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• 2- and 3-isopropyl malic acid were identified and quantified in wine. • Combined MS techniques were applied to achieve definitive identification. • An analytical method was developed and validated to quantify both isomers. • The average contents of the two acids were assessed in a group of ten wines. Organic acids of wine comprise one of the main taste groups, that of sourness. Two isomeric compounds with molecular weight of 176 u have been identified in wine using two LC-MS systems, LC-IT (ion trap) and LC-Q-Orbitrap. The two isomers are organic acids, 3-isopropylmalic acid (3-IPMA) never identified in wines, and 2-isopropylmalic acid (2-IPMA), never quantified in wines. After the definitive identification against the authentic standards, an analytical method for their determination in wines was optimised and validated using the LC-IT platform. Linearity was verified in the range 5–320 mg L−1 (correlation coefficients higher than 0.9914) and the recoveries obtained spiking the samples at two fortification levels were higher than 86.7%, with RSDs (n = 9) lower than 15.1%. Finally, the two compounds were quantified in ten red and white Italian wines, and average concentrations were determined at 1.78 mg L−1 (0.56–4.13) and 23.0 mg L−1 (6.7–41.6) of 3-IPMA and 2-IPMA, respectively. [ABSTRACT FROM AUTHOR]

Grape pomace contains high amounts of bioactive compounds, mainly polyphenols, with different concentrations depending on several factors: grape variety, vinification procedures, even within the same cultivar variation may be due to the geographic regions and wine vintage. Therefore, phenolic, antioxidant, macro- and micro-nutritional composition of wine waste (pomace and seed) originating from Lacrima di Morro d'Alba red grape variety and pomace of Verdicchio white variety were evaluated for the first time. LC-MS/MS analysis showed the presence of 32 phenolic compounds. The phenolic profile was different in pomace of both varieties: white grape pomaces showed the predominance of flavan-3-ols, while anthocyanins were predominant in red pomaces. Comparing seeds and pomace of Lacrima di Morro d'Alba, catechin and epicatechin are representative compounds in red grape seeds, while malvidin-3-galactoside and petunidin-3-glucoside are the most abundant compounds in pomace of all wineries. Highest TPC and antioxidant activities determined by UV–vis spectrophotometer were observed in seed samples. High dietary fibers, polyunsaturated fatty acids, minerals and protein contents were observed in all samples. Wine byproducts of both grape varieties appeared to be a good source of phenolic and nutritional compounds; therefore, they could be a cheap alternative for phenolics production and development of new functional foods. [ABSTRACT FROM AUTHOR]

Abstract: Rapamycin or sirolimus is a carboxylic lactone-lactam macrolide with a potent immunosuppressive activity. It can be successfully used to impregnate stents inserted in coronary arteries during surgical applications, preventing fatal infection and rejection adverse effect. The chemical stability of rapamycin in several organic-volatile solvents (acetone, chloroform, dichloromethane, hexane, ethyl alcohol, ethyl acetate, methyl alcohol, pentane and tetrahydrofurane) was established by HPLC–DAD-MS in reverse phase analysis. Results permitted to exclude rapamycin chemical degradation and to reveal a typical chemical isomerization, favoured in accordance to the solvent used. Two typical peaks appear, denominated β and γ, the time retention of which are, respectively, 11.3 and 15.0min. Thanks to data recovered by NMR, spectrophotometric UV and mass analyses, it was possible to establish that both peaks correspond to two different isomeric forms of rapamycin. In addition, it was possible to establish that the relative percentage peak area varies according to the solvent and to the experimental time. The two isomeric forms are in equilibrium and each solvent concurs to differently displace this equilibrium versus one form rather than another, according to their both polarity index and aproticity. [Copyright &y& Elsevier]

This study quantified, for the first time, 2-isopropylmalic and 3-isopropylmalic acids, in green, roasted and espresso coffee by UHPLC-MS/MS. Moreover, it reports the influence of postharvest processing methods (natural, washed and honey) on their content. New extraction techniques were developed and validated from three coffee matrices (green, roasted and espresso). Honey coffee exhibited levels substantially higher of 2-isopropylmalic acid than those processed by natural and washed methods (p < 0.05). Specifically, 2-isopropylmalic acid levels in honey green, roasted and espresso coffee samples were 48.24 ± 7.31 ng/g, 168.8 ± 10.88 ng/g and 177.5 ± 9.49 ng/g, respectively. This research highlights the significant impact of processing methods on the chemical profile of coffee and introduces 2-isopropylmalic and 3-isopropylmalic acids as potential quality indicators. Moreover, it suggests that the fermentation stage during processing may play a crucial role in their formation, laying the foundation for optimizing coffee processing to enhance quality. [Display omitted] • First quantification of 2-IPMA and 3-IPMA in coffee. • Honey processing boosts 2-IPMA levels. • Novel extraction methods for malic acid derivatives in coffee. • Link between processing methods and chemical profiles. • Potential new indicators of coffee quality. [ABSTRACT FROM AUTHOR]

