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In this paper, the preliminary results of a study aimed to discriminate between the different species of lichens, from which orchil dyes originate, are presented. A multi-analytical approach has been used to analyze several species of lichens, in particular Roccella tinctoria DC, Lasallia pustulata L. and Ochrolechia tartarea L., in an attempt to identify distinguishing markers within different orchil mixtures. In the first part of the research, samples of yarns dyed with the different species, prepared in laboratory after the proper raw lichens treatment, have been subjected to SERS on fiber analyses. Hence an innovative ammonia protocol has been applied to all the specimens. Firstly, in order to evaluate the difference among the different species, HPTLC has been applied to the extracts of dyed yarns and the dye baths. All the spots present on the TLC plates have been analyzed through SERS (HPTLC-SERS), in order to obtain a SERS database of each single compound, fixed on the yarns. Then, HPTLC-MS and HPLC-MS experiments have been carried out, in order to deep into the identification of compounds corresponding to each spot. [ABSTRACT FROM AUTHOR]

Trifluoromethyl aldimines derived from α-amino esters have proven to be very good starting materials to obtain the title compounds. A Ag 2 O-catalyzed Mannich-type/cyclization cascade reaction starting from suitable α-isocyano acetates leads to enantiopure valuable trans -carboxylic trifluoromethyl substituted 2-imidazolines by a highly stereoselective addition without the need to add organocatalysts. [ABSTRACT FROM AUTHOR]

The phytochemical analysis on the leaves of a new population of Araucaria columnaris (G.Forst.) Hook. was reported. Seven compounds were identified i.e., 15-agathic acid methyl ester (1), ladanein (2), 7,4′,7″,4‴-tetra- O -methyl-robustaflavone (3), 3- O - trans - p -coumaroyl-quinic acid (4), 4- O - trans - p -coumaroyl-quinic acid (5), 5- O - trans - p -coumaroyl-quinic acid (6) and shikimic acid (7). Chromatographic and spectroscopic techniques were utilized for this. Their presence is important from the chemophenetic point of view, but further research is necessary to make final conclusions on this species. • The phytochemical analysis on the leaves of Araucaria columnaris was reported. • This study regards a new European population. • Seven compounds were successfully identified. • Four compounds are new for the family, two for the genus and one for the species. • The chemotaxonomic importance of these compounds was adequately discussed. [ABSTRACT FROM AUTHOR]

Aqueous extracts of roasted pistachio (Pistacia vera) from different geographic origin were analyzed by 1H nuclear magnetic resonance (NMR) spectroscopy. Forty-eight water-soluble metabolites, classified in organic acids, amino acids, carbohydrates and miscellaneous metabolites, were identified by means of 1D and 2D NMR experiments, and twenty-eight of them were quantified. The different metabolite contents highlighted that pistachios from different regions have peculiar metabolic features that could be employed for quality control and to improve the requisites for protected or certified designation of origin regulations. For these purposes, multivariate statistic analysis (PCA and PLS-DA) was applied to the obtained metabolite profiles in order to assess the geographic origin of nuts from Aleppo (Syria), Sanliurfa (Turkey), Rafsanjan (Iran) and Bronte (Italy), and spontaneous clustering was observed. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • A sample of Euphorbia peplus L. collected in Central Italy was studied for its phytochemical profile. • The analysis was carried out by means of Column Chromatography, NMR Spectroscopy and Mass Spectrometry. • Fourteen compounds were identified belonging to 5 different classes of natural compounds. • An NMR semi-quantitative analysis was performed on the diterpene fraction. • The chemotaxonomic and ethnopharmacological relevance of the results were extensively discussed. Abstract In this work, the phytochemical profile of the ethanolic extract of Euphorbia peplus L. collected in Central Italy, was reported. This specimen had never been studied before and the analysis was accomplished by means of Column Chromatography for the separation procedure and by means of NMR Spectroscopy and Mass Spectrometry for the identification step. In particular, fourteen compounds were evidenced belonging to five different classes of natural compounds i.e. triterpenoids (pentacyclic and saponin), peculiar diterpenoids (jatrophanes and pepluanes), flavonoids (flavonols), caffeoyl-quinic acids and rare disaccharides. In addition to this, a semi-quantitative analysis on the diterpenoid fraction, by means of NMR Spectroscopy, was also performed in order to provide the real quantities of these compounds in the same fraction and in the total extract. Due to the pronounced chemo variability observed in Euphorbia spp., the availability of a reliable and quick analytical technique, such as that reported in the present study, could be a useful tool in the standardization of plant materials to be used in pharmacological studies or for ethnomedicinal purposes. The technical details for both the general phytochemical analysis and the specific quantitative one, were inserted in this paper. Moreover, the chemotaxonomic and ethnopharmacological relevance of these compounds was also discussed. [ABSTRACT FROM AUTHOR]

