Carbamoylimidazolium and thiocarbamoylimidazolium salts: novel reagents for the synthesis of ureas, thioureas, carbamates, thiocarbamates and amides

Carbamoylimidazolium salts act as efficient N,N-disubstituted carbamoylating reagents. These salts are readily prepared by the sequential treatment of secondary amines with N,N′-carbonyldiimidazole (CDI) and iodomethane. The carbamoylimidazolium salts are more efficient carbamoyl transfer reagents than the intermediate carbamoylimidazoles, as a result of the ‘imidazolium’ effect. Kinetic studies on the base promoted hydrolysis of both carbamoylimidazoles and carbamoylimidazolium salts reveal over a hundred-fold rate acceleration. The salts react with amines, thiols, phenols/alcohols, and carboxylic acids in high yields, without the need for subsequent chromatographic purification of the products, producing ureas, thiocarbamates, carbamates, and amides, respectively. Analogous thiocarbamoylimidazolium salts were also synthesized from secondary amines and N,N′-thiocarbonyldiimidazole (TCDI), followed by methylation with iodomethane.     

Hemocompatibile Thin Films Assessed under Blood Flow Shear Forces

The aim of this study was to minimize the risk of life-threatening thromboembolism in the ventricle through the use of a new biomimetic heart valve based on metal–polymer composites. Finite volume element simulations of blood adhesion to the material were carried out, encompassing radial flow and the cone and plane test together with determination of the effect of boundary conditions. Both tilt-disc and bicuspid valves do not have optimized blood flow due to their design based on rigid valve materials (leaflet made of pyrolytic carbon). The main objective was the development of materials with specific properties dedicated to contact with blood. Materials were evaluated by dynamic tests using blood, concentrates, and whole human blood. Hemostability tests under hydrodynamic conditions were related to the mechanical properties of thin-film materials obtained from tribological tests. The quality of the coatings was high enough to avoid damage to the coating even as they were exposed up to maximum loading. Analysis towards blood concentrates of the hydrogenated carbon sample and the nitrogen-doped hydrogenated carbon sample revealed that the interaction of the coating with erythrocytes was the strongest. Hemocompatibility evaluation under hydrodynamic conditions confirmed very good properties of the developed coatings.     

Polyphenolic Characterization,Antioxidant, Antihyaluronidase and Antimicrobial Activity of Young Leaves and Stem Extracts from Rubus caesius L.

Fruits are the main food part of the European dewberry (Rubus caesius L.), known as a source of polyphenols and antioxidants, while very little attention is paid to leaves and stems, especially young first-year stems. The purpose of this work was to analyze for the first time water and ethanol extracts obtained from young, freshly developed, leaves and stems of the European dewberry to determine their antioxidant and biological activity, whereas most of the papers describe biological properties of leaves collected during summer or autumn. As the phytochemical profile changes during the growing season, the quantitative and qualitative content of flavonoid glycosides and flavonoid aglycones was analyzed using reversed phase liquid chromatography/electrospray ionization triple quadrupole mass spectrometry (LC-ESI-MS/MS) with multiple reaction monitoring (MRM). The ability to inhibit hyaluronidase as well as antioxidant activity (2,2 diphenyl-1-picrylhydrazyl: DPPH and ferric antioxidant power: FRAP) were estimated. Extracts were also analyzed against Gram-positive and Gram-negative bacteria. The results of the qualitative phytochemical analysis indicated the presence of flavonoid aglycones and flavonoid glycosides, with the highest amount of tiliroside, hyperoside, isoquercetin, astragalin, rutin and catechin in ethanol extracts. DPPH and FRAP tests proved the high antioxidant activity of the extracts from leaves or stems and the antihyaluronidase assay revealed for the first time that water and ethanol extracts obtained from the stems exhibited the ability to inhibit hyaluronidase activity resulting in an IC₅₀ of 55.24 ± 3.21 and 68.7 ± 1.61 μg/mL, respectively. The antimicrobial activity has never been analyzed for European dewberry and was the highest for Clostridium bifermentans and Clostridium sporogenes—anaerobic sporulation rods as well as Enterococcus faecalis for both water and ethanol extracts.     