• 2-IPMA and 3-IPMA were quantified in forty wines by HPLC-MS/MS triple quadrupole. • Red wines seem to be correlated with high amounts of 2-IPMA. • White wines were characterized by low levels of both organic acids. • Both acids showed mild antibacterial and bactericidal activity against human pathogens. • Only 3-IPMA showed a mild antioxidant activity. 2-Isopropylmalic acid (2-IPMA) and 3-isopropylmalic acid (3-IPMA), recently discovered in wines, were simultaneously quantified in forty wines by UHPLC-MS/MS triple quadrupole. Principal component analysis displayed that red wines were more correlated with high amounts of 2-IPMA (average content 31.60 mg/L); white wines were mostly characterized by low levels of both organic acids. No correlation of theirs levels to other wine features (wine ageing or alcoholic content) were found. 2-IPMA and 3-IPMA showed MICs values of 4096 mg/L and MBCs values of 8192 mg/L or higher against several food borne pathogens. In association, an interesting lower MIC and MBC values (2048 mg/L and 4096 mg/L respectively) were observed against Y. enterocolitica. Interestingly, 3-IPMA showed a mild antioxidant activity by DPPH assay (EC 50 = 3940 mg/L), higher than that of 2-IPMA (EC 50 > 4800 mg/L). No toxicity of these compounds against human colorectal and liver cells (TB assay) was observed. [ABSTRACT FROM AUTHOR]

Pulses, which include lentils, beans, chickpeas, peas, and soybeans, provide an important source of proteins, dietary fibers, minerals and vitamins, as well as such important bioactive molecules as polyphenols. The presence of polyphenols is often related to the colour of the pulse and to its antioxidant activity. The aim of this work was to set up a new HPLC-DAD method for simultaneously analysing 14 polyphenolic compounds, including two anthocyanins, in different varieties of pulses and to correlate the polyphenol content with the seed coat colour and the antioxidant activity. The total content of the analysed polyphenols ranged from 3 mg/kg for dehulled red lentils to 1630.5 mg/kg for ruviotto beans. Samples with dark testa (or seed coat), namely black lentils and diavoli beans, had higher antioxidant activity than those with pale testa, and a positive correlation was found between total phenolic content (TPC) and IC 50 for dark coloured varieties. [ABSTRACT FROM AUTHOR]

Even if the acids composition and their role in coffee still need to be clarified, acidity is one of the main sought-after features in coffee and it is becoming one of the main quality markers. Hence, the aim of this paper was to evaluate the main parameters influencing coffee acidity with a focus on carboxylic acids. To the best of our knowledge, this is the first study regarding filter coffee prepared from specialty and mainstream coffee, differently roasted and through eight diverse extraction methods. Coffee cup chemical composition in terms of organic and chlorogenic acids, caffein and physicochemical parameters were correlated with perceived sourness and mouthfeel to better understand the influence of extracted compounds on the final beverage acidity. Statistical tools revealed that a major impact of chlorogenic acids emerged in pH and titratable acidity, while the sensorial sourness appeared more correlated with organic acids concentration. Thus, these findings suggests that organic acids could be potential predictors of beverage perceived acidity. • The highest organic acids level was found in Ibrik coffee beverage. • Brewing pressure and temperature influence the extraction of organic acids. • In specialty coffee pH and titratable acidity are influenced by CQAs. • In mainstream coffee the CQAs mainly impact the perceived sourness. • Organic acids concentration can predict perceived acidity in specialty coffee. [ABSTRACT FROM AUTHOR]

The root of Gentiana lutea L., famous for its bitter properties, is often used in alcoholic bitter beverages, food products and traditional medicine to stimulate the appetite and improve digestion. This study presents a new, fast, and accurate HPLC method using HPLC/ESI-MS and HPLC/DAD for simultaneous analysis of iridoids (loganic acid), secoiridoids (gentiopicroside, sweroside, swertiamarin, amarogentin) and xanthones (isogentisin) in different populations of G . lutea L., cultivated in the Monti Sibillini National Park, obtained wild there, or purchased commercially. Comparison of HPLC/ESI-MS and HPLC/DAD indicated that HPLC/ESI-MS is more sensitive, reliable and selective. Analysis of twenty samples showed that gentiopicroside is the most dominant compound (1.85–3.97%), followed by loganic acid (0.11–1.30%), isogentisin (0.03–0.48%), sweroside (0.05–0.35%), swertiamarin (0.08–0.30%), and amarogentin (0.01–0.07%). The results confirmed the high quality of the G . lutea cultivated in the Monti Sibillini National Park. [ABSTRACT FROM AUTHOR]