Tansy daisy ( Tanacetum macrophyllum (Waldst. et Kit.) Schultz Bip., Asteraceae) is a perennial herb worldwide cultivated for ornamental and industrial purposes. Sometimes, this species is misidentified by herb collectors and botanists with its family mate Achillea grandifolia (white yarrow). In the present work, we have analysed the essential oil and ethanolic extract obtained from the aerial parts of tansy daisy cultivated in Italy and evaluated the biological activity in terms of cytotoxic, antioxidant and anticholinesterase activities. The essential oil was analysed by gas chromatographic and mass spectrometry (GC–MS) and showed oxygenated monoterpenes, namely camphor, linalool and 1,8-cineole, and sesquiterpenes, namely germacrene D and 10- epi -γ-eudesmol, as the major components. The ethanolic extract of aerial parts was subjected to chromatographic separation and this permitted the identification of 12 polar compounds belonging to five different classes of natural products, namely flavonoids (apigenin, cirsimaritin, apigenin-7- O -glucoside, apigenin-7- O -glucuronide, kaempferol-7- O -glucoside and kaempferol-7- O -glucuronide), dicaffeoylquinic derivatives (3,5-dicaffeoylquinic and 4,5-dicaffeoylquinic acids), caffeoylquinic acids (chlorogenic acid), free organic acids (shikimic and quinic acids) and glycosidic organic acids (4- O -β- d -glucopyranosyl-vanillic acid); among them apigenin and kaempferol derivatives were the most abundant. Finally, the essential oil from the leaves, containing high levels of germacrene D and 10- epi -γ-eudesmol, was highly effective against the proliferation of A375 (melanoma) and HCT116 (colon carcinoma) human tumor cells, showing IC 50 values of 9.2 and 8.5 μg/mL, respectively. On the other hand, the ethanolic extract scavenged the DPPH and ABTS + radicals, showing IC 50 of 32.7 and 37.2 μg/mL, respectively. The inhibitory properties of tansy daisy essential oils and ethanol extract on the acetylcholinesterase enzyme were also evaluated. These findings provided new insights into the phytochemistry of the species and its possible applications on an industrial level. [ABSTRACT FROM AUTHOR]

In this work, the first specific phytochemical analysis on Odontites vulgaris Moench collected in Central Italy was performed. The aerial parts ethanolic extract was studied and eight compounds were identified: pheophytin a (1), aucubin (2), catalpol (3), shanzhiside methyl ester (4), melampyroside (5), 8- epi -loganin (6), caryoptoside (7) and quinic acid (8). To the best of our knowledge, in this study, compounds (7–8) resulted to be isolated from the genus for the first time. The chemophenetic markers of the family and order were evidenced and several important ecological conclusions could be drawn. The ethanolic extract was also tested for several biological activities showing high effects in the antioxidant, cytoprotective and aflatoxin B1 production inhibitory assays. A brief explanation on these activities under the phytochemical standpoint was also included. [Display omitted] • Phytochemical analysis on the aerial parts of Odontites vulgaris Moench was reported. • A new population from Central Italy was studied. • Chemophenetic evaluation of the phytochemical results was added. • Biological activities of the ethanolic extract were performed. • The correlation between biological activities and phytochemistry was discussed. [ABSTRACT FROM AUTHOR]

Preparation and characterization of a block-like l , d -octapeptide-dextran conjugate DEX 29 -(l -Val- d -Val) 4 self-assembling into nanowire structures is reported. The conjugate was prepared by solid phase click-chemistry on an alkyne group N-terminus functionalized peptide with a regularly alternating enantiomeric sequence. Low molecular weight dextran (X n = 29) with moderately low dispersity (1.30) was prepared by controlled acid hydrolysis and dialysis with selected cut-off and functionalized with an azido group on the reducing end by reductive amination. The strong hydrogen bonds and hydrophobic interactions of the (l -Val- d -Val) 4 linear peptide drive the conjugate to self-assemble into long (0.1–1 μm) nanowires. To our knowledge, this is the first example of a peptide-polysaccharide conjugate that can self-assemble into a nanowire architecture. [ABSTRACT FROM AUTHOR]

Hepatitis C virus (HCV) infection induces a long-term inflammatory response and oxidative-stress in the liver microenvironment, leading to hepatic fibrosis and metabolic alterations. Direct-acting-antiviral-agents (DAAs) induce HCV-clearance, even though liver damage is only partially restored. In this context, understanding the impact of viral-eradication on liver metabolic activities could allow optimizing the metabolic care of the patient. The present prospective longitudinal study aims at characterizing the urinary metabolic profile of HCV-induced severe liver fibrosis and the metabolic changes induced by DAAs and HCV-clearance by nuclear magnetic resonance-based metabolomics. The urinary metabolic profile of 23 HCV males with severe liver fibrosis and 20 age-matched healthy-controls was analyzed by NMR-based-metabolomics before starting DAAs, at the end-of-therapy, after one and three months of follow-up. The urinary metabolic profile of patients with severe liver fibrosis was associated to pseudouridine, hypoxanthine, methylguanidine and dimethylamine, highlighting a profile related to oxidative damage, and to tyrosine and glutamine, related to a decreased breakdown of aromatic aminoacids and ammonia detoxification, respectively. 1-methylnicotinamide, a catabolic intermediate of nicotinamide-adenine-dinucleotide, was significantly increased in HCV-patients and restored after HCV-clearance, probably due to the reduced hepatic inflammation. 3-hydroxy-3-methylbutyrate, an intermediate of leucine-catabolism which was permanently restored after HCV-clearance, suggested an improvement of skeletal muscle protein synthesis. Finally, 3-hydroxyisobutyrate and 2,3-dihydroxy-2-methylbutyrate, intermediates of valine-catabolism, glycine and choline increased temporarily during therapy, resulting as potential biomarkers of DAAs systemic effects. [Display omitted] • Urinary metabotypes were related to liver fibrosis, HCV-clearance and DAA treatment. • Severe liver fibrosis urinary metabotype was evidenced despite HCV eradication. • 1-MNA decrease after HCV-clearance was associated to a reduced hepatic inflammation. • 3-HMB increase after HCV-clearance was associated to protein synthesis in muscles. • Transient modifications of amino acid metabolism were induced by DAA treatment. [ABSTRACT FROM AUTHOR]

