Amide,urea and thiourea‐containing triphenylene derivatives: influence of H‐bonding on mesomorphic properties

The synthesis and thermotropic properties are reported for a series of hexaalkoxytriphenylenes that contain an amide, urea or thiourea group in one of their alkoxy tails. The intermolecular hydrogen bonding abilities of these molecules have a disturbing influence on the formation and stability of the columnar liquid crystalline phases. The stronger the hydrogen bonding the more the liquid crystallinity is suppressed, probably due to disturbance of the π–π stacking of the triphenylene discs. As a direct result, urea‐ and amide‐containing triphenylene derivatives are not liquid crystalline, but several thiourea derivatives show hexagonal columnar mesophases.     

Mesomorphic behaviour and TSDC measurements of ortho-metallated palladium(II) and platinum(II) complexes with S,O-donor co-ligands

A series of ortho-metallated Pd and Pt complexes containing an imine ligand carrying three alkoxy chains and N-benzoylthiourea derivatives as co-ligands were prepared and their liquid crystalline properties investigated. Their structures were assigned based on elemental analysis, IR and ¹H NMR spectroscopy, whereas thermal properties were investigated by differential scanning calotimetry and polarising optical microscopy. All the compounds exhibit monotropic transitions involving nematic and smectic A phases, with the mesomorphic behaviour strongly related to the type of N-benzoylthiourea as well as the metal centre used. The thermally stimulated depolarisation current technique was employed to determine the conduction mechanism, phase transition temperature and the activation energies for one of the ortho-metallated Pd complexes.     

Spectral characterisation of new organic fluorescent dyes with an alkoxysilane moiety and their utilisation for the labelling of layered silicates

New fluorescence dyes with an alkoxysilane moiety were synthesised by the condensation of 3-(triethoxysilyl)-1-propanamine (3-aminopropyltriethoxysilane) with 4,10-benzothioxanthene-3,1′-dicarboxylic acid anhydride (BTXA) and N,N-dimethylaminonaphthalene-1,8-dicarboxylic acid anhydride (DMANA), which was accompanied by the formation of an imidic bridge. The compounds N-(3-(triethoxysilyl)propyl)-thioxantheno[2,1,9-dej]isoquinoline-1,3-dione (BTX-S) and 4-(N′, N′-dimethyl)-N-(triethoxysilyl)propyl-1,8-naphthalene dicarboxylic acid imide (DMAN-S) were characterised by steady-state and time-resolved fluorescence spectroscopy in chloroform and ethanol. Both conjugates (BTX-S and DMAN-S) exhibited absorption and emission bands in the same region as the un-substituted BTXA and DMANA. An important Stokes shift was observed for DMAN-S in ethanol. A high fluorescence quantum yield was observed for BTX-S in both solvents and for DMAN-S in chloroform. In addition, the newly developed fluorescent silane dyes were covalently attached to the microscopic particles of layered silicates and on the surface of SiO₂ wafers as a proof of concept for fluorescence particle (surface) visualisation. The surface wafer modification was precisely characterised by X-ray photoelectron spectroscopy (XPS). Successful covalent linkage onto the particles of layered silicates was proved by confocal laser scanning microscopy technique.     

“Surface water” and “strong-bonded water” in cyclodextrins: a Karl Fischer titration approach

Cyclodextrins are some of the most used carriers for bioactive compounds (as host–guest complex) and many factors influence the association–dissociation of this complex, some of them being related to hydrophobicity. In the solid state, cyclodextrins contain two types of water molecules: “surface” water molecules (especially close to the crystal surface) and “strong-bonded” water molecules (especially from the cyclodextrin cavity), but the classification is hard to do, and the concentration of these water molecules are relatively difficult to estimate by simple methods. In the present study we used the volumetric Karl Fischer titration to estimate these types of water molecules in cyclodextrins by means of the rate of water reaction (related to diffusion from cyclodextrin crystals). “Surface” water molecules are titrated with rates between 1.8–2.8 mM/s for α-cyclodextrin, while for β-cyclodextrin these rates are little bit higher (2.9–3.4 mM/s). The rates corresponding to “strong-bonded” water molecules are approximately tens fold lower (0.05–0.3 mM/s for α-cyclodextrin and 0.15–0.33 mM/s for β-cyclodextrin). The approximate ratio between “surface” and “strong-bonded” water molecules could also be estimated by this simple and rapid method.     