[Display omitted] • Microwave hydrodiffusion and gravity evaluated for pomegranate juice production. • MHG can increase the juice yield up to 55%. • MHG gave a juice rich in catechin and delphinidin-3,5-glucoside. • The lyophilized juices possess anti-glucosidase and anti-glycation activity. Green technologies based on microwaves have been developed by the food industry to produce organoleptically acceptable fruit juices without preliminary processing. Microwave irradiation coupled with hydrodiffusion and gravity (MHG) combines microwave heating with the earth's gravity, allowing the collection of hydrophilic substances released from the irradiated matrix. To the best of our knowledge, MHG extraction has never been experimented to produce pomegranate juice. In this work, we have evaluated it as a potential alternative to the conventional squeezing. A central composite design study (CCD) allowed the selection of the best extractive conditions (irradiation power and extraction time) to obtain a pomegranate juice with higher yield, polyphenol (e.g., catechin and delphinidin-3,5-glucoside) content, and related bioactivities (antioxidant and antidiabetic) than the one obtained by squeezing while maintaining the chemical-physical properties. Thus, this technique appears to be a functional alternative to producing high value pomegranate juice. [ABSTRACT FROM AUTHOR]

Three saponins, including two dimeric triterpenoid glucosides possessing an unusual skeleton, ivorenosides A and B, and a monomeric triterpenoid saponin (ivorenoside C), together with the known sericoside, were isolated from the bark of Terminalia ivorensis. Their structures were established on the basis of 1D and 2D NMR data, chemical methods and tandem MS–MS spectrometry as a dimer of β-ᴅ-glucopyranosyl-18,19-seco-2α,3β,19,19,24-pentahydroxyolean-12-en-28-oate and β-ᴅ-glucopyranosyl-2α,3β,19α,24-tetrahydroxyolean-12-en-28-oate (ivorenoside A, 1), a dimer of β-ᴅ-glucopyranosyl-18,19-seco-24-carboxyl-2α,3β,19,19-tetrahydroxyolean-12-en-28-oate and β-ᴅ-glucopyranosyl-2α,3β,19α,24-tetrahydroxyolean-12-en-28-oate (ivorenoside B, 2) and β-ᴅ-glucopyranosyl-2α,3β,19β,24-tetrahydroxyolean-11-oxo-olean-12-en-28-oate (ivorenoside C, 3). Ivorenosides A and B are the first examples in nature of dimeric triterpenoid saponins with a 18,19-seco E ring of one of the two units. These isolated compounds were evaluated for their antioxidant properties and further for their cytotoxic activity against four human cancer cell lines. Ivorenoside B and C exhibited scavenging activity against DPPH and ABTS+ radicals with IC50 values comparable with that of the standard drug Trolox and ivorenoside A showed antiproliferative activity against MDA-MB-231 and HCT116 human cancer cell lines with IC50 values of 3.96 and 3.43 μM, respectively. [ABSTRACT FROM AUTHOR]

Abstract: The aim of this work was to develop and validate a method to assess the dissolution behaviour of rociverine sugar-coated tablets. In our laboratories, an HPLC–MS in reverse phase method of analysis was developed for the dosage of unknown rociverine solution. This analytical method was applied to determine the dissolution rate of rociverine tablets produced by the industrial procedure, because there is no official method description. Dissolution tests were carried out in sink conditions as follows: dissolution medium HCl 0.01N, paddle rotation speed 50rpm and vessel volume 1000ml. The dissolution test gave satisfactory results: 95% of the drug was dissolved within 30min and drug dissolution was concluded after 60min. The method was demonstrated to be adequate for Quality Control of rociverine tablets. Validation was inferred from specificity, linearity, precision, accuracy and robustness. [Copyright &y& Elsevier]

Syntheses and spectroscopic features (IR, NMR and ESI MS) are reported for five 1:2 adducts of CuX with dppe (X=I, ClO4, NCS, O3SCF3 (≡tfs)BH4 dppe=Ph2P(CH2)2PPh2). ESI MS and 31P NMR spectroscopy indicate that these species dissociate in solution yielding free diphosphine and 3:2 species. A single crystal X-ray structure determination has been carried out on Cu(dppe)2NCS defining a four-coordinate complex of the form [(P,P′-dpex)M(P-dpex)X] for M=Cu, the thiocyanate being N-bound; the ionic [Cu(P,P′-dppe)2]tfs has also been structurally characterized. [Copyright &y& Elsevier]

New organotin(IV) derivatives containing the anionic dihydrobis(1-imidazolyl)borate [H2B(im)2]− have been synthesized from the reaction between SnRnX4−n (R=Me, Ph, nBu or Cy; n=1–3) acceptors and [K{H2B(im)2}·(DMAC)] (DMAC=dimethylacetamide). Mono-nuclear complexes of the type {[H2B(im)2]RnSnCl4−n−1} have been obtained, which have been fully characterized by elemental analyses and FT-IR in the solid state and by NMR (1H and 119Sn) spectroscopy, conductivity measurements and electrospray ionization mass spectrometry (ESIMS) in solution. ESIMS spectra of a methanol solution of the complexes show the existence of hydrolysed species for mono- and di-organotin(IV) derivatives, while non-hydrolysed aggregates are detected for triorganotin(IV) derivatives. [Copyright &y& Elsevier]

