutical interest, being used as decoctions for hypertension treatment due their detoxifying, diuretic, stimulant and dermatological protective properties; leaves, that after collection of fruits are generally thrown away, could be an interesting byproduct, source of bioactive compounds for cosmetic and pharmaceutical industry. In the present work, the metabolite profiles of F. vesca leaves coming from populations spontaneously growing in the underwood (wild) and in crop (cultivated) and from autochthonous and non-autochthonous germplasm of Campania region (Italy) were investigated by LC-ESI/LTQOrbitrap/MS analysis. 27 metabolites mainly belonging to organic acids, flavonoids, catechin and its oligomers, and ellagitannins were putatively identified. Antioxidant activity was tested for each sample, in particular cultivated samples and wild samples with autochthonous germplasm of Campania region showed higher antioxidant activity compared to the non autochthonous ones. Moreover, in this study, it was possible to predict antioxidant metabolites, markers of this species, using LC-MS spectra and multivariate regression data analysis.

Introduction\ud\udMyrtus communis L. (Myrtaceae) is a self‐seeded shrub, widespread in Sardinia, with anti‐inflammatory, antiseptic, antimicrobial, hypoglycemic and balsamic properties. Its berries, employed for the production of sweet myrtle liqueur, are characterised by a high content of bioactive polyphenols, mainly anthocyanins. Anthocyanin composition is quite specific for vegetables/fruits and can be used as a fingerprint to determine the authenticity, geographical origin and quality of raw materials, products and extracts. \ud\ud\udObjective\ud\udTo rapidly analyse and determine anthocyanins in 17 samples of Myrtus communis berries by developing a platform based on the integration of UHPLC–MS/MS quantitative data and multivariate analysis with the aim of extracting the most information possible from the data. \ud\ud\udMethodology\ud\udUHPLC‐ESI‐MS/MS methods, working in positive ion mode, were performed for the detection and determination of target compounds in multiple reaction monitoring (MRM) mode. Optimal chromatographic conditions were achieved using an XSelect HSS T3 column and a gradient elution with 0.1% formic acid in water and 0.1% formic acid in acetonitrile. Principal component analysis (PCA) was applied to the quantitative data to correlate and discriminate 17 geographical collections of Myrtus communis. \ud\ud\udResults\ud\udThe developed quantitative method was reliable, sensitive and specific and was successfully applied to the quantification of 17 anthocyanins. Peonidin‐3‐O‐glucoside was the most abundant compound in all the extracts investigated. \ud\ud\udConclusion\ud\udThe developed methodology allows the identification of quali‐quantitative differences among M. communis samples and thus defines the quality and value of this raw material for marketed products. Moreover, the reported data have an immediate commercial value due to the current interest in developing antioxidant nutraceuticals from Mediterranean plants, including Sardinian Myrtus communis.

Antiphospholipid syndrome (APS) is a rheumatic inflammatory chronic autoimmune disease inducing hypercoagulable state associated with vascular thrombosis and pregnancy loss in women. Cardiac, cerebral and vascular strokes in these patients are responsible for reduction in life expectancy. Timely diagnosis and accurate monitoring of disease are decisive to improve the accuracy of therapy. In the present work, we present a NMR-based metabolomic study of blood sera of APS patients. Our data show that individuals suffering APS have a characteristic metabolomic profile with abnormalities associated to the metabolism of methyl group donors, ketone bodies and amino acids. We have identified for the first time the metabolomic fingerprint characterizing APS disease having potential application to improve APS timely diagnosis and appropriate therapeutic approaches.

