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The treatment of used vegetable oil (UVO) with seven different adsorbents and through two different procedures (stirring and gravity filtration) was explored. Important differences in terms of density, turbidity, electrical resistance, free fatty acids (FFAs) content and relative fatty acid distribution were observed. Different outcomes were shown depending both on the adsorbent and on the procedure. Lower values of density and FFAs were registered for oils treated by gravity filtration with portland (respectively 0.6% and 0.81 g/ml) and celite (respectively 0.7% and 0.72 g/ml). Considering the undesired leaching from the powder to the oil, related to the turbidity, the celite resulted more suitable for the oil recycling (241 Nephelometric Turbidity Unit (NTU) for portland vs 184 NTU for celite). In addition, Fourier-transform infrared spectroscopy combined with multivariate analysis allowed to determine a chemical fingerprint relative characteristic of vegetable oils recycled by gravity or by adsorption by stirring.

Wine comprises a beloved food and human companion since the early times of humans on earth. In this study, wine samples of different type (red, white, and rose) and variety (Agiorgitiko, Augoustiatis, Cabernet Sauvignon, Syrah, Vlahiko, Assyrtiko, Chardonnay, Debina, Moschofilero, Vidiano, Syrah plus Mandilari, and Xinomavro) were subjected to physico-chemical and aroma compounds analyses, in an effort to characterize their identity and discriminate these samples according to variety using statistics. Results showed significant differences (p

The treatment of used vegetable oils (UVOs) with clays represents a pivotal step in their industrial recycling process as well as one of the most challenging topics for researchers. In particular, cheap, effective, and sustainable powders need to be explored in order to develop new processes which produce beneficial results in relation to economic and environmental aspects. In this context, five samples within commercial and waste vegetable oils were treated with two sodium- and calcium-based bentonites employing a low oil/bentonite ratio (0.15 wt%). The outcomes of the processes were monitored by FT-IR spectroscopy and compared with the data relative to the parent commercial edible oil. In particular, treatment of FT-IR data by multivariate statistical analysis allowed us to determine a chemical fingerprint characteristic of each sample. Important relationships between the overall chemical composition and the specific clay employed and the treatment time (2 or 4 h) were highlighted. Finally, N2 physisorption, TEM microscopy, and FT-IR analyses of the more efficient Na bentonite allowed us to characterize the material and thus to furnish all the information needed to set-up a general protocol for the partial regeneration of waste vegetable oil destined for further processing.

Three ternary mixtures composed by choline chloride (ChCl), ethylene glycol (EG) and a second hydrogen bond donor (HBD) as ethanol (A), 2-propanol (B), and glycerol (C) were studied in terms of composition related to the band gap energy (BGE). A Design of Experiments (DoE) approach, and in particular a Simple Lattice three-components design, was employed for determining the variation of the BGE upon the composition of each system. UV-VIS analysis and subsequent Tauc plot methodology provided the data requested from the DoE and multivariate statistical analysis revealed a drop of the BGE in correspondence to specific binary compositions for systems A and B. In particular, a BGE of 3.85 eV was registered for the mixtures ChCl/EtOH (1:1), and ChCl/2-propanol (1:1), which represents one of the lowest values ever observed for these systems.

The synthesis of heteroleptic monomeric cationic Rh(I) bis-diphosphine complex [Rh(dppe)(dppp)]Cl (dppe = 1,2-bis-(diphenylphosphino)ethane and dppp = 1,3-bis-(diphenylphosphino)propane) was achieved by reaction between the neutral dimeric complex [Rh2(dppe)2(μ2-Cl)2] and the dppp ligand. The corresponding complex [Rh(dppe)(dppp)]BF4 was instead obtained from reaction between [Rh(dppe)(nbd)]BF4 (nbd = bicyclo-[2.2.1]-hepta-2,5-diene) and the dppp ligand. Previous protocols had extended to the synthesis of the analogous homoleptic complexes containing two dppe or two dppp ligands. The structural analysis of such complexes conducted in the solid state by single-crystal x-ray crystallography and in solution by 31P and 1H NMR revealed a distorted square planar geometry where the anion and the cation are not bonded each other. Nevertheless, important differences in reactivity can be found if same complexes with different anions are compared, as in the case of the phosphine exchange reaction between [Rh(dppp)2]X (X = Cl−, BF4−) and the dppe ligand or in the case of the employment of such complexes as catalytic precursors for the transfer hydrogenation reaction from 2-propanol to acetophenone.