• Development of a new derivatization method for plant sterols/stanols. • The highest yields of derivatization were obtained using DMAP as catalyst, CH 2 Cl 2 as solvent at 40 °C for 30 min. • Dansylation improves the UV detection of plant sterols/stanols. • Dansylation allows the analysis of phytosterols by ESI-MS. • The derivatization method enhances the chromatographic separation of plant sterols/stanols. HPLC analyses of phytosterols are associated with the issues of sensitivity due to their high lipophilicity and their lack of chromophore. These problems could be solved through chemical modifications of plant sterols/stanols structures. Therefore, the present study aims to develop a new method for phytosterols derivatization. This method was performed using dansyl chloride (4 mg ml−1) as derivatizing agent and different reaction parameters have been optimized. The highest yields of phytosterol derivatization were obtained with 4‐dimethylaminopyridine (DMAP) as catalyst at a concentration of 8 mg ml−1 and dichloromethane as reaction solvent. In addition, 40 ˚C was the best reaction temperature for 30 min as the best reaction time. This derivatization method presented a high reproducibility (%RSD = 1.2–2.7%) and a good linearity (R2 = 0.9982–0.9999). The UV absorption intensities after derivatization showed a 23-fold increment for plant sterols and a 400-fold increment for plant stanols. Moreover, this derivatization method allowed the use of high and more selective wavelengths of detection and improved the chromatographic separation of phytosterols. Furthermore, the developed method allowed the ESI-MS ionization and analysis of phytosterols. This method can therefore contribute to the improvement of the HPLC analyses of plant sterols/stanols. [ABSTRACT FROM AUTHOR]

In recent years, special attention has been paid to the A 3 adenosine receptor (A 3 AR) as a possible pharmacological target to treat intestinal inflammation. In this work, it was set up a novel method to quantify the concentration of a promising anti-inflammatory agent inside and outside of intestinal barrier using the everted gut sac technique. The compound chosen for the present study is one of the most potent and selective A 3 AR agonist reported so far, named AR 170 (N 6 -methyl-2-phenylethynyl-5′- N -methylcarboxamidoadenosine). In order to evaluate the intestinal absorption of AR 170 the radioligand binding assay in comparison with HPLC-DAD was used. Results showed that the compound is absorbed via passive diffusion by paracellular pathway. The concentrations determined in the serosal (inside the sac) fluid by radioligand binding assay are in good agreement with those obtained through the widely used HPLC/MS protocol, demonstrating the reliability of the method. It is worthwhile to note that the radioligand binding assay allows detecting very low concentrations of analyte, thus offering an excellent tool to measure the intestinal absorption of receptor ligands. Moreover, the AR 170 quantity outside the gut sac and the interaction with A 3 AR could presuppose good topical anti-inflammatory effects of this compound. [ABSTRACT FROM AUTHOR]

Abstract Fraxinus angustifolia subsp. angustifolia is a plant with an age-old use for the production of manna. However, it is also a valuable source of fixed oil rich-seeds. In the present study we examined the chemical and biological properties of this oil in order to support a possible application in foodstuffs, nutraceuticals and cosmetics. Fatty acid composition, volatile and phenolic substances were evaluated. Oleic and linoleic acid represented 45.5% and 50.0%, respectively, of the total fatty acid composition. Among polar phenolic substances identified (secoiridoids, phenylethanoid glycosides, phenolic acids and alcohols, flavonoids, coumarins) isoverbascoside is for the first time reported in this species. Volatiles were mainly characterized by sesquiterpenes. The oil showed good antioxidant activity, in terms of ABTS radical scavenging activity, with an IC 50 value of 28.2 μg/mL. The antiproliferative activity was also investigated: amelanotic melanoma (C32) and lung carcinoma (A549) cells were the most sensitive with IC 50 values comparable to that of the positive control vinblastine. These findings shed light on the potential use of F. angustifolia subsp. angustifolia fixed oil in nutraceutics and cosmetics. Graphical abstract Unlabelled Image Highlights • Fixed oil extracted from the seeds of F. angustifolia subsp. Angustifolia investigated. • Volatile substances are mainly characterized by sesquiterpenes. • Among phenolics, for the first time isoverbascoside is detected in this oil. • A promising ABTS radical scavenging activity was found (IC 50 28.2 μg/mL). • IC 50 values similar to vinblastine are provided against C32 and A549 cancer cells. [ABSTRACT FROM AUTHOR]

The aim of the study was to identify new potential chemical markers of extra virgin olive oil (EVOO) quality by using a multicomponent analysis approach. Sixty-six EVOOs were purchased from the Italian market and classified according to their price as low price EVOOs (LEVOOs) and high price EVOOs (HEVOOs) costing 3.60–5.90 euro/L and 7.49–29.80 euro/L respectively. Sensory and chemical parameters strictly related to olive oil quality have been investigated, like volatile substances, polar phenolic substances, antioxidant activity, fatty acid composition, and α-tocopherol. Significant differences in terms of chemical composition and sensory features have been highlighted between the two EVOOs classes investigated, proving a generally lower level of quality of LEVOOs, clearly showed also by means of principal component analysis. Among the most interesting outcomes, R ratio (free tyrosol and hydroxytyrosol over total free and bound forms), measuring the extent of secoiridoids hydrolysis, resulted to be significantly higher in LEVOOs than in HEVOOs. Other key differences were found in the volatile substances composition, in the stearic acid percentage and in p -coumaric acid content. [ABSTRACT FROM AUTHOR]