Sodium lauryl ether sulfates (SLES) are a class of surfactants, among the most used in the formulations of healthcare products. Although largely used in industry, literature studies are hereto completely missing of the characterization of some species, as sodium lauryl triether sulfates (E3S), and of the effect of several assembly parameters, as temperature. Moreover, drastic disparity of assembly performance subsists among laboratory synthesized and industrial raw SLES, generating problems in the real-world applications of formulations design. We report on the self-assembly analysis of industrial grade sodium lauryl monoether sulfate (E1S), sodium lauryl diether sulfate (E2S) and laboratory synthesized E3S. The surfactants were studied in a large range of NaCl concentrations (0.1–1 M NaCl) and as function of the temperature by crossing Surface Tension, Small-Angle X-ray Scattering and Dynamic Light Scattering measurements. Such analysis enabled to establish systematic relationship between the molecular structure and assembly properties of the surfactants and to define size and morphologies variations of the aggregates. We observed that i) core-shell spherical aggregates evolve towards elongated core-shell structures upon addition of NaCl, ii) the elongation is higher the lower the number of the ether groups iii) E3S is greatly stable in the analyzed temperature range (20 °C - 60 °C), iv) the industrial grade SLES exhibit a minimum of the surface tension and an anticipated self-assembly as a function of concentration, probably due to the presence of hydrophobic impurities. Impurities are also detected by DLS in unfiltered samples of the industrial grade SLES as large particles. Moreover, a case of industrial interest was investigated: the instability of formulations comprising of E3S and 3,4,5-trimethoxybenzoic acid. Such information enriches the quite small literature on pure SLES self-assembly, rationalizing new and literature data within a unified framework. [Display omitted] [ABSTRACT FROM AUTHOR]

Abstract: Background: Resveratrol, a polyphenol found in plant products, has been shown to regulate many cellular processes and to display multiple protective and therapeutic effects. Several in vitro and in vivo studies have demonstrated the influence of resveratrol on multiple intracellular targets that may regulate metabolic homeostasis. Methods: We analysed the metabolic modifications induced by resveratrol treatment in a human hepatoblastoma line, HepG2 cells, using a 1H-NMR spectroscopy-based metabolomics approach that allows the simultaneous screening of multiple metabolic pathways. Results: Results demonstrated that cells cultured in the presence or absence of resveratrol displayed different metabolic profiles: the treatment induced a decreased utilisation of glucose and amino acids for purposes of energy production and synthesis associated to a decreased release of lactate in the culture medium and an increase in succinate utilisation. At the same time, resveratrol treatment slowed the cell cycle in the S phase without inducing apoptosis, and increased Sirt1 expression, also affecting its intracellular localisation. Conclusions: Our results show that the metabolomic analysis of the exometabolome of resveratrol-treated HepG2 cells indicates a metabolic switch from glucose and amino acid utilisation to fat utilisation for the production of energy, and seem in agreement with an effect mediated via AMPK- and Sirt1-activation. General significance: NMR-based metabolomics has been applied in a hepatocyte cell culture model in relation to resveratrol treatment; such an approach could be transferred to evaluate the effects of nutritional compounds with health impact. [Copyright &y& Elsevier]

Abstract: The synthesis and characterization of a tetranuclear Pt complex, cis–trans–cis–trans tetra[μ-2,6-diethynyl-4-nitroaniline-bis(tri(p-tolyl)phosphine) platinum(II)], namely [L2Pt-DENA]4 with L=tri-p-tolylphosphine, is reported. The complex was obtained by the dehydrohalogenative condensation of 2,6-diethynyl-4-nitroaniline (DENA) with cis-[dichlorobis(tri(p-tolyl)phosphine)platinum(II)]. The single crystal structure determination of [L2Pt-DENA]4 indicated the formation of a neutral molecular cycle with four alternating platinum units in cis and trans configurations, all bridged with DENA spacers with the presence of solvent (toluene) crystallization molecules. A twisted tetranuclear cyclic feature was identified. The formation of intermolecular stacks of the tetranuclear complex in solution was assessed by means of nuclear Overhauser enhancement spectroscopy (NOESY) and rotating frame Overhauser effect spectroscopy (ROESY) characterizations. [Copyright &y& Elsevier]

[Display omitted] • Hydrophilic gold nanoparticles for melamine detection were prepared. • The melamine was successfully detected in the range 2.5−500 ppm. • The sensing method based on the melamine-induced aggregation of AuNPs. • The recognition process is mediated by electrostatic interactions. In the last years, intense efforts have been made in order to obtain colloidal-based systems capable of pointing out the presence of melamine in food samples. In this work, we reported about the recognition of melamine in aqueous solution, using gold nanoparticles stabilized with 3-mercapto-1-propanesulfonate (AuNPs-3MPS), with the aim of deepening how the recognition process works. AuNPs were synthesized using a wet chemical reduction method. The synthesized AuNPs-3MPS probe was fully characterized, before and after the recognition process, by both physicochemical (UV–vis, FT-IR, 1H-NMR, DLS and ζ-potential) and morphostructural techniques (AFM, HR-TEM). The chemical and electronic structure was also investigated by SR-XPS. The sensing method is based on the melamine-induced aggregation of AuNPs; the presence of melamine was successfully detected in the range of 2.5−500 ppm. The results achieved also demonstrate that negatively charged AuNPs-3MPS are potentially useful for determining melamine contents in aqueous solution. SR-XPS measurements allowed to understand interaction mechanism between the probe and the analyte. The presence of sulfonate groups allows a mutual interaction mediated by electrostatic bonds between nanoparticles surface thiols and positively charged amino groups of melamine molecules. [ABSTRACT FROM AUTHOR]

