Antioxidant polysaccharide-enriched fractions obtained from olive leaves by ultrasound-assisted extraction with α-amylase inhibition, and antiproliferative activities.

Polysaccharide-rich materials were extracted from the alcohol-insoluble solids of Olea europaea l. **leaves. Structural characteristics were determined by colorimetric techniques, FT-IR, GC-MS, SEC/MALS/VD/DRI, and NMR (1H,13C). The extract and its main macromolecular components were characterized to assess their ability toward antioxidant, α-amylase inhibition, and antiproliferative activities. Results revealed that the ultrasound olive leave extract comprises polysaccharides with uronic acid, galactose, arabinose, and glucose in molar percentages of 11.7%, 11.3%, 7.5%, and 4.9% respectively, constituting 41% of the total mass. In addition, polyphenols (21%) and proteins (9%) are associated with these polysaccharides. Further, the extract showed noticeable ORAC and free radical scavenging abilities, in addition to high in vitro antiproliferative activity against Caco-2 colon carcinoma cell lines. Similarly, the extract exhibited a strong, uncompetitive inhibition of α-amylase by 75% in the presence of the extract with 0.75 µg/mL of concentration. This research concludes that ultrasound extraction method can be used for the extraction of polysaccharide-polyphenol-protein complexes. These conjugates exhibit the potential for combined biological activities resulting from a synergistic effect of its compounds, making them promising ingredients for the development of functional food.

Recycling of used vegetable oils by powder adsorption.

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.

Geographical variation of the chemical composition in essential oils extracted from Sardinian Salvia verbenaca.

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.

Behavior of Ternary Mixtures of Hydrogen Bond Acceptors and Donors in Terms of Band Gap Energies.

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.

Promising Technological and Industrial Applications of Deep Eutectic Systems.

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.

Antimicrobial Activity and Chemical Characterization of a Non-Polar Extract of Saffron Stamens in Food Matrix.

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.

Connecting chloride solvation with hydration in deep eutectic systems.

The Deep Eutectic Solvents/Systems (DESs) choline chloride:urea (xChCl = 0.33) and choline chloride:glycolic acid (xChCl = 0.5) were investigated using viscosity-corrected 35Cl NMR spectroscopy and molecular dynamics simulations to probe the role of chloride as a function of water content. Three Cl- solvation regimes are revealed, with high-symmetry environments for pure and highly dilute DES, and an unusual low-symmetry interstitial region where the primary coordination sphere is most disordered.

Optimization of Nazarov Cyclization of 2,4-Dimethyl-1,5-diphenylpenta-1,4-dien-3-one in Deep Eutectic Solvents by a Design of Experiments Approach.

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 °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 °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.

13C NMR-Based Chemical Fingerprint for the Varietal and Geographical Discrimination of Wines.

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'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.

An Integrated Approach to Optimizing Cellulose Mercerization.

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 °C in 24 h with 18%wt NaOH.

Band-Gap Energies of Choline Chloride and Triphenylmethylphosphoniumbromide-Based Systems.

UV-VIS spectroscopy analysis of six mixtures containing choline chloride or triphenylmethylphosphonium bromide as the hydrogen bond acceptor (HBA) and different hydrogen bond donors (HBDs, nickel sulphate, imidazole, d-glucose, ethylene glycol, and glycerol) allowed to determine the indirect and direct band-gap energies through the Tauc plot method. Band-gap energies were compared to those relative to known choline chloride-containing deep band-gap systems. The measurements reported here confirmed the tendency of alcohols or Lewis acids to increment band-gap energy when employed as HBDs. Indirect band-gap energy of 3.74 eV was obtained in the case of the triphenylmethylphosphonium bromide/ethylene glycol system, which represents the smallest transition energy ever reported to date for such kind of systems.

Innovative applications of waste cooking oil as raw material.

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.

Improving the recycling technology of waste cooking oils: Chemical fingerprint as tool for non-biodiesel application.

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 New Synthetic Spiroketal: Studies on Antitumor Activity on Murine Melanoma Model In Vivo and Mechanism of Action In Vitro.

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.

Synthesis and Enantiomeric Separation of a Novel Spiroketal Derivative: A Potent Human Telomerase Inhibitor with High in Vitro Anticancer Activity.

The synthesis, the enantiomeric separation, and the characterization of new simple spiroketal derivatives have been performed. The synthesized compounds have shown a very high anticancer activity. Cell proliferation assay showed that they induce a remarkable inhibition of cell proliferation in all cell lines treated, depending on culture time and concentration. The compounds have also shown a potent nanomolar human telomerase inhibition activity and apoptosis induction. CD melting experiments demonstrate that spiroketal does not affect the G-quadruplex (G4) thermal stability. Docking studies showed that telomerase inhibition could be determined by a spiroketal interaction with the telomerase enzyme.

Volatiles, color characteristics and other physico-chemical parameters of commercial Moroccan honeys.

Seven commercial Moroccan honeys were considered for chemical characterisation. Volatile fraction, total polyphenols content, antioxidant and antiradical activities were evaluated by employing different analytical methodologies. Several physical parameters such as refractive index, pH, water content, solids content and colour were measured. Volatile fraction revealed an abundant presence of cis- and trans-linalool oxide in the seven studied samples. The presence of high levels of compounds related to the Maillard reaction, like furfural and hydroxymethylfurfural, could be the result of thermal treatments used to liquefy commercial honeys or of long storage times. The CIE L*a*b*C*(ab)h°(ab) chromatic coordinates confirmed the advanced stage of the Maillard reaction, showing L* values lower than the common values found for honey of similar typologies.