Central European Journal of Chemistry

The ability of new chelate ligands, benzoxazol-5-yl-alanine derivatives substituted in position 2 by heteroaromatic substituent, to form complexes with selected metal ions in acetonitrile are studied by means of absorption and steady-state and time-resolved fluorescence spectroscopy. Among the ligands studied, only azaaromatic derivatives form stable complexes with transition metal ions in the ground state. Their absorption bands are bathochromically shifted enabling to use those ligands as ratiometric sensors. The fluorescence of each ligand is quenched by metal ions, however, in the presence of Cd(II) and Zn(II) ions a new red shifted emission band is observed.

The inclusion of vanadocene dichloride (VDC) and 1,1′-dimethyl vanadocene dichloride (MeVDC) into cyclodextrines (α-CD, β-CD and γ-CD) was studied by EPR spectroscopy. It was found that VDC and MeVDC with β-CD and γ-CD form true inclusion compounds, but with α-CD, VDC and MeVDC gave only fine dispersion mixtures. The inclusion was validated by anisotropic EPR spectra of solid samples. In addition, the antimicrobial was validated by anisotropic EPR spectra of solid samples. In addition, the antimicrobial behavior (against E. coli) of each of the complexes was determined. It was established that not only did VDC and MeVDC cause elongation of E. coli, but also the new vanadocene inclusion complexes were effective in this regard.

Effects of chlorides of univalent (LiCl, NaCl, KCl), bivalent (MgCl2, BaCl2) and trivalent (AlCl3) metals at different concentration (0.001–0.1 M) on the behavior of nanosilica A-200 (0.5–5 wt.%) in aqueous media are analyzed using photon correlation spectroscopy (particle size distribution, PSD), electrophoresis (zeta potential ζ), potentiometric titration (surface charge density), and estimation of screening length of primary particles and their aggregates. The zeta potential and the PSD are affected by silica content, pH, and concentration and type of dissolved salts. Smaller but more strongly hydrated Li+ cations caused stronger nonlinear dependences of the zeta potential on pH and salt content than Na+ or K+. This nonlinearity is much stronger at a lower content of silica (0.5–1 wt.%) than at C A-200 = 2.5 or 5 wt.%. At a high concentration of nanosilica (5 wt.%) the effect of K+ ions causes stronger diminution of the negative value of the zeta potential due to better adsorption of larger cations. Therefore, the influence of K+ on increasing screening length is stronger than that of Na+ for both primary nanoparticles and their aggregates. A similar difference in the ζ values is observed for different in size cations Ba2+ and Mg2+.

Starting from N-hydroxyphthalimide 1 and the reactive fluoro- or chloro-nitroaryl derivatives 2, 3 and 4a-e (2-chloro-3,5-dinitropyridine; 3, NBD-chloride; 4a, 1-fluoro-2,4-dinitrobenzene; 4b, picryl chloride; 4c, 4-chloro-3,5-dinitrobenzotrifluoride; 4d, 2-chloro-3,5- dinitrobenzotrifluoride; 4e, 4-chloro-3,5-dinitrobenzoic acid) the corresponding N-(2-nitroaryloxy)-phthalimide derivatives 5a-e, or 6 and 7 were obtained and characterized by IR, UV-Vis 1H-NMR and 13C-NMR spectroscopy. The TLC behavior and the hydrophobicity of these derivatives have been experimentally evaluated by RM0 parameters (using RP-TLC). The experimental RM0 parameters were compared with the calculated partition coefficient, log P. A QSPR study was also performed to establish possible correlations between the structure and physical properties (λmax and RM0) of compounds 5a-e, 6, and 7.

Thermodynamic description is presented for the ternary Cu-Ni-Pb system. Optimized parameters of the sub-systems, Cu-Ni, Cu-Pb and Ni-Pb, are taken from earlier assessments and those of the ternary system are optimized in this study by using the experimental phase equilibrium and thermodynamic data. Better agreement is obtained by the present optimization. Calculated results are compared with the original experimental data to demonstrate the successfulness of this assessment. Moreover, a geometric model (general solution model) is used to estimate ternary integral molar Gibbs excess energies of the liquid phase from the bibary systems only. These values, however, disagree with the quantities obtained by thermodynamic optimizations.