• Six divers were monitored during two experiments of exposure to hyperbaric atmosphere in dry and wet conditions • 30 minutes at 3 atmospheres increased the urinary excretion of 8-oxoGuo and 8-oxodGuo after 1.5 hours in dry and 4 hours in wet conditions • The levels of 8-oxoGuo and 8-oxodGuo tend to return to the baseline after 12 hours • NMR untargeted profiling of urine has individuate some statistically significant differences between Dry and Wet sessions • NMR shows that Hypoxanthine level increases during the wet exposure similarly to those of 8-oxoGuo and 8-oxodGuo Occupational exposure to hyperbaric atmosphere occurs in workers who carry out their activity in environments where breathing air pressure is at least 10% higher than pressure at sea level, and operations can be divided in Dry or Wet activities. The increased air pressure implies the formation of reactive oxygen species (ROS) and reactive nitrogen species (RNS), consumption of antioxidants and reduction of antioxidant enzyme activity, causing lipid peroxidation, DNA and RNA damage. The present study was aimed to establish the relation between hyperbaric exposure and metabolic changes due to ROS unbalance, by means of the determination of urinary biomarkers of oxidatively generated damage to DNA and RNA during a controlled diving session. The investigated biomarkers were 8-oxo-7,8-dihydroguanine (8-oxoGua), 8-oxo-7,8-dihydroguanosine (8-oxoGuo), and 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodGuo). The experimental session involved six experienced divers subjected to 3 atmospheres absolute for 30 minutes in two different experiments, in both dry and wet conditions. Urine samples were collected at t = 0 (before exposure) and 30 (end of exposure),90, 240, 480 and 720 minutes. The concentration of 8-oxoGua, 8-oxoGuo, and 8-oxodGuo was determined by isotopic dilution high performance liquid chromatography (HPLC-MS/MS). In all subjects there is an increase of the urinary excretion of 8oxo-Guo and 8oxo-dGuo, in both conditions, after 1.5 - 4 hours from the start of the experiment, and that the values tend to return to the baseline after 12 hours. Besides that, also the nucleic magnetic resonance (NMR)-based untargeted metabolomics was employed for the same objective on the same samples, confirming a different metabolic response in the subjects exposed to dry or wet conditions. In particular, the observed hypoxanthine urinary level increases during the underwater hyperbaric exposure, in agreement with the trend observed for 8-oxoGuo and 8-oxodGuo levels. Present results confirmed the relationship between exposure and oxidative stress and depicted a clear temporal trend of the investigated biomarkers. Due to the possible negative consequences of oxidative stress on workers, present research shows a new line in term of risk prevention. [ABSTRACT FROM AUTHOR]

Abstract In this work, the fifth part of an ongoing phytochemical study on Wollemia nobilis was reported. The attention was now focused on the male reproduction organs of which the content in both primary and secondary metabolites was analyzed. Twenty compounds, belonging to seven different classes of natural compounds, were identified from the ethanolic extract by means of Column Chromatography and NMR and MS Spectroscopy. They all represent new compounds for the studied organ whereas some of them are also new constituents of the genus or even previously undescribed phytochemicals. Their presence was able to display a general overview of these organs from the phytochemical standpoint and to provide more elements in confirmation with the current botanical classification of the species. Moreover, they add a further experimental evidence of the tendency of this species to accumulate different metabolites in different organs. This characteristic as well as the occurrence of several compounds with added value, make this plant a possible candidate for large scale cultivation with extractive purposes to obtain useful phytochemicals for botanicals and pharmaceutical fields. Moreover, they offer the opportunity to develop an additional method of conservation and protection for this endangered and very rare species. Graphical abstract Unlabelled Image Highlights • Two new secondary metabolites were isolated and identified. • A differential accumulation of metabolites in the various organs was observed. • A possible sustainable source of added value phytochemicals was suggested. • The chemotaxonomy relevance of isolated compounds was discussed. [ABSTRACT FROM AUTHOR]

Abstract An undescribed labdane-like diterpene with a rare spiro-β-lactone function was identified from the ethanol extract of the male cones of the coniferous tree Wollemia nobilis. This spirolabdadienolide (IUPAC name: syn - ent -8(17),13-labdadien-19,18-olid-15-oic acid methyl ester; trivial name: wollemolide), was isolated by means of traditional and high performance chromatography techniques and structurally elucidated through NMR and MS. In addition, six further known metabolites were evidenced in the extract. Wollemolide, which may be considered an additional chemotaxonomic marker, and 4′- O -methyl-scutellarein, a simple flavonoid, had not been isolated in our previous phytochemical study on the same plant organ. This demonstrates how the molecular pattern of a plant species is in continuous movement and changes with the passing of time according to the climate of the year. Graphical abstract Image 1 Highlights • A reassessment of Wollemia nobilis male cones was carried out. • An undescribed syn - ent -labdadiene derivative was isolated. • A seasonal variability of metabolites was observed. • This is the first report on the presence of simple flavonoids in W. nobilis. • The chemosystematic relevance of isolated compounds was discussed. [ABSTRACT FROM AUTHOR]