Clams have long been a fisheries and aquaculture sector of great importance in Italy, the main resource of fisheries is the Chamelea gallina of indigenous origin, whereas clams breeding is supported almost entirely by the Tapes philippinarum , a species of Indo-Pacific origin. Bivalve molluscs quality depends mainly on the water quality, and then by a series of factors such as water temperature and salinity, gametogenic cycle, food availability, and environmental conditions, that affect the Condition Index. In this work crude extracts obtained from the edible part of Chamelea gallina and Tapes philippinarum were analyzed by a proteomic approach based on a two-dimensional gel electrophoresis followed by liquid chromatography-tandem mass spectrometry, in order to detect biomarkers useful for identification of the two kinds of clams and to assess their nutritional characteristics. As a result, four differentially expressed spots were found and identified, namely enolase, cyclophilin-A, ribosomal protein L13 and actin-1. [ABSTRACT FROM AUTHOR]

Legumes are an excellent source of macronutrients and phytochemicals as isoflavones. The aim of this work was to develop a new analytical method for determining five isoflavone compounds, three of which are aglycons, namely daidzein, genistein, biochanin A, and two of which, daidzin and genistin, are glycosilated, in lentils and other pulses, using an effective clean-up system and UHPLC–MS/MS (triple quadrupole) method. The recoveries obtained by spiking the lentil samples with a standard mixture of isoflavones at three levels of fortification (5, 25 and 100 μg kg −1 ) were in the range of 54.4–111.1%, 68.6–91.1%, and 84.4–114%, respectively. The method was applied to analyse 48 lentil samples from central Italy and pulses for determining the isoflavone content, which was found to range from 1.1 to 95.6 μg kg −1 . [ABSTRACT FROM AUTHOR]

In the present work we carried out a phytochemical and biological investigation on three Hypericum species, i.e. Hypericum reflexum , Hypericum canariense and Hypericum grandifolium , from the Canary Islands where they are traditionally used as diuretic, wound healing, vermifuge, sedative and antidepressive agents. The polar extracts of the top flowering aerial parts, prepared by Soxhlet apparatus using a methanol–acetone (1:1) extracting mixture, were analyzed by HPLC-DAD and HPLC-MS for the content of eight biomarkers such as hypericin, hyperforin, chlorogenic acid, rutin, hyperoside, isoquercitrin, quercitrin and quercetin, whereas the hydrodistilled essential oils were analyzed by GC-FID and GC-MS. The three Hypericum species had different results in both polar and volatile constituents, H . reflexum being the only one endowed with a small amount of naphtodianthrones (hypericin and pseudohypericin), and containing high levels of chlorogenic acid, rutin and volatile mono- and sesquiterpenes. After chemical characterization, all products were in vitro biologically assayed for antiproliferative activity on human tumor cell lines by MTT assay, for antioxidant potential by DPPH, ABTS and FRAP assays, and for antimicrobial activity by the agar disc diffusion and microdilution methods. Results revealed interesting bioactivities and differences between polar extracts and essential oils, with the former being endowed with significant antioxidant activity and the latter with comparable inhibition effects on the tumor cells (A375, MDA-MB 231 and HCT 116) to that of cisplatin. [ABSTRACT FROM AUTHOR]

The purpose of this study was to investigate the effect of pH and method of crystallization on the solid physical form of indomethacin (IDM). IDM, a non steroidal anti-inflammatory drug poorly soluble in water, underwent two different crystallization methods: crystallization by solvent evaporation under reduced pressure at 50.0 °C (method A), and crystallization by cooling of solution from 50.0 to 5.0 °C (method B). In both cases, several aqueous ethanolic solutions of IDM of different pHs were prepared. pHs were adjusted by adding acidic solutions (HCl 2 M) or alkali (NaOH or NH 4 OH 2 M) to an aqueous ethanolic solution of IDM. Thus, several batches were recovered after crystallization. The chemical stability of IDM was verified through 1 H NMR and mass spectroscopy (FIA-ESI-MS), that revealed that IDM degraded in strong alkali media (pH ≥ 12). Crystals obtained under different crystallization conditions at pHs of 1.0, 4.5, 7.0, 8.0, 10.0 and chemically stable were thus characterized for crystal habit by scanning electron microscopy, for thermal behaviour by differential scanning calorimetry, and thermogravimetry, and for solid state by X-ray powder diffractometry. Under the Method A, IDM always crystallized into pure metastable alpha form when solutions were acidified or alkalized respectively with HCl and NH 4 OH. On the contrary, in presence of NaOH, IDM crystallized under a mixture of alpha and sodium trihydrate form, because the presence of the sodium counter ion orientates the crystallization towards the formation of the trihydrate salt. Under the method B, at pH of 1.0, IDM crystallized under the alpha form; at pH 4.5, IDM crystallized under the form alpha in presence of some nuclei of gamma form; at pH 7.0, 8.0, and 10.0 for NH 4 OH, IDM crystallized under the most stable polymorph gamma form, whereas in presence of NaOH, a mix of alpha, and salt forms was formed whatever the pH of the solution. [ABSTRACT FROM AUTHOR]