A new combined “untargeted” and “targeted” metabolomics approach to investigate Rosmarinus officinalis L. plants was proposed by using the merging of high-performance thin-layer chromatography (HPTLC) assay and liquid chromatography mass spectrometry (LC–MS) with principal component analysis (PCA). Rapid fingerprints of Rosmarinus extracts were obtained and compared by using HPTLC technique; targeted compounds were identified and quantified by LC–MS/MS (MRM), while the antioxidant capacity of extracts was evaluated by methods based on the ability to scavenge radicals such as ABTS+* and DPPH*, since the metabolite expression is generally correlated with the biological activity. By HPTLC fingerprints, a rapid visual comparison of secondary metabolites in Rosmarinus samples from different places of collection was obtained and PCA was performed providing an overview of the capacity of the HPTLC variables to discriminate samples. HPTLC fingerprint assisted by PCA results a reliable untargeted approach for the discrimination and classification of different samples on the basis of their geographical area, from west to east of Sardinia. The ‘targeted’ approach was performed by developing LC–MS/MS (MRM) method allowing the identification and quantification of 12 compounds belonging to the family of flavonoids and phenolic acids. The combination of quantitative data with PCA allowed to discriminate La Maddalena Rosmarinus sample from others, in a correlated way with antioxidant activities results, showing values significantly higher. A positive Pearson correlation between antioxidant activity measured with DPPH and ABTS and total phenolic contents, finally confirmed that antioxidant activity depends on phenolic amounts.

The antinociceptive activity of the Maytenus rigida Mart. (Celastraceae) ethanol extract and its ethyl acetate fraction as well as of (-)-4'-methylepigallocatechin (1), a previously isolated compound, was demonstrated in vivo. ED50 for 1 in the writhing test was 14.14 mg/kg. The acetic acid-induced writhing was inhibited by 98.4, 84.4, and 58.3%, respectively, when mice were treated with the ethanol extract, ethyl acetate fraction, and 1. In the hot plate test, mice pretreated with 1 showed significantly increased reaction times (60-89%). Oral administration of 1 significantly inhibited first and second phases of the formalin-induced pain (50 and 26.5%, respectively), whereas indomethacin inhibited only the second phase of the test (41.2%). Ethanol extract and its fraction showed effects on inflammatory pain, while neurogenic and inflammatory pain suppression by 1 is a strong indication of the presence of both central and peripheral effects and suggests its analgesic and anti-inflammatory potential.

Food supplements based on Vitex agnus castus L. (Verbenaceae) fruits, also known as chasteberry, are routinely used by women against somatic and psychic premenstrual symptoms such as depression, sadness or irritability. With the aim of highlighting the differences in the chemical profiles of cultivated fruits and different parts of wild plants (fruits, leaves and sprouts) of V. agnus castus , a method concerning with the quali–quantitative study of the derived hydroalcoholic extracts was carried out by using high-performance liquid chromatography coupled to electrospray negative ionization Orbitrap multicollisional high resolution mass spectrometry (LC/ESI/(Orbitrap)MS n ) and high-performance liquid chromatography coupled to electrospray negative ionization triple quadrupole tandem mass spectrometry (LC/ESI/(QqQ)MS) in multiple reaction monitoring (MRM) mode.

In the present study, metabolic changes in secondary metabolites of Fragaria ananassa Duch. fruits during ripening were evaluated, and in particular, the differences between fruits obtained from either organic or conventional, non-organic crops. Extracts from ripe and unripe fruits of Fragaria ananassa var. Candonga were analyzed by direct infusion mass spectrometry using an instrument equipped with an ion trap analyzer (DI-ESI-IT-MS) and by liquid chromatography coupled to high resolution mass spectrometry using a mass spectrometer equipped with an ESI source and an Orbitrap analyzer (LC-ESI-FT-MS). Chromatograms were evaluated using the free software package MZmine and the resulting metabolomics data were processed. Data sets were analyzed by Principal Component Analysis (PCA) and Partial Least Squares Discriminant Analysis (PLS-DA). All the differences between the fruits collected from organic crops and conventional crops were underlined. In addition, LC-ESI-FT-MS analyses were useful to achieve a comprehensive characterization of metabolic profiles of strawberries (flavonoids, anthocyanins and catechins were identified in the extracts). Flavonoids and anthocyanins were present with similar metabolic profile in F. ananassa obtained from organic and conventional, non-organic crops with differences from ripe and unripe fruits. Phenolic compounds thus are not responsive for the classification observed by untargeted metabolomic approach. © 2015 Elsevier Ltd.