Abstract The influence of Synthetic Organic Pigments in the degradation of Acrylem AC 33, a waterborne acrylic binder, after UVB-artificial exposure was furtherly investigated, extending the study to other pigments classes (anthraquinones, phthalocyanines, diketo-pyrrolo-pyrroles) in addition to previously studied azo-pigments. Together with Fourier Transform Infrared, both in Attenuated Reflectance and Transmission mode, and Nuclear Magnetic Resonance spectroscopies, Raman spectroscopy was also used to observe ageing processes that pigments are subjected to. Specific effects, relative to the presence of different pigments, have been observed also in this study; moreover, Raman spectroscopy highlighted photoinduced effects on some pigments, which could result useful in Cultural Heritage diagnostics, especially for street artworks. Highlights • Combination of NMR, FTIR and Raman spectroscopies to study UVB induced degradation phenomena. • Influence of carbonyl, phthalocyanines and diketo-pyrrolo-pyrrole pigments on UV degradation of acrylic binder. • Variations in Raman spectra of pigments deriving from UVB photodegradation. [ABSTRACT FROM AUTHOR]

The preparation and characterization of a novel linear d , l -octapeptide-poly(ethylene glycol) conjugate, formulated as biocompatible nanocarrier of hydrophobic drugs, was reported. The PEGylated d , l -octapeptide was designed to self-assemble in core-shell nanoparticles with rod-like morphology obtained by exploiting the self-assembling properties of linear peptides with regularly alternating enantiomeric sequences in tubular structures. The conformational properties of the conjugate and its self-assembling capability were assessed through dynamic light scattering, energy filtered-transmission electron microscopy, scanning electron microscopy, circular dichroism, fluorescence, and proton nuclear magnetic resonance spectroscopy. Furthermore, the upload in peptide-polymer nanoparticles of curcumin, adopted as model of hydrophobic drugs, was performed. In fact, despite accumulating evidence suggests that curcumin has different therapeutic activities, its use in medicine is limited to the very low water solubility, low bioavailability and chemical instability. This work addresses such drawbacks showing that nanoparticles obtained by For-( d -Phe- l -Cys(Acm)) 4 -NH-(CH 2 -CH 2 -O) 45 -CH 3 self-assembly are effective carriers for curcumin with high drug loading and sustained drug release. [ABSTRACT FROM AUTHOR]

Helichrysum stoechas (L.) Moench is one of the scientific names of everlasting flower, which has traditionally been used as an ornamental, medicinal and food plant. The aim of this study was to identify the main phytochemical constituents as well as to evaluate the potential of this plant in terms of antioxidant, antidiabetic and neuroprotective activities. The phytochemical analysis of the methanolic extract allowed for the identification of ten constituents mainly of phenolic nature and with chemosystematic relevance: two heterodimeric phloroglucinols, arzanol ( 1 ) and compound ( 3 ), one homodimeric α-pyrone, helipyrone ( 2 ), three phenolic acids, p -hydroxybenzoic ( 4 ), caffeic ( 5 ) and neochlorogenic ( 6 ) acids, one polymethoxylated and two glycosidic flavonoids, 5,7-dihydroxy-3,6,8-trimethoxyflavone ( 7 ), isoquercitrin ( 8 ) and quercetagetin-7- O -glucopyranoside ( 9 ) together with santinol B ( 10 ). Bioassays showed significant antioxidant and antiproliferative effects and for the first time the potential of Helichrysum stoechas to inhibit the MAO-A, AChE and TYR enzymes, as well as to exert anti-α-glucosidase and anti-dipeptidyl peptidase-4 activities. [ABSTRACT FROM AUTHOR]

Caralluma fimbriata Wall. is currently used as a “natural slimming” food supplement, likely due to its content in pregnane glycosides. In the present study, a commercially available Caralluma fimbriata extract (Slimaluma ® ; CFE, 100 mg/kg) has been evaluated for its ability to affect the ingestive behaviour in female rats, also with reference to the modulation of the brain neuropeptides NPY and ORX.The interference of CFE with α-amylase and lipase enzymes has been investigated in vitro , as possible peripheral mechanism of action. Also, the chemical composition of CFE has been assessed by NMR and spectrophotometric analysis. Results from in vivo study showed that CFE induced effects neither on blood parameters, nor on liver and gut histomorphology. Interestingly, a reduction in body weight gain with an increase in water intake and hypothalamic levels of NPY and ORX peptides were found. Phytochemical analysis, showed CFE contained about 12% of pregnane glycosides and 1.3% of polyphenols. Present results suggest possible effects of C. fimbriata on ingestive behaviour, likely mediated by central and peripheral mechanisms. [ABSTRACT FROM AUTHOR]