The production of saffron spice generates large quantities of plant by-products: over 90% of the plant material collected is discarded, and a consideration fraction of this waste is plant stamens. This work investigated the chemical composition and the antimicrobial activities of the non-polar fraction extracted from four different saffron flower stamens. The chemical composition of ethereal extracts of the saffron stamens was qualitatively assessed by means of gas–chromatography-mass spectrometry (GC-MS) and nuclear magnetic resonance (NMR) analyses. These analyses revealed ethereal extracts to possess a high polyunsaturated fatty acid content. In vitro antibacterial activity of stamen extracts showed no large differences between Gram-positive and Gram-negative bacteria in terms of minimal inhibitory concentration (MIC). In food matrix microbial analysis of the bacterial strains belonging to the main foodborne pathogen species, including Staphylococcus aureus DSM 20231, Escherichia coli DSM 30083, and Listeria monocytogenes DSM 20600, using low-fat UHT milk, revealed a statistically significant reduction in the number of cells (particularly for E. coli and S. aureus with a complete elimination of the population of the two target bacteria following incubation in diethyl ether extracts of saffron stamen (DES) at high concentrations tested, both at 37 °C and 6 °C (for 48 h and 7 days, respectively). A synergic effect was observed when the pathogens were incubated at 6 °C with DES. This work shows these by-products to be excellent sources of bioactive compounds, which could be exploited in high-added-value products, such as food, cosmetics, and drugs.

Three ternary mixtures composed by choline chloride (ChCl), ethylene glycol (EG), and a second hydrogen bond donor (HBD) as ethanol (A), 2-propanol (B), and glycerol (C) were studied in terms of composition related to the band gap energy (BGE). A Design of Experiments (DoE) approach, and in particular a Simple Lattice three-components design, was employed for determining the variation of the BGE upon the composition of each system. UV-VIS analysis and subsequent Tauc plot methodology provided the data requested from the DoE, and multivariate statistical analysis revealed a drop of the BGE in correspondence to specific binary compositions for systems A and B. In particular, a BGE of 3.85 eV was registered for the mixtures ChCl/EtOH (1:1) and ChCl/2-propanol (1:1), which represents one of the lowest values ever observed for these systems.

The selective formation of the heterocyclic salt ((1,4-dioxane-2,5-diyl)-bis-(methylene))-bis-(triphenylphosphonium) chloride was observed when epichlorohydrin and triphenylphosphine were reacted in CH2Cl2 at room temperature. Slow evaporation from a mixture of ethanol and ethyl acetate allows to isolate monocrystals of the heterocyclic phosphonium salt. Mechanistic investigations point to the formation of the zwitterionic intermediate 1-chloro-3-(triphenylphosphonio)-propan-2-olate, which can dimerize and generate the 1,4-dioxane derivative. In the exclusive presence of a Brønsted acid as HCl, which usually facilitates epoxide ring opening, the exclusive formation of 1,3-dichloro-2-propanol was although observed. Also, when epichlorohydrin, PPh3, and a stoichiometric amount of HCl were mixed, (2-chloro-3-hydroxypropyl)-triphenylphosphonium chloride was formed and its isolation in pure form provides monocrystals subjectable to X-ray analysis.

Deep Eutectic Systems (DESs) are obtained by combining Hydrogen Bond Acceptors (HBAs) and Hydrogen Bond Donors (HBDs) in specific molar ratios. Since their first appearance in the literature in 2003, they have shown a wide range of applications, ranging from the selective extraction of biomass or metals to medicine, as well as from pollution control systems to catalytic active solvents and co-solvents. The very peculiar physical properties of DESs, such as the elevated density and viscosity, reduced conductivity, improved solvent ability and a peculiar optical behavior, can be exploited for engineering modular systems which cannot be obtained with other non-eutectic mixtures. In the present review, selected DESs research fields, as their use in materials synthesis, as solvents for volatile organic compounds, as ingredients in pharmaceutical formulations and as active solvents and cosolvents in organic synthesis, are reported and discussed in terms of application and future perspectives.