Yamogenin-Induced Cell Cycle Arrest,Oxidative Stress,and Apoptosis in Human Ovarian Cancer Cell Line

Steroidal saponins are a group of compounds with complex structures and biological activities. They have anti-inflammatory, antimicrobial, fungicidal, and antitumor properties. Yamogenin is one of the spirostane saponins and occurs in Trigonella foenum-graecum, Asparagus officinalis, and Dioscorea collettii. It is a stereoisomer of diosgenin—a well-known compound whose activity and mechanisms of action in cancer cells are determined. However, the antitumor effect of yamogenin is still little known, and the mechanism of action has not been determined. In this study, we evaluated the effect of yamogenin on human ovarian cancer SKOV-3 cells in vitro by determining the cellular factors that trigger cell death. The viability of the cells was assessed with a Real-Time xCELLigence system and the cell cycle arrest with flow cytometry. The activity of initiator and executioner caspases (-8, -9, and -3/7) was estimated with luminometry and flow cytometry, respectively. The mitochondrial membrane depolarization, the level of oxidative stress, and DNA damage in the yamogenin-treated cells were also evaluated by flow cytometry. Genes expression analysis at the mRNA level was conducted with Real-Time PCR. Bid activation and chromatin condensation were estimated with fluorescent microscopy. The obtained results indicate that yamogenin has cytotoxic activity in SKOV-3 cells with an IC₅₀ value of 23.90 ± 1.48 µg/mL and strongly inhibits the cell cycle in the sub-G1 phase. The compound also triggers cell death with a significant decrease in mitochondrial membrane potential, an increase in the level of oxidative stress (over two times higher in comparison to the control), and activation of caspase-8, -9, -3/7, as well as Bid. The results of genes expression indicate that the Tumor Necrosis Factor (TNF) Receptor Superfamily Members (TNF, TNFRSF10, TNFRSF10B, TNFRSF1B, and TNFRSF25), Fas Associated via Death Domain (FADD), and Death Effector Domain Containing 2 (DEDD2) were significantly upregulated and their relative expression was at least two times higher than in the control. Our work shows that yamogenin induces apoptosis in ovarian cancer cells, and both the extrinsic and mitochondrial—intrinsic pathways are involved in this process.     

Synthesis,Characterization and Biological Investigations of Half-Sandwich Ruthenium(II) Complexes Containing Benzimidazole Moiety

Half-sandwich Ru(II) complexes belong to group of biologically active metallo-compounds with promising antimicrobial and anticancer activity. Herein, we report the synthesis and characterization of arene ruthenium complexes containing benzimidazole moiety, namely, [(η⁶-p-cymene)RuCl(bimCOO)] (1) and [(η⁶-p-cymene)RuCl₂(bim)] (2) (where bimCOO = benzimidazole-2-carboxylate and bim = 1-H-benzimidazole). The compounds were characterized by ¹H NMR, ¹³C NMR, IR, UV–vis and CV. Molecular structures of the complexes were determined by SC-XRD analysis, and the results indicated the presence of a pseudo-tetrahedral (piano stool) geometry. Interactions in the crystals of the Ru complexes using the Hirshfeld surface analysis were also examined. In addition, the biological studies of the complexes, such as antimicrobial assays (against planktonic and adherent microbes), cytotoxicity and lipophilicity, were performed. Antibacterial activity of the complexes was evaluated against S. aureus, E. coli, P. aeruginosa PAO1 and LES B58. Cytotoxic activity was tested against primary human fibroblasts and adenocarcinoma human alveolar basal epithelial cells. Obtained biological results show that the ruthenium compounds have bacteriostatic activity toward Pseudomonas aeruginosa PAO1 strain and are not toxic to normal cells. A molecular docking study was applied as a predictive source of information about the plausibility of examined structures binding with HSA as a transporting system.     

Effect of the Addition of Lemongrass (Cymbopogon citratus) on the Quality and Microbiological Stability of Craft Wheat Beers

Lemongrass (Cymbopogon citratus) is a valuable source of vitamins, macro- and microelements, and essential oils. The purpose of this study was to compare the physicochemical properties, sensory properties, antioxidant activity, and microbiological stability of wheat beers enriched with varying additions of crushed lemongrass. Sensory evaluation showed that wheat beers enriched with 2.5% m/v lemongrass were characterised by balanced taste and aroma (overall impression). Physicochemical analysis of the wheat beers showed that increasing the concentration of lemongrass in the finished product negatively affected the ethanol content. Alcohol content in wheat beer enriched with 1% m/v lemongrass was on average 14.74% higher than wheat beer enriched with 2.5% m/v lemongrass and on average 17.93% higher than wheat beer enriched with 5% m/v addition of lemongrass. The concentration of lemongrass in the finished product also increased the acidity of the beers and affected the colour of the wheat beers compared to the control beer. The total polyphenol content and antioxidant activity of lemongrass-enriched wheat beers varied. Of the lemongrass-enriched beers analysed, the beer product with 5% m/v lemongrass was the most microbiologically stable. According to the study, crushed lemongrass-enriched wheat beer may represent a new trend in the brewing industry, but the brewing process still needs to be improved.     