In this paper, an innovative alkaline mild extraction method has been applied to characterize the dyes present in lake-pigment and textile, prepared from American and Armenian cochineal. This extraction methodology, successfully employed for the conservation of glycosyl moieties in anthraquinone dyes from madder ( Rubia tinctorum L.), is applied on cochineal lake and textiles in order to evaluate if its application results in obtaining new information about cochineal dyes composition. Furthermore, in this paper, a slightly modified ammonia-Na 2 EDTA extraction methodology is presented. The modification of the extraction methodology resulted to be necessary to ensure its applicability to this class of natural dyes. Once optimized the protocol, the extracts have been analyzed through HPLC-HRMS, in order to characterize the present compounds. In particular, basing on the MS/MS paths reported in literature, it has been possible to recognize several O -glycosyl compounds, never found before in American cochineal dyed yarns or lake pigments extracts. In particular, for the first time, an O -glycoside of flavokermesic acid, known as pp6, suggested until this moment as a marker of Polish cochineal, has been recognized in both lake-pigment and dyed yarns prepared from American cochineal. In addition, it has been possible to compare the composition of American cochineal dyed yarns ammonia-Na 2 EDTA extracts with those obtained from Armenian cochineal dyed yarn, extracted with the same protocol. [ABSTRACT FROM AUTHOR]

Olive oil mill wastewaters (OMW) cause serious environmental pollution problems due to their high level of production and specific chemical characteristics. An innovative disposal treatment and simultaneous valorization technology consists of using OMW as a no-cost substrate for mixed microbial culture (MMC)-based polyhydroxyalkanoates (PHAs) production process. Here, an MMC multi-stage process was developed in which after acidogenic fermentation, OMW was subjected to a solid liquid separation step by centrifugation. The resulting solid fraction was converted into methane through anaerobic digestion in order to recover energy for the process, whereas the liquid fraction was used as feedstock for both the biomass selection and the PHA accumulation step. Most of OMW soluble chemical oxygen demand (COD) content in the liquid fraction (approximately 70%) was removed in a sequencing batch reactor (SBR) obtaining a high PHA production (about 532 mgCOD, in the feast phase). In particular, the strategy to uncouple COD feed from nitrogen supply within the SBR cycle, along with the operation of a settling phase before the famine phase, allowed to enhance the selective pressure towards PHA-storing microorganisms. Polymer production significantly increased in the accumulation reactor up to approximately 2470 mgCOD/L. Finally, anaerobic digestion tests on the OMW solid fraction showed a relevant COD conversion into methane (up to 100%). [ABSTRACT FROM AUTHOR]

In this study, The behavior of Acrylem AC 33–a waterborne paint binder, chemically a ethyl acrylate-methyl methacrylate copolymer-after an UVB-artificial ageing was evaluated. In particular, it has been investigated its behavior in presence of three different azo-pigments – Pigment Red 9, Pigment Yellow 3 and Pigment Yellow 74-, in order to evaluate the effects of these pigments on photodegradation processes of the medium. For this aim, Fourier Transformed InfraRed, both in Attenuated Reflectance and transmission mode, and Nuclear Magnetic Resonance Spectroscopies were used. Thanks to this multianalytical approach, the chemical variations, both on the surface and on the bulk of the pictorial film, have been assessed and the degradation products of surfactant present in the binder were identified. Furthermore, specific effects of these synthetic organic pigments on the photodegradation of the matrix and its additives were observed. The information obtained from this study can be employed in the characterization of differential ageing phenomena in artworks, especially in case of outdoor exposition as it occurs in street-art conditions. [ABSTRACT FROM AUTHOR]

Teucrium polium L. is a species with ancient ethno-botanical uses for its anti-inflammatory action which is mainly due to the phenolics content. On the other side, the presence of neo -clerodanes, which exert hepatotoxic action, may explain why in recent years the medicinal uses of this species have drastically diminished. In this paper we report on the isolation of a new natural neo -clerodane diterpenoid, namely 20- O -acetyl-teucrasiatin ( 2 ), together with other twelve relevant compounds in the fields of chemotaxonomy and ethnomedicine. Nevertheless, the total absence of iridoids and in particular of the chemotaxonomic markers of the family and of the genus itself, may reveal an intraspecific variability of T. polium with different chemotypes which may contain or not iridoids. [ABSTRACT FROM AUTHOR]

In this paper, we present a new alkaline mild extraction technique of madder dyes in lake and textile, based on the use of ammonia, in association with disodium EDTA. This method was developed in order to preserve the glycoside compounds fixed on the fiber or present in the lake. This new methodology was performed on samples of dyed textile and lake, prepared following the ancient recipes. At first, the extracts, obtained from these samples, were analyzed and characterized by 1D and 2D NMR (DOSY) and ESI-MS. In the second step, we evaluated the applicability and the efficiency of extraction on real samples of 1 mg, analyzed by HPLC–DAD and HPLC–MS. These analyses allow us to recognize the signals, referable to glycoside compounds, also in 1 mg samples. The new proposed method was compared with a commonly applied mild extraction method reported in literature (DMF–Na 2 EDTA method). Finally, the results obtained from the different analytical techniques applied allow us to conclude that the ammonia extracts of madder dyed yarn and lake are mainly composed of glycosylated anthraquinones, according to literature. [ABSTRACT FROM AUTHOR]