Smyrnium olusatrum (Apiaceae), well known as wild celery, is a biennal celery-scented plant used for many centuries as a vegetable, then abandoned after the introduction of celery. In the present work, the essential oil obtained from inflorescences and the amounts of its main constituents isofuranodiene, curzerene and germacrone were analyzed by GC as well as by HPLC because of their degradation (Cope rearrangement) occurring at high temperatures. The oil and the main constituents were assayed for cytotoxic activity on the human colon cancer cell line (HCT116) by MTT assay. Flower oil and isofuranodiene showed noteworthy activity on tumor cells with IC50 of 10.71 and 15.06 μg/ml, respectively. Analysis of the cytotoxic activity showed that wild celery oil and isofuranodiene are able to induce apoptosis in colon cancer cells in a time and concentration-dependent manner suggesting a potential role as models for the development of chemopreventive agents. [ABSTRACT FROM AUTHOR]

Highlights: [•] The protozoan toxin climacostol exerts prooxidant activity in the presence of Cu(II) ions. [•] Climacostol binds to DNA. [•] The prooxidant activity can damage plasmid and eukaryotic DNA. [Copyright &y& Elsevier]

Abstract: Smyrnium olusatrum, better known as Alexanders or wild celery, is a biennal herb used in cuisine for many centuries by Romans in many dishes, where it has now been replaced by celery. In order to provide additional evidences so that this forgotten vegetable can be reconsidered in the human diet, as well as in pharmaceutics, the essential oils obtained from different parts and its main isolated furanosesquiterpenes were in vitro biologically assayed for antiproliferative activity on human tumor cell lines by MTT assay, for antioxidant potential by DPPH, ABTS and FRAP assays, and for antimicrobial activity by the agar disc diffusion method. The essential oils showed cytotoxic effects on tested human tumor cell lines, related to the furanosesquiterpenoid content; the IC50 values on colon carcinoma, glioblastoma, and breast adenocarcinoma cells were 8.51, 13.35, and 14.81μg/ml, respectively. Isofuranodiene and 1β-acetoxyfuranoeudesm-4(15)-ene resulted the most active constituents. The essential oils possessed also radical scavenging activity. [Copyright &y& Elsevier]

Abstract: Smyrnium olusatrum, well known as wild celery or Alexanders, is a biennial herb belonging to the Apiaceae and used for many centuries as an edible vegetable because of the aromatic flavour of its parts. Its use on the table has decreased since the Middle Ages when it was replaced by common celery (Apium graveolens). In the present work the composition of the essential oils obtained by hydrodistillation of various plant parts was investigated by gas chromatography (GC–FID and GC–MS), while quantitation of a heat-sensitive compound, isofuranodiene, known for its anticancer activity, and of its Cope rearrangement product curzerene, was achieved by HPLC-DAD. All essential oils were composed mainly of furanosesquiterpenoids (54.1–76.2%) with isofuranodiene (19.5–45.8%) as the main constituent. Results showed that GC analysis provides underestimation (up to five times) of isofuranodiene levels in essential oils and that curzerene could be considered an artifact since it is produced during heating of plant material, occurring during hydrodistillation. [Copyright &y& Elsevier]

Abstract: The aroma profile and the final quality of espresso coffee (EC) are influenced by such technical conditions as the EC machine extraction temperature and the pressure used. The effect of these two parameters on EC quality were studied in combination by headspace solid phase micro extraction–gas chromatography–mass spectrometry (SPME–GC–MS) and sensory profile. Moreover, 10 key odorants at the best EC machine settings were examined to compare the two coffee cultivars (Arabica and Robusta) and two EC machines [Aurelia Competizione (A) and Leva Arduino (B)]. The data obtained provides important information about espresso making technique, suggesting that the usual espresso machine temperature and pressure settings (i.e. 92°C and 9bar) are very close to those needed to obtain the best quality espresso. This confirms the traditional wisdom of coffee making, which judges 25ml, the typical volume of a certified Italian EC, to be ideal for very strong aroma intensity. [Copyright &y& Elsevier]