Feasibility of Defatted Juice from Sea-Buckthorn Berries (Hippophae rhamnoides L.) as a Wheat Beer Enhancer

Juice made from sea-buckthorn berries (Hippophae rhamnoides L.) is a valuable source of bioactive compounds, vitamins, as well as micro- and macronutrients. By applying defatted sea-buckthorn juice, it is possible to enhance wheat beer and change its sensory properties and the contents of bioactive compounds in the finished product. A sensory assessment showed that wheat beers with a 5% v/v addition of sea-buckthorn juice were characterised by a balanced taste and aroma (overall impression). Physicochemical analyses showed that, compared to the control samples, wheat beers enhanced with defatted sea-buckthorn juice at a rate of 5% v/v or 10% v/v had high total acidity with respective mean values of 5.30 and 6.88 (0.1 M NaOH/100 mL), energy values lower on average by 4.04% and 8.35%, respective polyphenol contents of 274.1 mg GAE/L and 249.7 mg GAE/L, as well as higher antioxidant activity (measured using DPPH, FRAP, and ABTS assays). The findings show that the samples of wheat beer enhanced with sea-buckthorn juice had average ascorbic acid contents of 2.5 and 4.5 mg/100 mL (in samples with 5% v/v and 10% v/v additions, respectively) and contained flavone glycosides, e.g., kaempferol-3-O-glucuronide-7-O-hexoside. Based on the current findings, it can be concluded that wheat beer enhanced with sea-buckthorn juice could emerge as a new trend in the brewing industry.     

Sustainable Drying and Torrefaction Processes of Miscanthus for Use as a Pelletized Solid Biofuel and Biocarbon-Carrier for Fertilizers

Miscanthus is resistant to dry, frosty winters in Poland and most European Union countries. Miscanthus gives higher yields compared to native species. Farmers can produce Miscanthus pellets after drying it for their own heating purposes. From the third year, the most efficient plant development begins, resulting in a yield of 25–30 tons of dry matter from an area of 1 hectare. Laboratory scale tests were carried out on the processes of drying, compacting, and torrefaction of this biomass type. The analysis of the drying process was conducted at three temperature levels of the drying agent (60, 100, and 140 °C). Compaction on a hydraulic press was carried out in the pressure range characteristic of a pressure agglomeration (130.8–457.8 MPa) at different moisture contents of the raw material (0.5% and 10%). The main interest in this part was to assess the influence of drying temperature, moisture content, and compaction pressure on the specific densities (DE) and the mechanical durability of the pellets (DU). In the next step, laboratory analyses of the torrefaction process were carried out, initially using the Thermogravimetric Analysis TGA and Differential Scaning Calorimeter DSC techniques (to assess activation energy (EA)), followed by a flow reactor operating at five temperature levels (225, 250, 275, 300, and 525 °C). A SEM analysis of Miscanthus after torrefaction processes at three different temperatures was performed. Both the parameters of biochar (proximate and ultimate analysis) and the quality of the torgas (volatile organic content (VOC)) were analyzed. The results show that both drying temperature and moisture level will affect the quality of the pellets. Analysis of the torrefaction process shows clearly that the optimum process temperature would be around 300–340 °C from a mass loss ratio and economical perspective.     

Structural and Optical Properties of Pure and Sulfur-Doped Silicate–Phosphate Glass

A series of silicate–phosphate glass materials from the SiO₂-P₂O₅-K₂O-MgO system (pure and doped with sulfur ions) were synthesized by melting raw material mixtures that contained activated carbon as a reducer. The bulk composition of glass was confirmed with X-ray fluorescence spectroscopy. The homogeneity of the glass was confirmed through elemental mapping at the microstructural level with scanning electron microscopy combined with an analysis of the microregions with energy-dispersive X-ray spectroscopy. The structural and optical properties of the glass were studied by using spectroscopic techniques. The infrared spectroscopy studies that were conducted showed that the addition of sulfur caused changes in the silicate–phosphate networks, as they became more polymerized, which was likely related to the accumulation of potassium near the sulfur ions. By using irradiation with an optical parametric oscillator (OPO) nanosecond laser system operating at the second harmonic wavelength, the glass samples emitted a wide spectrum of luminescence, peaking at about 700 nm when excited by UV light (210–280 nm). The influence of the glass composition and the laser-processing parameters on the emission characteristics is presented and discussed. This work also referred to the density, molar volume, and theoretical optical basicity of pure and sulfur-doped glass.