The goal of this study was to develop an optimized drug delivery carrier for oral mucosa applications able to release in situ bioactive molecules by using biopolymeric materials. Among them chitosan and poly(lactic-co-glycolic acid) (PLGA) have gained considerable attention as biocompatible carriers able to improve the delivery of active agents. The formulation of such vehicles in the form of nanoparticles (NPs) could permit to exploit the peculiar properties of nanomaterials in order to enhance the efficacy of active agents. Chitosan (CS) and PLGA chlorexidine dihydrochloride (CHX)-loaded NPs were synthesized by ionotropic gelation and osmosis based methodology respectively. In order to facilitate NPs adhesion on human dental surfaces, two different strategies were employed: PLGA particles with an external shell of CS to produce a positive surface charge allowing CHX loaded PLGA NPs to interact with the negative charged dental surfaces, while CS particles were functionalized with peptidomimetic derivative glutathione (GSH). The morphology was investigated by scanning electron microscopy. A sustained release profile of CHX from CS NPs was achieved. CS-based NPs adhered on human tooth surfaces in a simulated brushing and rinsing process and their in vitro toxicity evaluation on Human Gingival Fibroblasts (HGFs) was between 20 and 60% in all experimental conditions. Thanks to their adhesion properties and low cytotoxicity, the synthesized CS-based formulations may be efficiently exploited for therapy purposes or to enhance in vivo dental care (i.e. preparation of toothpastes or other cosmetics for daily oral care). [ABSTRACT FROM AUTHOR]

Abstract: Background: Aging is characterized by derangements in multiple metabolic pathways that progressively constrict the homeostatic reserve (homeostenosis). The signature of metabolic alterations that accompany aging can be retrieved through the metabolomic profiling of biological fluids. Objective: To characterize the age-related changes in urinary and fecal metabolic profiles of BALB/c mice through a 1H nuclear magnetic resonance (NMR)-based metabolomic approach. Methods: Young (n=19) and old (n=13) male BALB/c mice were fed ad libitum standard laboratory chow. Twenty four-hour feces and urine were collected using metabolic cages and analyzed by high-resolution 1H NMR spectroscopy combined with multivariate statistical analyses. Results: An age-related metabolic phenotype was detected both in urine and feces. The metabolic signature of aging consisted of changes in levels of metabolites associated with amino acid metabolism, tricarboxylic acid cycle, tryptophan–nicotinamide adenine dinucleotide pathway, and host–microbiota metabolic axis. Conclusions: Our 1H NMR-based metabolomic approach was able to characterize the effect of age on urinary and fecal metabotypes. The implementation of this analytical strategy may increase our understanding of the metabolic alterations involved in the aging process and assist in the design of anti-aging interventions. [Copyright &y& Elsevier]

Abstract: During the 2009 FINA World Aquatics Championships high-tech swimsuits were used to add buoyancy, stability, speed and endurance. The design of a material must meet several requirements. In particular, it is of crucial importance the in-depth investigation of the chemical and physical characteristics of the material itself. Data relating to the mobility of water molecules adsorbed by polymer network is a key element in view of properties in understanding the material since they are related to inter-relationship between the fluid medium and macromolecules. In the present work, the water in interaction with the polymer network of fabrics for competition swimsuit has been studied by Time Domain NMR (TD NMR) in order to better understand the molecular motions of polymer chains and solvent molecules inside the structure. Commercial materials, consisting of polyamide and elastane in different ratios, have been examined by NMR relaxometry. Results showed the presence of several types of water, each one characterized by its mobility. Using qualitative and quantitative analyses of NMR, data have been evaluated on the mechanical characteristics of the examined materials. The developed methodology in this paper is a general approach that opens up new perspectives for the study of swim wear fabric. [Copyright &y& Elsevier]

Abstract: Chiral racemic α-diimines, tested in aziridination reactions with NsONHCO2Et, for the first time led to the synthesis of (±)-bidiaziridines, stereoselectively derived from the corresponding meso (E-s-trans-E)-α-diimines. Moreover, a minor bidiaziridine isomer, probably a meso form that was lost under classical work-up conditions, can be obtained by adding water to the crude mixtures at the end of amination reactions. The results definitively prove that the imine aziridination by carbamates is a two-step domino process. The structures of the compounds were determined using 2D NMR on purified bidiaziridines. [Copyright &y& Elsevier]

Age-related dysbioses of intestinal microbiota and decline in the overall metabolic homeostasis are frequently found in the elderly. Probiotic supplementation may represent a way to prevent or reduce the senescence-associated metabolic disorders. The present study evaluated the metabolic impact of Lactobacillus acidophilus La5 and Bifidobacterium lactis Bb12 supplementation in relation to age by analyzing urine and feces metabolic profiles using ¹H-nuclear magnetic resonance spectroscopy and multivariate analysis. Adult (3 mo old) and aged (16 mo old) mice received an oral supplementation of the 2 probiotics (1 x 109 colony-forming units/d each) or phosphate buffered saline (control) daily for 30 d. Urine and feces were collected for 48 h before the end of the study. Partial least squares-discriminant analysis showed that the urinary discriminant metabolites for the probiotic treatment included higher dimethylglycine in adult and aged mice, lower sarcosine and nicotinate in adult mice, higher N-methylnicotinamide in adult mice and lower N-methylnicotinamide in aged mice compared with their controls. These results indicate a probiotic-induced modulation of homocysteine and NAD metabolism pathways, which have important implications because these pathways are involved in essential cellular processes that can be altered in senescence. The probiotic supplementation also modified the fecal metabolic profiles, inducing in both adult and aged mice higher 4-hydroxyphenylacetate and lower xylose in treated mice compared with their control mice, whereas valerate was greater in treated adult mice and lower in treated aged mice compared with their controls. The ANOVA simultaneous component analysis on urinary and fecal metabolic profiling showed an age x treatment interaction (P < 0.05}, confirming the age-related modulation of the metabolic response to probiotic supplementation. The results suggest that L. acidophilus and B. lactis may prevent or reduce age-related metabolic dysfunction. [ABSTRACT FROM AUTHOR]