Silica surface was modified with phenylboronic acid derivatives. The structures of the functionalized supports were characterized by FT-IR spectroscopy, 13C CP/MAS NMR spectrometry, elemental and thermogravimetric analysis. The solid supports were effectively applied as artificial receptors for sugars in aqueous solutions. Alizarin Red S. (ARS) was used to detect colour change upon carbohydrate (sugar) binding. The association constants of the supports studied-ARS complex and the functionalized silica-sugar (glucose) complex were calculated. The parameters obtained were comparable with those for the phenylboronic acids used for the silica gel modification. The competitive binding of the functionalized silica surface with ARS and sugar were studied by UV/VIS measurements.

Poly(vinylalcohol)/poly(ethyleneglycol)/poly(ethyleneimine) blend membranes were prepared by solution casting followed by solvent evaporation. The chemical structure of the prepared membranes was analyzed by FTIR and DSC. The sorption behavior as well as the permeabilities of the membranes for pure CO2 and N2 were investigated. The results show that the PVA/PEI/PEG membranes possess a higher permeability of CO2 and a lower permeability of N2. The membrane displays a CO2 permeability of 27 Barrer, and a N2 permeability of 3 Barrer at 25°C and 1 bar. CO2 sorption behavior of the composite membrane, which can be classified as a dual-mode sorption model, and N2 sorption behavior of the copolymeric membrane is in agreement with the Fickian diffusion model.

Cis-diamminedichloroplatinum(II) (cisplatin) was immobilized in a star-shaped polymer carrier. In order to define whether this polymer could be used as a drug delivery system for cisplatin, its characteristics, e.g. loading efficiency and release profile of cisplatin from the polymer in phosphate buffered saline (PBS), have to be assessed, and hence an appropriate analytical procedure for precise and reliable determination of Pt(II) must be established. Optimal instrumental parameters for Pt measurement by commonly used atomic spectrometric methods ETAAS and ICP-OES in various examined media were defined. Matrix interferences observed that were related to both techniques were evaluated, and analytical figures of merit were compared and critically discussed.

The Co-Pd/SiO2 and Co-Cu/SiO2 catalysts were prepared via solvated metal atom impregnation (SMAI) method and investigated for the Fischer-Tropsch (F-T) synthesis. The catalysts contained 5wt.% Co and a weight ratio of Pd (or Cu) to Co of 1/30. XPS indicated that Co, Pd and Cu were in metallic state. The results of XPS and magnetic measurements showed that Co and Pd (Cu) were alloyed. The Co particles on the catalysts were very highly dispersed and they displayed superparamagnetic behavior. FT-IR indicated that the electrons shifted from Cu and Pd to Co. Catalytic tests showed that CO hydrogenation rates followed the order Pd-Co > Cu-Co > Co.

Ethambutol (ETB) is a first-line antitubercular drug effective against actively growing Mycobacterium tuberculosis. Resistance of the mycobacterium to ethambutol among tuberculosis (TB) patients results from inadequate or inappropriate dosing of treatment or using low quality medication. It is therefore necessary to develop reliable methods for determining ethambutol metabolic profiles of patients at point of care for proper dosing. Herein an efficient ETB sensor device is illustrated. It consists of a graphite-polyurethane composite electrode. In order to characterise the electrochemical behaviour of ethambutol at pH = 8.0 voltammetric studies were performed. The detector was assembled in a flow injection apparatus and operated at +1.2 V (vs. Ag/AgCl(NaCl sat.)). The influence of sample volume and flow rate was studied. The linear response for the method was extended up to a 1.1 mmol L−1 ethambutol solution with a detection limit of 0.0634 mmol L−1. The reproducibility of current responses for injections of 0.7 mmol L−1 ethambutol solution was evaluated to be 5.1% (n = 30) and the analytical frequency was 161 determinations h−1. Two different samples were successfully analysed and the results were in good agreement with those obtained using capillary zone electrophoresis (CZE).