The employment of easily affordable ruthenium(II)-complexes as pre-catalysts in the transfer hydrogenation of carbonyl compounds in deep eutectic media is described for the first time. The eutectic mixture tetrabutylammonium bromide/formic acid = 1/1 (TBABr/HCOOH = 1/1) acts both as reaction medium and hydrogen source. The addition of a base is required for the process to occur. An extensive optimization of the reaction conditions has been carried out, in terms of catalyst loading, type of complexes, H2-donors, reaction temperature and time. The combination of the dimeric complex [RuCl(p-cymene)-μ-Cl]2 (0.01–0.05 eq.) and the ligand dppf (1,1′-ferrocenediyl-bis(diphenylphosphine)ferrocene) in 1/1 molar ratio has proven to be a suitable catalytic system for the reduction of several and diverse aldehydes and ketones to their corresponding alcohols under mild conditions (40–60 °C) in air, showing from moderate to excellent tolerability towards different functional groups (halogen, cyano, nitro, phenol). The reduction of imine compounds to their corresponding amine derivatives was also studied. In addition, the comparison between the results obtained in TBABr/HCOOH and in organic solvents suggests a non-innocent effect of the DES medium during the process.

Films with different morphology can be obtained by mixing fish gelatin, Tara gum and glycerol in different ratio and by subjecting the Tara gum to a ball milling treatment before its use. The amount of the plasticizer glycerol, as well as the type of Tara gum employed (as received or milled) resulted, from SEM and AFM analyses, to strong influencing the morphology of the films and their density. Also, the morphological differences determine different thermal and mechanical behaviours. In particular, the employment of milled Tara gum allows to improve the thermal stability, as well as the mechanical properties of the polymers. A similar outcome can be obtained by increasing the glycerol content, which can be used up to 20 wt%. Glycerol amounts exceeding that percentage, are detrimental for the quality of the films and reduce their thermal and mechanical performances., FEDER (Fondo Europeo de Desarrollo Regional) and both the Spanish Agencia Estatal de Investigacióon (MAT2017–84501-R; MAT2017-88923-P) and the Consejería de Educación, Junta de Castilla y León (BU306P18)

The unprecedented Nazarov cyclization of a model divinyl ketone using phosphonium-based Deep Eutectic Solvents as sustainable non-innocent reaction media is described. A two-level full factorial Design of Experiments was conducted for elucidating the effect of the components of the eutectic mixture and optimizing the reaction conditions in terms of temperature, time, and substrate concentration. In the presence of the Deep Eutectic Solvent (DES) triphenylmethylphosphonium bromide/ethylene glycol, it was possible to convert more than 80% of the 2,4-dimethyl-1,5-diphenylpenta-1,4-dien-3-one, with a specific conversion, into the cyclopentenone Nazarov derivative of 62% (16 h, 60 &deg, C). For the reactions conducted in the DES triphenylmethylphosphonium bromide/acetic acid, quantitative conversions were obtained with percentages of the Nazarov product above 95% even at 25 &deg, C. Surface Responding Analysis of the optimized data furnished a useful tool to determine the best operating conditions leading to quantitative conversion of the starting material, with complete suppression of undesired side-reactions, high yields and selectivity. After optimization, it was possible to convert more than 90% of the model substrate into the desired cyclopentenone with cis percentages up to 77%. Experimental validation of the implemented model confirmed the robustness and the suitability of the procedure, leading to possible further extension to this specific combination of experimental designs to other substrates or even to other synthetic processes of industrial interest.

Due to the ever-increasing worldwide interest in the exploitation of waste vegetable oils, the development of analytical tools able to detect their adulteration with edible oils, is considered a priority for the scientific and industrial community. In this work, edible and waste vegetable oils have been analysed by Fourier Transform-InfraRed (FT-IR) and Ultraviolet-Visible (UV–VIS) spectroscopies and the corresponding spectral data subjected to statistical multivariate analysis for classification purposes. In particular, Principal Component Analysis (PCA) and Partial Least Square Discriminant Analysis (PLS-DA) were performed in order to develop an analytical tool which is able to distinguish between edible and waste vegetable oil. Qualitative analysis of the spectra suggested FT-IR and UV–VIS as the more suitable techniques to distinguish between wastes and edible samples. Also, statistical multivariate analysis revealed that FT-IR-based methodology is more adequate for the target, even if the elevated sensibility of the method produces an undesired distinction between edible oils of the same type. Finally, further attempts on UV–VIS data obtained in reflection mode allowed to produce a good dataset which after statistical treatment gave a clear differentiation between edible and waste oil samples.