Moringa oleifera is a medicinal plant and an excellent dietary source of micronutrients (vitamins and minerals) and health-promoting phytochemicals (phenolic compounds, glucosinolates and isothiocyanates). Glucosinolates and isothiocyanates are known to possess anti-carcinogenic and antioxidant effects and have attracted great interest from both toxicological and pharmacological points of view, as they are able to induce phase 2 detoxification enzymes and to inhibit phase 1 activation enzymes. Phenolic compounds possess antioxidant properties and may exert a preventative effect in regards to the development of chronic degenerative diseases. The aim of this work was to assess the profile and the level of bioactive compounds in all parts of M. oleifera seedlings, by using different MS approaches. First, flow injection electrospray ionization mass spectrometry (FI-ESI-MS) fingerprinting techniques and chemometrics (PCA) were used to achieve the characterization of the different plant's organs in terms of profile of phenolic compounds and glucosinolates. Second, LC-MS and LC-MS/MS qualitative and quantitative methods were used for the identification and/or determination of phenolics and glucosinolates in M. oleifera.

Potentilla erecta (L.) is known for the high concentration of proanthocyanidin oligomers (PAs) in its underground parts. The use of its preparations as food supplements and the lack of chemical–analytical studies concerning with an efficient chromatographic separation procedure for these compounds led us to develop a strategy to profile PAs occurring in this species. Their presence has been rationalised on the basis of mass spectrometric profiles. Direct flow injection/electrospray ionisation (ESI)/ion trap (IT) mass spectrometry was used to investigate the hydroalcoholic extract of P. erecta. To achieve deeper structural information and to focus the analysis on PAs with high polimerisation degree (DP), matrix assisted laser desorption ionisation (MALDI)-time of flight (TOF)-mass spectrometry, was used. Finally, liquid chromatography tandem mass spectrometry (LC–MS 2 ) analyses were executed by using a diol stationary phase to detect PAs from DP1 to DP10. Results suggested that all of them were B-type procyanidins with 4→8 linkages.

Phytochemical investigation of the methanolic extract of Byrsonima crassifolia's bark led to the isolation of 8 known phenolic compounds 5-O-galloylquinic acid, 3-O-galloylquinic acid, 3,4-di-O-galloylquinic acid, 3,5-di-O-galloylquinic acid, 3,4,5-tri-O-galloylquinic acid, (+)-epicatechin-3-gallate along with (+)-catechin and (+)-epicatechin. Due to their biological value, in the present study, a high-performance liquid chromatography–tandem mass spectrometry (LC–MS/MS) method, working in multiple reaction monitoring (MRM) mode, has been developed to quantify these compounds. B. crassifolia bark resulted in a rich source of phenolic compounds and particularly of galloyl derivates. The proposed analytical method is promising to be applied to other galloyl derivatives to quantify these bioactive compounds in raw material and final products.

Liquid chromatography electrospray mass spectrometry (LC-ESI/MS) has been applied to the full characterization of saponins and phenolics in hydroalcoholic extracts of roots of liquorice (Glycyrrhiza glabra). Relative quantitative analyses of the samples with respect to the phenolic constituents and to a group of saponins related to glycyrrhizic acid were performed using LC-ESI/MS. For the saponin constituents, full scan LC-MS/MS fragmentation of the protonated (positive ion mode) or deprotonated (negative ion mode) molecular species generated diagnostic fragment ions that provided information concerning the triterpene skeleton and the number and nature of the substituents. On the basis of the specific fragmentation of glycyrrhizic acid, an LC-MS/MS method was developed in order to quantify the analyte in the liquorice root samples. Chinese G. glabra roots contained the highest levels of glycyrrhizic acid, followed by those from Italy (Calabria).

Acacia nilotica (L.) Del. syn is a species rich in polyphenolic constituents, in which catechins are hypothesized to possess antioxidant properties and to play a role in the anti-inflammatory activity of several plants. Due to the complexity of catechin derivatives, the investigation of this class of natural compounds has been limited by difficulties in their separation. In this paper, rationalization of the phenolics occurring in the 80% EtOH extract of Acacia nilotica pods, on the basis of ESI-MS and ESI-MS/MS profiles, has been proposed. Additionally, an LC-ESI-MS qualitative study has been performed by using a C18 polar endcapped stationary phase. The fragmentation pattern obtained evidenced the presence in A. nilotica pods of galloylated catechin- and gallocatechin derivatives along with galloylated glucose derivatives. The structures were confirmed by NMR, after isolation of the pure compounds. In addition, the radical scavenging activities of extracts and pure compounds were investigated, by using the TEAC assay. Furthermore quantitative analyses were performed by LC-ESI-MS/MS, confirming the interest of this species as a rich source of very strong antioxidant principles.