Abstract: Montepulciano is one of the most famous and important red-berried grapes of Italy. This article presents and discusses a comparative study of aroma profile and phenolic content of the Montepulciano wine from the Marches and the Abruzzo regions. The volatile composition of wines was determined by using headspace solid phase microextraction (HS-SPME) coupled with gas chromatography–mass spectrometry (GC–MS). The PDMS fibre was chosen. The dominating esters in Montepulciano wines were ethyl hexanoate, ethyl decanoate, and ethyl octanoate, whereas phenyl ethanol and 3-methyl-1-butanol were dominating alcohols. Phenolic compounds, namely gallic acid, p-coumaric acid, trans-ferulic acid, caffeic acid, trans-resveratrol, (+)-catechin and (−)-epicatechin, were examined using HPLC–MS with direct injection of wine samples. The total phenolic content of the analysed wines was in the range of 30.4–61.9mgl−1. The presence of high amounts of esters seems to characterise the volatiles of Montepulciano wines from the Marches, whereas a high level of alcohols was found in Montepulciano wines from Abruzzo. Moreover, multivariate chemometric techniques, such as cluster analysis and principal component analysis, supported this thesis. Headspace solid phase microextraction and gas chromatography–mass spectrometry were used to analyse 20 commercial wine samples (Montepulciano monovarietal red wines) from the Marches (10 samples) and Abruzzo (10 samples). [Copyright &y& Elsevier]

Abstract: Three new triterpenoid saponins, elucidated as 3-O-β-d-glucopyranosyloleanolic acid 28-O-β-d-xylopyranosyl-(1→4)-α-l-rhamnopyranosyl-(1→2)-β-d-xylopyranoside (parkioside A, 1), 3-O-[β-d-apifuranosyl-(1→3)-β-d-glucopyranosyl]oleanolic acid 28-O-[β-d-apifuranosyl-(1→3)-β-d-xylopyranosyl-(1→4)-[α-l-rhamnopyranosyl-(1→3)]-α-l-rhamnopyranosyl-(1→2)β-d-xylopyranoside (parkioside B, 2) and 3-O-β-d-glucuronopyranosyl-16α-hydroxyprotobassic acid 28-O-α-l-rhamnopyranosyl-(1→3)-β-d-xylopyranosyl-(1→4)-α-l-rhamnopyranosyl-(1→2)-β-d-xylopyranoside (parkioside C, 3), were isolated from the n-BuOH extract of the root bark of Butyrospermum parkii, along with the known 3-O-β-d-glucopyranosyloleanolic acid (androseptoside A). The structures of the isolated compounds were established on the basis of chemical and spectroscopic methods, mainly 1D and 2D NMR data and mass spectrometry. The new compounds were tested for both radical scavenging and cytotoxic activities. Compound 2 showed cytotoxic activity against A375 and T98G cell lines, with IC50 values of 2.74 and 2.93μM, respectively. Furthermore, it showed an antioxidant activity comparable to that of Trolox or butylated hydroxytoluene (BHT), used as controls, against 2,2-diphenyl-1-picryl hydrazyl (DPPH), 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS), oxygen and nitric oxide radicals. [Copyright &y& Elsevier]

Abstract: This present study was undertaken to examine treating effects of St. John''s Wort (SJW) extract on nociceptive perception of STZ-diabetic animals based on its potential antidiabetic and antinociceptive activities. One week administrations of SJW extract (125 and 250mg/kg) induced significant decrease in high blood glucose levels of three weeks STZ-diabetic rats and improved their dysregulated metabolic parameters. In addition, SJW extract treatment caused restoration in the mechanical hyperalgesia of diabetic animals. These findings provide a rationale for the traditional use of SJW against diabetes and display the potential of this plant as a new drug candidate/source for the treatment of diabetic pain. [Copyright &y& Elsevier]

Abstract: l-DOPA, the immediate biological precursor of dopamine, is still considered the drug of choice in the treatment of Parkinson’s disease. However, therapy with l-DOPA is associated with a number of acute problems. With the aim to increase the bioavailability after oral administration, we designed a multi-protected l-DOPA prodrugs able to release the drug by both spontaneous chemical or enzyme catalyzed hydrolysis. The new compounds have been synthesized and preliminarily evaluated for their water solubility, log P, chemical stability, and enzymatic stability. The results indicate that the incorporation of the amino acidic moiety of l-DOPA into an imidazoline-4-one ring provides prodrugs sufficiently stable to potentially cross unchanged the acidic environment of the stomach, and to be absorbed from the intestine. They also might be able to release l-DOPA in human plasma after enzymatic hydrolysis. The ability of prodrugs 6a–b to increase basal levels of striatal DA, and influence brain neurochemistry associated with dopaminergic activity following oral administration, as well as the radical-scavenging activity against DPPH for compounds 6a–b and 15a are also reported. [Copyright &y& Elsevier]