The development of analytical techniques for characterizing food samples, especially for the wine industry, is a main topic of research. Regarding the classification of wines based on their geographical origin, nuclear magnetic resonance (NMR) spectroscopy represents a fast and effective tool for determining chemical fingerprints. Herein, a 13C NMR dataset, which was acquired for classification of Grecian wines through multivariate statistics, is reported and described. Thus, the main qualitative differences between grapes of the same geographical origin, observable by the visual analysis of the 13C NMR data, are discussed.

A relevant improvement of the cultivar conditions of Rosmarinus officinalis L. in desert areas was achieved by a specific combination between irrigation system and soil conditioner. A drastic reduction of water employment was obtained without affect the quality of the plants, determined by monitoring growth parameters and essential oil characteristics. In particular, the effect of surface and subsurface drip irrigation systems and different soil conditioners on growth parameters, yield, and essential oil constituents of rosemary plant was assessed. Field experiments at the Agricultural Research Station (Al-Adlya farm), SEKEM group Company, El-Sharkiya Governorate, Egypt, conducted over the two seasons revealed the effectiveness of the subsurface irrigation system in obtaining better performances, especially in terms of water saving. The combination of subsurface irrigation and the conditioner Hundz soil with bentonite showed the maximum mean values of growth characters compared with other soil amendments during both seasons. The possibility to employ a water-saving irrigation system as the subsurface one without any drawback in the resulting plants was also explored in terms of molecular composition. GC-MS analysis of the essential oil extracted from plants growth under different irrigation conditions revealed a comparable composition in both cases. The goodness of the most performing system was also confirmed by the comparable yield of the essential oil.

An integrated approach, based on quantitative transmission mode powder X-ray diffraction (PXRD) combined with multivariate statistical analysis, has been applied to cellulose obtained from three different sources to correlate the mercerization degree and crystallinity with the cellulose type, temperature, and reaction time. The effects of the experimental conditions on the two outcomes were studied by design of experiments (DoE) and surface responding analysis (SRA) combined with principal component analysis (PCA). SRA showed a marked influence of the type of cellulose (wood cellulose from the kraft vs. sulfite process, WCK vs. WCS) on the conversion of cellulose I to cellulose II (CII%) during mercerization. A counterintuitive simultaneous effect of temperature and cellulose type was also highlighted. The data elaboration in the form of response surface plots provided an easy predictive tool for the optimum conditions to maximize the conversion. The simulation reported for WCK showed maximum conversion (96%) at 70 &deg, C in 24 h with 18%wt NaOH.

The employment of used vegetable oils (UVOs) as raw materials in key sectors as energy production or bio-lubricant synthesis represents one of the most relevant priorities in the European Union (EU) normative context. In many countries, the development of new production processes based on the circular economy model, as well as the definition of future energy and production targets, involve the utilization of wastes as raw material. In this context, the main currently applied EU regulations are presented and discussed. As in the EU, the general legislative process consists of the definition in each State Member of specific legislation, which transposes the EU indications. Two relevant countries are herein considered: Italy and Spain. Through the analysis of the conditions required in both countries for UVOs&rsquo, collection, disposal, storage, and recycling, a wide panorama of the current situation is provided.

The optical properties of nine choline-based Deep Eutectic Solvents (DESs) of the type choline+X− (X− = chloride or acetate)/Y (Y = ethylene glycol, glycolic or levulinic acid) were studied by measuring their band gap through the UV-VIS-based Tauc method. All the considered systems showed a direct optical transition. A correlation between band gap and eutectic composition was discovered by plotting the variation of the band gap versus the molar fraction of choline+X−/Y in the parent systems containing 10 wt% of H2O. The main parameters influencing the energy of the optical transition in these “Deep Band Gap Systems” (DeBaGS) where studied through Design of Experiments (DoE) combined with multivariate analysis. The effect on the band gap of the anion (chloride or acetate), the acid (levulinic or glycolic), the water, and the stirring time, considered as single factor or in combination was clarified. Thus a multivariate model was implemented through surface responding analysis which allows engineering such kind of systems and opening to further applications in material science.