The chemical analysis and quality control of Ginkgo leaves, extracts, phytopharmaceuticals and some herbal supplements is comprehensively reviewed. The review is an update of a similar, earlier review in this journal [T.A. van Beek, J. Chromatogr. A 967 (2002) 21-55]. Since 2001 over 3000 papers on Ginkgo biloba have appeared, and about 400 of them pertain to chemical analysis in a broad sense and are cited herein. The more important ones are discussed and, where relevant, compared with the best methods published prior to 2002. In the same period over 2500 patents were filed on Ginkgo and the very few related to analysis are mentioned as well. Important constituents include terpene trilactones, i.e. ginkgolide A, B, C, J and bilobalide, flavonol glycosides, biflavones, proanthocyanidins, alkylphenols, simple phenolic acids, 6-hydroxykynurenic acid, 4-O-methylpyridoxine and polyprenols. In the most common so-called "standardised" Ginkgo extracts and phytopharmaceuticals several of these classes are no longer present. About 130 new papers deal with the analysis of the terpene trilactones. They are mostly extracted with methanol or water or mixtures thereof. Supercritical fluid extraction and pressurised water extraction are also possible. Sample clean-up is mostly by liquid-liquid extraction with ethyl acetate although no sample clean-up at all in combination with LC/MS/MS is gaining in importance. Separation and detection can be routinely carried out by RP-HPLC with ELSD, RI or MS, or by GC/FID or GC/MS after silylation. Hydrolysis followed by LC/MS allows the simultaneous analysis of terpene trilactones and flavonol aglycones. No quantitative procedure for all major flavonol glycosides has yet been published because they are not commercially available. The quantitation of a few available glycosides has been carried out but does not serve a real purpose. After acidic hydrolysis to the aglycones quercetin, kaempferol and isorhamnetin and separation by HPLC, quantitation is straightforward and yields by recalculation an estimation of the original total flavonol glycoside content. A profile of the genuine flavonol glycosides can detect poor storage or adulteration. Although the toxicity of Ginkgo alkylphenols upon oral administration has never been undoubtedly proven, most suppliers limit their content in extracts to 5 ppm and dozens of papers on their analysis were published. One procedure in which a methanolic extract is directly injected on a C8 HPLC column appears superior in terms of sensitivity (5 ppm), separation, simplicity and validation and will be incorporated in the European Pharmacopoeia. Alternatively GC/MS and ELISA methods can be used. A sharp contrast to the plethora of papers on terpene trilactones, flavonol glycosides, and ginkgolic acids forms the low number of papers on biflavones, proanthocyanidins, simple phenolics, simple acids, and other constituents that make up the remaining 70% of Ginkgo standardised extracts. More research in this direction is clearly needed. For the analysis of Ginkgo proanthocyanidins (7%) for instance, no reliable assays are yet existing. Finally the growing literature on pharmacokinetic and fingerprinting studies of Ginkgo is briefly summarised.

Six secondary metabolites from the methanolic extract of Sweetia panamensis (Fabaceae) bark were isolated and characterised. Along with the pyrones desmethylangonine β-d-O-glucopyranoside and desmethylangonine β-d-O-glucopyranosyl-(1→6)-O-β-d-glucopyranoside, already reported in this species, 5-O-caffeoylquinic acid (chlorogenic acid), 4-O-caffeoylquinic acid, 3-O-caffeoylquinic acid and the isoflavonoid 5-O-methylgenistein 7-O-β-d-glucopyranoside were isolated for the first time from S. panamensis. Additionally, an LC-ESI-MS qualitative analysis was performed and an ultra performance liquid chromatography (UPLC) method was developed and validated for the determination of these compounds. The UPLC method was applied to the quantitative analysis of plant samples. Pyrones and caffeoylquinic acids resulted to be the main compounds in the extract; in particular desmethylangonine β-d-O-glucopyranosyl-(1→6)-O-β-d-glucopyranoside was the most abundant compound.