Abstract: Two triterpenoid saponins have been isolated from the seed kernels of Entada rheedii. Their structures have been established using 1D- and 2D-NMR and mass spectrometry as 3-O-β-d-xylopyranosyl-(1→3)-O-α-l-arabinopyranosyl-(1→6)-2-acetylamino-2-deoxy-β-d-glucopyranosylentagenic acid 28-O-β-apiofuranosyl-(1→3)-β-d-xylopyranosyl-(1→2)-β-d-glucopyranoside (Rheediinoside A, 1) and 3-O-β-d-glucopyranosyl-(1→3)-O-[β-d-xylopyranosyl-(1→3)-α-l-arabinopyranosyl-(1→6)]-2-acetylamino-2-deoxy-β-d-glucopyranosylentagenic acid 28-O-β-apiofuranosyl-(1→3)-β-d-xylopyranosyl-(1→2)-β-d-glucopyranoside (Rheediinoside B, 2). Compounds 1 and 2 were tested for their antiproliferative activity against T98G, A431, PC3 and B16-F1 cell lines, and further for their antioxidant properties. Moderate cytotoxic potency and antioxidant properties were found for these compounds whereas Rheediinoside B was in all assays more active than Rheediinoside A. [Copyright &y& Elsevier]

• Organic chicken meat in biodegradable packaging. • Renewable and compostable biopackaging to preserve chicken meat. • Chicken meat shelf-life study through chemical, microbiological and sensorial parameters. • New biopackaging can preserve organic chicken meat similarly to plastic material. Widespread use of traditional packaging constitutes a serious ecological problem leading to a shift to biodegradable and compostable materials. The aim of this work is to study the ability of a new biopackaging (BP), based on biodegradable and compostable material, to preserve the quality of organic chicken meat for 14 days in comparison with a polyethylene terephthalate (PET) material. Results showed that the indices of Biogenic Amines (BAs) and the 18 monitored Volatile Organic Compounds (VOCs) have a similar trend in both packaged meats. For example, the total BAs concentration in meat increased from 390 to 961 mg Kg−1 in BP and from 393 to 800 mg Kg−1 in PET, as well as the microbiological counts. The new biopackaging (BP) showed similar properties of non-biodegradable material (PET) to preserve the shelf life of organic chicken meat and it could be used instead of plastic materials to promote a circular economy. [ABSTRACT FROM AUTHOR]

Abstract: One of the most discussed and studied aspects of the silver(I) coordination complexes chemistry is the influence of the counterions in the solid state structures and in the ligand exchange reactions occurring in solution; this kind of chemistry is pretty rare in the gold(I) coordination derivatives. Some silver(I) and gold(I) complexes of the type L2M2X2 (where L is 1-benzyl-2-imidazolyl diphenylphosphine I, M=Ag, X=BF4 II; X=NO3 III, X=CF3SO3 IV, X=BAr4 V), L3M2X2 (M=Ag, X=NO3 VI, X=BF4 VII, X=BAr4 VIII, X=CF3SO3 IX), LAuCl (X), L2Au2X2 (X=BF4, XI) and L2AuBF4 (XII) have been synthesized. The solid state structures of the compounds I, II, III, and X have been already reported, that of XII will be published elsewhere, whilst the unprecedented structure of IX is discussed here. From the analysis of the structures, it can be argued that in the silver(I) complexes the counterions deeply affect the structure by strongly interacting with the metal centres. Here we report, in addition to the discussion of the structure of IX, the study of these complexes by the ESI mass spectrometry with the target of both studying the counterion effect in the ionization process, and to characterize the above described complexes by this new soft mass spectrometry technique. [Copyright &y& Elsevier]

[Display omitted] • A fast LC–MS/MS method for the analysis of 98 NPS from hair is described. • Various NPS targeted including tryptamines, cathinones, opioids, and cannabinoids. • NPS extraction with M3® reagent followed by acidic and basic purification. • The method validation showed good performance parameters and reduced matrix effect. • It can be applied to routine toxicological studies in analytical laboratories. In this study, a rapid liquid chromatography-tandem mass spectrometry (LC–MS/MS) method has been developed and validated for the targeted analysis of 98 New Psychoactive Substances (NPS) from the hair matrix. The monitored compounds included various chemical classes (7 phenethylamines, 10 tryptamines, 18 cathinones, 24 synthetic opioids, and 38 synthetic cannabinoids) with emphasis given to newly emerged NPS. The method employed a direct extraction process through the incubation of hair samples (25 mg) and internal standards with M3® reagent at 100 °C for 60 min, followed by extract purification through acid and basic liquid-liquid micro-extraction (LLME). Extracted compounds were analyzed through LC–MS/MS system operating in multiple reaction monitoring mode. NPS were separated in 9.5 min with a Poroshell 120 EC-C18 column (2.7 μm, 4.6 × 50 mm) using a gradient eluting mobile phase composed of water and acetonitrile/water (95:5) both containing 0.1 % of formic acid. The developed and validated method shows a good precision (≤ 15 %), linearity (R2 between 0.993 and 0.999), selectivity, and sensitivity (LOD: 0.6–10.3 pg mg−1 and LOQ: 2.1–34.4 pg mg−1). The method showed also reduced matrix effect and acceptable recovery for most of the targeted compounds. Our results showed that this method is suitable for quantifying NPS in hair matrix and could be employed in the context of routine analyses in analytical laboratories. [ABSTRACT FROM AUTHOR]