The identification and quantification of free fatty acids (FFA) in edible and non-edible vegetable oils, including waste cooking oils, is a crucial index to assess their quality and drives their use in different application fields. NMR spectroscopy represents an alternative tool to conventional methods for the determination of FFA content, providing us with interesting advantages. Here the approaches reported in the literature based on 1H, 13C and 31P NMR are illustrated and compared, highlighting the pros and cons of the suggested strategies.

Multivariate Surface Responding Analysis (SRA) was employed for optimize the water treatment procedure of Waste Cooking Oils (WCOs) in terms of density and flash point temperature. The simultaneously effect of pH, oil/water ratio, temperature, time and of their combinations on the process outcome were elucidated and exploited for enhance the quality of the recycled oil and the sustainability of the overall treatment.

A relevant improvement of the cultivar conditions of Rosmarinus officinalis L. in desert areas was achieved by a specific combination between an irrigation system and soil conditioner. A drastic reduction in water employment was obtained without affecting the quality of the plants, which was determined by monitoring the growth parameters and essential oil characteristics. In particular, the effect of surface and subsurface drip irrigation systems and different soil conditioners on the growth parameters, yield, and essential oil constituents of rosemary plants was assessed. Field experiments at the Agricultural Research Station (Al-Adlya farm), SEKEM Group Company, El-Sharkiya Governorate, Egypt, conducted over the two seasons, revealed the effectiveness of subsurface irrigation systems in obtaining better performances, especially in terms of saving water. The combination of subsurface irrigation and the conditioner HUNDZ soil with bentonite showed the maximum mean values of growth characteristics compared with other soil amendments during both seasons. The possibility to employ a water-saving irrigation system at the subsurface level without any drawback in the resulting plants was also explored in terms of molecular composition. Gas chromatography-mass (GC-MS) analysis of the essential oils extracted from plants grown under different irrigation conditions revealed a comparable composition in both cases. The quality of the system that showed the best performance was also confirmed by the comparable yield of the essential oil.

Recently, the interest in converting waste cooking oils (WCOs) to raw materials has grown exponentially. The driving force of such a trend is mainly represented by the increasing number of WCO applications, combined with the definition, in many countries, of new regulations on waste management. From an industrial perspective, the simple chemical composition of WCOs make them suitable as valuable chemical building blocks, in fuel, materials, and lubricant productions. The sustainability of such applications is sprightly related to proper recycling procedures. In this context, the development of new recycling processes, as well as the optimization of the existing ones, represents a priority for applied chemistry, chemical engineering, and material science. With the aim of providing useful updates to the scientific community involved in vegetable oil processing, the current available technologies for WCO recycling are herein reported, described, and discussed. In detail, two main types of WCO treatments will be considered: chemical transformations, to exploit the chemical functional groups present in the waste for the synthesis of added value products, and physical treatments as extraction, filtration, and distillation procedures. The first part, regarding chemical synthesis, will be connected mostly to the production of fuels. The second part, concerning physical treatments, will focus on bio-lubricant production. Moreover, during the description of filtering procedures, a special focus will be given to the development and applicability of new materials and technologies for WCO treatments.

Salvia verbenaca is a perennial herbaceous plant well appreciated as medicinal herb which can be found in Mediterranean area, Europe, Africa and Asia. In this study, S. verbenaca flowers and leaves were collected in six different geographical areas of Sardinia (Italy). Information about the variation of the chemical composition of plants grown in different locations were obtained from gas chromatography analysis of the extracted essential oils. Gas chromatography analysis detected 33 compounds, which have been grouped in oxygenated monoterpenes, monoterpene hydrocarbons, sesquiterpenes and other compounds. The chemical composition of each group resulted significantly affected by sampling site in terms of geography and altitude. Concerning the geographical distribution of the detected chemicals, sesquiterpenes were found in considerable amount in three localities, monoterpenes hydrocarbons in two and other compounds were predominant only in one site. Regarding the altitude level, monoterpenes, sesquiterpenes and other compounds were predominant, respectively, at medium and medium-high altitude.