Yuccaols (A, B, C) are phenolic constituents isolated from Yucca schidigera bark characterized by unusual spirostructures made up of a C15 unit and a stilbenic portion closely related to resveratrol. These novel compounds are of particular interest for their antioxidant and anti-inflammatory properties. However, their effects on cell proliferation, migration, and platelet-activating factor (PAF) biosynthesis remain unknown. PAF, a potent mediator of inflammation, is known to promote angiogenesis and in vitro migration of endothelial cells and Kaposi's sarcoma (KS) cells. The objective of our study was to determine the effect of Yuccaols and resveratrol on the vascular endothelial growth factor (VEGF)-induced proliferation, migration, and PAF biosynthesis in KS cells. The results indicated that Yuccaols (25 microM) were more effective than resveratrol (25 microM) in inhibiting the VEGF-induced KS cell proliferation. Western blot analysis revealed that Yuccaols reduced the VEGF-induced phosphorylation of p38 and p42/44, thus indicating a possible interference with the mechanism underlying the VEGF-stimulated cell proliferation. Furthermore, Yuccaols completely inhibited the VEGF-stimulated PAF biosynthesis catalyzed by the acetyl-CoA:lyso-PAF acetyltransferase and enhanced its degradation through the PAF-dependent CoA-independent transacetylase (250% of control). In addition, Yuccaol C abrogated the PAF-induced cell motility whereas Yuccaol A and Yuccaol B reduced the cell migration from 7.6 microm/h to 6.1 microm/h and 5.6 microm/h, respectively. These results indicate that the anti-inflammatory properties attributed to Yucca schidigera can be ascribed to both resveratrol and Yuccaols and provide the first evidences of the anti-tumor and anti-invasive properties of these novel phenolic compounds.

The isolation of six flavon glycosides (1−6), among them four new natural compounds (1−4), from the CHCl3/MeOH extract of the fruits of Cyclanthera pedata is reported. All of the structures were elucidated by spectroscopic methods, including the concerted application of one-dimensional (1H, 1H TOCSY, 13C, and 13C DEPT-NMR) and two-dimensional NMR techniques (DQF-COSY, HSQC, and HMBC). For all of the isolated compounds the antioxidant activity was determined by measuring the free radical scavenging activity, using the Trolox equivalent antioxidant capacity (TEAC) method, and the coupled oxidation of β-carotene and linoleic acid. Keywords: Cyclanthera pedata; Cucurbitaceae; flavone glycosides; NMR; antioxidant activity

Potentilla anserina L. (Rosaceae) is known for its beneficial effects of prevention of pre-menstrual syndrome (PMS). For this reason P. anserina is processed into many food supplements and pharmaceutical preparations. Here we analyzed hydroalcoholic reference extracts and compared them with various extracts of different pharmacies using an integrative metabolomics platform comprising GC-MS and LC-MS analysis and software toolboxes for data alignment (MetMAX Beta 1.0) and multivariate statistical analysis (COVAIN 1.0). Multivariate statistics of the integrated GC-MS and LC-MS data showed strong differences between the different plant extract formulations. Different groups of compounds such as chlorogenic acid, kaempferol 3-O-rutinoside, acacetin 7-O-rutinoside, and genistein were reported for the first time in this species. The typical fragmentation pathway of the isoflavone genistein confirmed the identification of this active compound that was present with different abundances in all the extracts analyzed. As a result we have revealed that different extraction procedures from different vendors produce different chemical compositions, e.g. different genistein concentrations. Consequently, the treatment may have different effects. The integrative metabolomics platform provides the highest resolution of the phytochemical composition and a mean to define subtle differences in plant extract formulations. Electronic supplementary material The online version of this article (doi:10.1007/s11306-012-0473-x) contains supplementary material, which is available to authorized users.