Invariance for stochastic differential systems with time-dependent constraining sets

The first part of this article presents invariance criteria for a stochastic differential equation whose state evolution is constrained by time-dependent security tubes. The key results of this section are derived by considering an equivalent problem where the square of distance function represents a viscosity solution to an adequately defined partial differential equation. The second part of the paper analyzes the broader context when solutions are constrained by more general time-dependent convex domains. The approach relies on forward stochastic variational inequalities with oblique reflection, the generalized subgradients acting as a reacting process that operates only when the solution reaches the boundary of the domain.     

Synthesis and antibacterial properties of new phenothiazinyl- and phenyl-nitrones

The synthesis of new phenothiazinyl- and phenyl-nitrones under classical versus microwave heating conditions is described. Better yields were obtained under microwave irradiation in the condensation reactions of phenothiazyl-carbaldehyde with hydroxylamine derivatives. The structures of the new phenothiazinyl-nitrones were assigned on the basis of MS, FT–IR and NMR spectra. The new nitrones and some known phenyl-nitrones were screened for their antibacterial and antifungal activity against several Candida species, Gram negative bacteria, such as E. coli, Citrobacter spp, Morganella spp, Pseudomonas aeruginosa, Klebsiella pneumoniae (± ESBL), Proteus spp, Acinetobacter spp and the Gram positive bacterium Staphylococcus aureus, with moderate results.     

Removal of zinc ions as zinc chloride complexes from strongly acidic aqueous solutions by ionic exchange

The aim of this study was to compare several anion exchangers and to investigate the capacity of Amberlite IRA410 to remove zinc as chloride [ZnCl₃]^? from hydrochloric solutions (1 M). Influence of the process parameters such as stirring rate, resin quantity and zinc initial concentration over the removal process, was considered. The highest experimental ionic exchange capacity between the considered anionic exchangers, in the same working conditions (500 rpm, 5 g resin and 500 mg L^?1), was obtained for Amberlite IRA410, 8.34 mg g^?1. With an increase of zinc ions concentration, ionic exchange capacity increased up to 19.31 mg g^?1 (1100 mg L^?1). The experimental data were analysed using Langmuir, Freundlich, Temkin and Dubinin-Radushkevich isotherm models. The results were also analyzed using sorption kinetics models, pseudo-first-, pseudo-second-order, intra-particle and film diffusion models. From the Dubinin-Radushkevich and Temkin isotherm models the mean free energy and heat of sorption were calculated to be 7.45 kJ mol^?1, respectively 1×10^?4 kJ mol^?1, which indicates that zinc sorption is characterized by a physisorption process. Kinetic studies showed that the adsorption followed a pseudo-second-order kinetic model.     

Glass foam from window panes and bottle glass wastes

Glass foams are building materials that now compete with classic insulating polymeric and fiber materials for thermal enveloping. The low flammability, high chemical durability and thermal stability are distinct advantages over polymeric materials. The present paper proposes the possibility of producing glass foam using two types of recycled glass wastes (window panes and bottle glass) together with plaster wastes from used ceramic casting molds as foaming agent. Optical microscopy, measurements of apparent porosity and density, hydrolytic and chemical stability, as well as thermal conductivity were used in order to characterize the obtained glass foams as insulator materials for the building industry. The apparent porosity of glass foams ranges between 20.19–54.54% when using window glass wastes, and 18.77–51.75% with bottle glass wastes. Thermal conductivity was less than 0.25 W mK-1 for all the studied glasses. The obtained results confirm that there exists an alternative method for producing glass foams, for example, from glass wastes and used ceramic plaster molds, which are utilized as foaming agents with good chemical stability and insulating properties.     

A Combined Experimental and Computational Study of Chrysanthemin as a Pigment for Dye-Sensitized Solar Cells

The theoretical study of chrysanthemin (cyanidin 3-glucoside) as a pigment for TiO₂-based dye-sensitized solar cells (DSSCs) was performed with the GAUSSSIAN 09 simulation. The electronic spectra of neutral and anionic chrysanthemin molecules were calculated by density functional theory with B3LYP functional and DGDZVP basis set. A better energy level alignment was found for partially deprotonated molecules of chrysanthemin, with the excited photoelectron having enough energy in order to be transferred to the conduction band of TiO₂ semiconductor in DSSCs. In addition, we used the raw aqueous extracts of roselle (Hibiscus sabdariffa) calyces as the source of chrysanthemin and the extracts with various pH values were tested in DSSCs. The extracts and photosensitized semiconductor layers were characterized by UV-Vis spectroscopy, and DSSCs based on raw extracts were characterized by current density-voltage measurements.