The reduction of ketones through homogeneous transfer hydrogenation catalyzed by transition metals is one of the most important routes for obtaining alcohols from carbonyl compounds. The interest of this method increases when opportune catalytic precursors are able to perform the transformation in an asymmetric fashion, generating enantiomerically enriched chiral alcohols. This reaction has been extensively studied in terms of catalysts and variety of substrates. A large amount of information about the possible mechanisms is available nowadays, which has been of high importance for the development of systems with excellent outcomes in terms of conversion, enantioselectivity and Turn Over Frequency. On the other side, many mechanistic aspects are still unclear, especially for those catalytic precursors which have shown only moderate performances in transfer hydeogenation. This is the case of neutral [RuCl2(η6-arene)(P)] and cationic [Rh(PP)2]X (X = anion; P and PP = mono- and bidentate phosphine, respectively) complexes. Herein, a summary of the known information about the Transfer Hydrogenation catalyzed by these complexes is provided with a continuous focus on the more relevant mechanistic features.

Neutral dimeric rhodium diphosphine complexes are often employed as catalytic precursors in the presence of the solvent CH2Cl2. The possibility of a collateral reaction between the solvent and the catalytic precursor is never considered as the activation of CH2Cl2 by [Rh2(PP)2 (μ2-Cl)2] complexes is reputed difficult and uncommon. Herein we report the easy formation of three neutral dimeric Rh(III) complexes containing DPPP, DPPB and TangPhos through CH2Cl2 activation as an extension of the few examples reported so far. The system [Rh2 (DPPP)2 (μ2-Cl)2]/CH2Cl2 has been selected for a detailed mechanistic investigation. Kinetic studies based on 31P NMR monitoring combined with metathesis experiments reveal the fundamental role of a 14-electron intermediate [Rh(PP)Cl], which is involved in the CH2Cl2 activation.

The chemical composition and the color of samples of waste cooking oils (WCOs) were determined prior to and after filtration on two different pads of bentonite differing in particle size. The volatile fraction was monitored by headspace solid-phase microextraction (HS-SPME) coupled with gas-chromatography, while the variation of the composition of the main components was analyzed by 1H NMR. Both techniques allowed the detection of some decomposition products, such as polymers, terpenes, and derivatives of the Maillard process. The analysis of the chemical composition prior to and after bentonite treatment revealed a tendency for the clays to retain specific chemical groups (such as carboxylic acids or double bonds), independent of their particle size. A pair comparison test was conducted in order to detect the sensory differences of the intensity of aroma between the WCO treated with the two different bentonites. In addition, characterization of the bentonite by means of powder X-ray diffraction (XRD) and thermogravimetric measurements (TG) was performed.

The consideration towards waste cooking oils is changing from hazardous waste to valuable raw material for industrial application. During the last 5 years, some innovative processes based on the employment of recycled waste cooking oil have appeared in the literature. In this review article, the most recent and innovative applications of recycled waste cooking oil are reported and discussed. These include the production of bioplasticizers, the application of chemicals derived from waste cooking oils as energy vectors and the use of waste cooking oils as a solvent for pollutant agents.

Samples of sunflower Waste Cooking Oils (WCOs) subjected to several cycles of frying were treated with water under four different combinations of temperature and pH. The variation of the chemical composition of the oil samples was monitored through headspace Solid-Phase Microextraction (HS-SPME) coupled with gas-chromatographic technique (GC), 1H NMR spectroscopy and ESI+ mass spectrometry measurements. The possibility to modify the chemical composition of the recycled vegetable oil by tuning the water treatment parameters was exploited for the designing of a mini-plant for the production of bio-lubricants. A full description of the proposed prototype is also reported.