Abstract: The aim of this study was to individuate, by bioassay-guided fractionation, promising antifungal fractions and/or constituents from Hypericum perforatum subsp. angustifolium in vitro roots. Treatments with chitosan, O-carboxymethylchitosan (CMC) and its derivatives were used to improve xanthone production in the roots. The bioassay-guided fractionation of CMC-treated roots led to the individuation of an ethyl acetate fraction, containing the highest amount of xanthones (6.8%) and showing the best antifungal activity with minimal inhibitory concentration (MIC) values of 53.82, 14.18, and 36.52 μg/ml, against Candida spp., Cryptococcus neoformans and dermatophytes, respectively. From this fraction the prenylated xanthone, biyouxanthone D has been isolated and represented the 44.59% of all xanthones detected. For the first time in the present paper biyouxanthone D has been found in H. perforatum roots and tested against C. neoformans, dermatophytes, and Candida species. The xanthone showed the greatest antifungal activity against C. neoformans and dermatophytes, with MIC values of 20.16, 22.63 μg/ml. In conclusion, the results obtained in the present study demonstrated that CMC-treated Hpa in vitro root extracts represent a tool for the obtainment of promising candidates for further pharmacological and clinical studies. [Copyright &y& Elsevier]

Gold nanoparticles (AuNPs) are promising carriers in the field of nanomedicine and represent a very intriguing approach in drug delivery applications, due to their small size and enhanced properties. This work aims to highlight the interaction between functionalized AuNPs and the immune-system suppressant drug Methotrexate (MTX) at molecular level. Small and monodisperse (<2R H >5 ± 1 nm) gold nanoparticles were prepared by a simple chemical route using hydrophilic thiol 3-mercapto-1-propanesulfonate (3MPS) as a functionalizing/capping agent and act as a platform for post-synthesis conjugation of MTX via non-covalent interaction. The AuNPs-3MPS@MTX bioconjugate and the AuNPs alone were characterized to investigate their optical, chemical, and morphological properties. Moreover, NMR, AFM, SAXS, HR-TEM and SR-XPS data confirmed the spherical shape of AuNPs and allowed to determine the mechanisms behind such drug-nanoparticle physicochemical interactions. These analyses define the overall structure of drug-loaded AuNPs-3MPS and drug location on the colloidal nanoparticles surface. Based on the experimental data, it is notable to assert that MTX was successfully loaded on the negatively charged nanoparticles surface via electrostatic interactions. The physicochemical behavior leads to the formation of large clusters with close packed arrangement of AuNPs-3MPS@MTX. This self-assembling property is of importance for delivery purpose affecting the drug-loaded nanoparticle size, functionality, and morphology. Knowledge of how these systems behave will aid in increasing drug efficacy and in understanding the pharmacodynamics and pharmacokinetic properties, opening to new physicochemical insight for therapy and drug delivery systems. The interaction between methotrexate drug and 3-mercapto-1-propanesulfonate functionalized gold nanoparticles was studied with the aim to highlight the overall structure of drug-loaded nanoparticles. The nature of interaction can be categorized into electrostatic binding between amine groups of MTX and negatively charged thiols on gold nanoparticles surface. This interaction results in a formation of large clusters with densely packed arrangement, as demonstrated by combined SAXS, HR-TEM and SR-XPS studies. Unlabelled Image • Functionalized AuNPs loaded with Methotrexate drug. • The physicochemical interaction between AuNPs and MTX was clarified. • AFM, SAXS and HR-TEM analyses highlighted the formation of densely packed clusters. • NMR and SR-XPS data indicated an interaction via electrostatic binding. [ABSTRACT FROM AUTHOR]

The execution of many genetic programs, influenced by environmental conditions, is epigenetically controlled. Thus, small molecules of the intermediate metabolism being precursors of most of nutrition-deriving epigenetic modifications, sense the cell surrounding environment. Here we describe histone H4K16 acetylation distribution in S. cerevisiae nhp6ab mutant, using ChIP-seq analysis; its transcription profile by RNA-seq and its metabolic features by studying the metabolome. We then intersected these three -omic approaches to unveil common crosspoints (if any). In the nhp6ab mutant, the glucose metabolism is switched to pathways leading to Acetyl-CoA synthesis. These enhanced pathways could lead to histone hyperacetylation altering RNA transcription, particularly of those metabolic genes that maintain high Acetyl-CoA availability. Thus, the absence of chromatin regulators like Nhp6 A and B, interferes with a regulative circular mechanism where histone modification, transcription and metabolism influence each other and contribute to clarify the more general phenomenon in which gene regulation feeds metabolic alterations on epigenetic basis. This study allowed us to identify, in these two factors, a common element of regulation in metabolism and chromatin acetylation state that could represent a powerful tool to find out relationships existing between metabolism and gene expression in more complex systems. Unlabelled Image • nhp6ab Strain shows globally hyperacetylated histones particularly at H4K16. • Metabolomic analysis shows altered glucose metabolism in the nhp6ab mutant. • Transcriptome and H4K16 acetylome are altered in the nhp6ab mutant. • NHP6A/B Affect a circuit involving histone acetylation, metabolism and transcription. [ABSTRACT FROM AUTHOR]