Synthesis of Selected Mixed Oxide Materials with Tailored Photocatalytic Activity in the Degradation of Tetracycline.

The elimination of antibiotics occurring in the natural environment has become a great challenge in recent years. Among other techniques, the photocatalytic degradation of this type of pollutant seems to be a promising approach. Thus, the search for new photoactive materials is currently of great importance. The present study concerns the sol-gel synthesis of mono, binary and ternary TiO2-based materials, which are used as active photocatalysts. The main goal was to evaluate how the addition of selected components-zirconium dioxide (ZrO2) and/or zinc oxide (ZnO)-during the synthesis of TiO2-based materials and the temperature of thermal treatment affect the materials' physicochemical and photocatalytic properties. The fabricated mixed oxide materials underwent detailed physicochemical analysis, utilizing scanning-electron microscopy (SEM), X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), energy-dispersive X-ray spectroscopy (EDS), low-temperature N2 sorption (BET model), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). The synthesized mixed oxide materials were used as photocatalysts in the heterogeneous photodegradation of tetracycline (TC). The physicochemical properties of the fabricated photocatalysts, including morphology, crystalline and textural structure, as well as the pH of the reaction system in the photocatalytic tests, were taken into account in determining their photo-oxidation activity. LC-MS/MS analysis was used to identify the possible degradation products of the selected antibiotic.

Structural Characterization of Co-Crystals of Chlordiazepoxide with p-Aminobenzoic Acid and Lorazepam with Nicotinamide by DSC, X-Ray Diffraction, FTIR and Raman Spectroscopy.

The low water solubility of benzodiazepines seriously affects their bioavailability and, in consequence, their biological activity. Since co-crystallization has been found to be a promising way to modify undesirable properties in active pharmaceutical ingredients, the objective of this study was to prepare co-crystals of two benzodiazepines, chlordiazepoxide and lorazepam. Using different co-crystallization procedures, slurry evaporation and liquid-assisted grinding, co-crystals of chlordiazepoxide with p-aminobenzoic acid and lorazepam with nicotinamide were prepared for the first time. Confirmation that co-crystals were obtained was achieved through a comparison of the data acquired for both co-crystals using differential scanning calorimetry (DSC), powder X-ray diffraction (PXRD), Fourier-transform infrared (FTIR) and Raman spectroscopy, with comparisons acquired for the physical mixtures of both benzodiazepines and coformers. The compatibility of PXRD patterns of both benzodiazepines co-crystals with those contained in the base Powder Diffraction File (PDF-4+) suggests that new crystal structures were indeed created under the co-crystallization procedure. Single-crystal X-ray diffraction revealed that a chlordiazepoxide co-crystal with p-aminobenzoic acid and a lorazepam co-crystal with nicotinamide crystallized in the monoclinic P21/n and P21/c space group, respectively, with one molecule of benzodiazepine and one of coformer in the asymmetric unit. FTIR and Raman spectroscopy corroborated that benzodiazepine and coformer are linked by a hydrogen bond without proton exchange. Furthermore, a DSC study revealed that single endothermic DSC peaks assigned to the melting of co-crystals differ slightly depending on the co-crystallization procedures and solvent used, as well as differing from those of starting components.

Molecular and Supermolecular Structure of Commercial Pyrodextrins.

Size exclusion chromatography with triple detection as well as infrared spectroscopy studies of commercially available pyrodextrins proved that these molecules are characterized not only by significantly lower molecular mass, in comparison to that of native starch, but also by increased branching. Therefore, pyrodextrins adopt a very compact structure in solution and show Newtonian behavior under shear in spite of their molecular masses of tens of thousands Daltons. The results also indicate that 50% reduction of digestibility of pyrodextrins is, to a minor extent, caused by formation of low-molecular color compounds containing carbonyl functional groups. The main reason is, as postulated in the literature, transglycosidation that leads to decreased occurrence of α-1,4-glycoside bonds in the molecular structure. In the process of dextrinization starch also undergoes changes in supermolecular structure, which, however, have no influence on digestibility. Likewise, the effect of formation of low-molecular colorful compounds containing carbonyl groups is not crucial.