Background:In a previous study, we synthesised a new spiroketal derivative, inspired to natural products, that has shown high antiproliferative activity, potent telomerase inhibition and proapoptotic activity on several human cell lines.Objective:This work focused on the study of in vivo antitumor effect of this synthetic spiroketal on a murine melanoma model. In order to shed additional light on the origin of the antitumor effect, in vitro studies were performed.Methods:Spiroketal was administered to B16F10 melanoma mice at a dose of 5 mg/Kg body weight via intraperitoneum at alternate days for 15 days. Tumor volume measures were made every 2 days starting after 12 days from cells injection. The effects of the spiroketal on tumor growth inhibition, apoptosis induction, and cell cycle modification were investigated in vitro on B16 cells. HIF1α gene expression, the inhibition of cells migration and the changes induced in cytoskeleton conformation were evaluated.Results:Spiroketal displayed proapoptotic activity and high antitumor activity in B16 cells with nanomolar IC50. Moreover it has shown to inhibit cell migration, to strongly reduce the HIF1α expression and to induce strongly deterioration of cytoskeleton structure. A potent dose-dependent antitumor efficacy in syngenic B16/C57BL/6J murine model of melanoma was observed with the suppression of tumor growth by an average of 90% at a dose of 5 mg/kg.Conclusion:The synthesized spiroketal shows high antitumor activity in the B16 cells in vitro at nM concentration and a dose-dependent antitumor efficacy in syngenic B16/C57BL/6J mice. The results suggest that this natural product inspired spiroketal may have a potential application in melanoma therapy.

International audience; Efficient renewable and nontoxic absorbents can now be designed to eliminate air pollutants such as volatile organic compounds (VOCs) from confined atmospheres. New hybrid materials result from the combination of deep eutectic systems (DESs) with well-known VOC capture agents like β-cyclodextrin (βCD). However, a question arises: does βCD retain its encapsulation ability in DESs? Multiple nuclear magnetic resonance (NMR) techniques are used here to demonstrate the formation of inclusion complexes of βCD with two VOCs, aniline and toluene, in the pure DES reline and in reline/water mixtures. Complexation-induced chemical shift changes and intermolecular host–guest nuclear Overhauser effects (NOEs) in the rotating frame give evidence of genuine encapsulation in the βCD cavity, and complementary information on the dynamics of the VOC is gathered via relaxation and diffusion experiments. This work shows how different NMR techniques can contribute to the design of task-specific sustainable materials for absorption/extraction processes.

Samples of sunflower Waste Cooking Oils (WCOs) subjected to several cycles of frying were treated with water under four different combinations of temperature and pH. Several aspects of the chemical composition of edible, non-treated and processed samples was determined by three different analytic techniques: headspace Solid-Phase Microextraction (HS-SPME) coupled with gas-chromatography (GC), 1H NMR spectroscopy and ESI-MS spectrometry. Thus, a characteristic chemical fingerprint of each sample was derived and proposed as useful set of tools for the optimization of recycling of WCOs. On the basis of the presented results, a mini-plant for the production of bio-lubricants and bio-solvents with a circular economy approach was designed and herein described.

A fast, economic, and eco-friendly methodology for the wine variety and geographical origin differentiation using 13C nuclear magnetic resonance (NMR) data in combination with machine learning was developed. Wine samples of different grape varieties cultivated in different regions in Greece were subjected to 13C NMR analysis. The relative integrals of the 13C spectral window were processed and extracted to build a chemical fingerprint for the characterization of each specific wine variety, and then subjected to factor analysis, multivariate analysis of variance, and k-nearest neighbors analysis. The statistical analysis results showed that the 13C NMR fingerprint could be used as a rapid and accurate indicator of the wine variety differentiation. An almost perfect classification rate based on training (99.8%) and holdout methods (99.9%) was obtained. Results were further tested on the basis of Cronbach&rsquo, s alpha reliability analysis, where a very low random error (0.30) was estimated, indicating the accuracy and strength of the aforementioned methodology for the discrimination of the wine variety. The obtained data were grouped according to the geographical origin of wine samples and further subjected to principal component analysis (PCA) and partial least squares-discriminant analysis (PLS-DA). The PLS-DA and variable importance in projection (VIP) allowed the determination of a chemical fingerprint characteristic of each geographical group. The statistical analysis revealed the possibility of acquiring useful information on wines, by simply processing the 13C NMR raw data, without the need to determine any specific metabolomic profile. In total, the obtained fingerprint can be used for the development of rapid quality-control methodologies concerning wine.

The employment of clays in industry and on laboratory scale is still of interest, despite their long history. The chemical-physical characteristics of such material are strongly related to their geographical origin and the availability of proper characterization techniques is of great importance in order to gain as more information about their behavior when utilized as filling materials. In the present contribute a physical characterization by meaning of Thermogravimetry and N2 physisorption, including a thermal stability evaluation, of samples of Sardinian bentonite collected from the Alghero area (Italy) is reported.

The natural-like spiroketal, 2-hydroxy-8-methyl-1,7-dioxaspiro[5.5]undec-3-en-5-one (1) has been synthesised and has shown a potent antitumor activity against human tumor cells of different nature and histotype. We have now performed studies for verify its in vivo activity on a murine melanoma model and in vitro studies to shed some light on the mechanism of action.

A pulsed gradient spin echo experiment on [Rh2(1,3-bis-(diphenylphosphino)-propane)2(μ2-Cl)2] complex has been conducted in order to shed light on the supposed monomerisation process of [Rh2(diphosphine)2(μ2-Cl)2] complexes in solution. Such a process should generate a 14-electron [Rh(diphosphine)Cl] complex, which has only been postulated to date. Metathesis experiments on [Rh2(1,3-bis-(diphenylphosphino)-propane)2(μ2-Cl)2] and [Rh2(bis[2-(diphenylphosphino)phenyl]ether)2(μ2-Cl)2] complexes, analysed by 31P NMR, reveal that monomerisation of [Rh2(diphosphine)2(μ2-Cl)2] complexes is not restricted to the case of 1,3-bis-(diphenylphosphino)propane.

An unexpected reaction of pyridine with acetyl chloride to give N-acetyl-1,2 and 1,4-dihydropyridyl acetic acid (1, 2) in high yield and regioselectivity has been reported. The key step is the formation of a zwitterionic pyridinium ketene enolate. The effect of different activating agents on the reaction yield and selectivity has been studied. Platinum(IV) mediated hydrogenation of the corresponding methyl esters (7, 8) gave piperidine derivatives (9, 10). © 2014 Elsevier Ltd. All rights reserved.

Numerous complex natural products containing spiroketals framework, with a wide range of important biological activities, have been isolated over the years from marine or terrestrial sources. Many groups investigated the possibility to reduce the complexity of spiroketal natural products while preserving their biological activity, showing that simple natural inspired spiroketals can be privileged scaffolds for new interesting lead compounds. We have synthesized a new structurally simplified spiroketal that has shown a potent antitumor activity against tumor cells of different nature and histotype. The simple spiroketalic structure of this compound has three stereocentres and its synthesis afforded a stereoisomeric mixture. We carried out the synthesis and the characterization of the stereoisomeric mixture, the stereoisomeric separation and the biological evaluation both of the stereoisomeric mixture and the enantiomerically pure spiroketals.

Reduction of 1,2-diaryl-substituted ethenes with Na metal in dry THF allowed easy access to a variety of 1,2-diaryl-1,2-disodiumethanes. These diorganometallic intermediates were elaborated into the corresponding 1,2-diarylethanes (aqueous work up), or cycloalkylated with 1,3-dichloropropanes. The last reaction led to a highly diastereoselective synthesis of trans-1,2-diaryl-substituted cyclopentanes.

Recycling of waste cooking oil represents a source of convenient raw materials for industry. Within the large number of products derived from the treatment of waste cooking oil, eco-friendly lubricants grown in importance during the last years. Recycling process for such application consists usually of acid or basic degumming followed by a filtration step. The effect of the specific type of acid degumming on the density and on the flash point of the recycled oil was evaluated employing full factorial design. Two mathematical equations were derived which allow to estimate respectively the density and the flash point of the recycled oil, depending on the: (a) pH of the washing solution, (b) oil/water ratio, (c) temperature of the system, and (d) the stirring time. Practical applications Recycle of waste cooking oil presents several advantages. Mainly it is beneficial for the environment and considered as mandatory by law in several countries, and could furnish a useful low price raw material for several kind of industries. Recently, a multitude of local small scale industries have based their business on this topic and the recycling process employed often consists in a degumming step followed by filtration. This article deals with the tuning of the main parameters of the degumming step related with the density and the flash point of the final product. These parameters are important especially for lubricant synthesis.