The Influence of Processing and the Polymorphism of Lignocellulosic Fillers on the Structure and Properties of Composite Materials-A Review.

Cellulose is the most important and the most abundant plant natural polymer. It shows a number of interesting properties including those making it attractive as a filler of composite materials with a thermoplastic polymer matrix. Production of such composite materials, meeting the standards of green technology, has increased from 0.36 million tons in 2007 to 2.33 million tons in 2012. It is predicted that by 2020 their production will reach 3.45 million tons. Production of biocomposites with lignocellulosic components poses many problems that should be addressed. This paper is a review of the lignocellulosic materials currently used as polymer fillers. First, the many factors determining the macroscopic properties of such composites are described, with particular attention paid to the poor interphase adhesion between the polymer matrix and a lignocellulosic filler and to the effects of cellulose occurrence in polymorphic varieties. The phenomenon of cellulose polymorphism is very important from the point of view of controlling the nucleation abilities of the lignocellulosic filler and hence the mechanical properties of composites. Macroscopic properties of green composites depend also on the parameters of processing which determine the magnitude and range of shearing forces. The influence of shearing forces appearing upon processing the supermolecular structure of the polymer matrix is also discussed. An important problem from the viewpoint of ecology is the possibility of composite recycling which should be taken into account at the design stage. The methods for recycling of the composites made of thermoplastic polymers filled with renewable lignocellulosic materials are presented and discussed. This paper is a review prepared on the basis of currently available literature which describes the many aspects of the problems related to the possibility of using lignocellulosic components for production of composites with polymers.

Nickel hydroxide ageing time influence on its solubility in water acidified with sulphuric acid.

Nickel hydroxide samples freshly settled as well as stored over 1 month, 2 months and 6.5 years were examined for their solubility rate in diluted H2SO4 solutions of pH 1.9 and 2.8 as a function of time. Samples with a longer ageing history dissolved less readily than freshly settled ones. It was determined that the resistance to dissolving rose with sample ageing time and the solubility of the 6.5 years stored sample was particularly low. X-ray examination evidenced that during storage the crystallinity of Ni(OH)2 subsequently rose. The parallelity of both time-dependent phenomena allows the conclusion that with nickel hydroxide ageing the transformation of disordered nickel hydroxide species into crystalline Ni(OH)2 (without phase changes) is responsible for increasing nickel hydroxide resistance to dissolving in acidic solutions. Such decrease of nickel hydroxide solubility with ageing in case of waste nickel hydroxide, is worth to notice in a view of environment protection against pollution with electroplating waste.

Nickel immobilization in ceramic matrix admixed with waste nickel hydroxide.

WAXS examinations performed with nickel hydroxide samples heated to various temperatures showed that freshly settled wet nickel hydroxide sample contains some amount of crystalline beta-Ni(OH)(2) structure and its share increased when sample was dried during 3 weeks at ambient temperature. However, the share significantly decreased when the sample was dried at 110 degrees C and more so at 250 degrees C. Crystalline phase traces of Ni(OH)(2) disappeared after sample burning at 980 degrees C and instead the distinct presence of crystalline NiO was determined. The above samples were examined for solubility in stoichiometric amount of sulphuric acid diluted with water to pH 1.9 and 2.8. Solubility was determined by measuring nickel ion concentration in leachate by the AAS method. The dissolving rate was found to decrease with the rise of temperature to which the nickel hydroxide samples were heated. The solubility of Ni(OH)(2) sample burnt at 980 degrees C was undetectable during 90 h solubility-testing time likely due to its transformation into sparingly soluble crystalline NiO. The latter is considered to be the reason for effective immobilization of waste nickel hydroxide in ceramic prepared by blending with clay and sintering at 980 degrees C.