Band 10, Heft 6

This review covers almost two hundred and twenty heterobinuclear platinum compounds in which Pt⋯M separation is over 3.0 Å. The M is a transition metal (Cu, Ag, Au, Ti, V, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni and Pd). There is an example of a lanthanide, Yb and a actinide, U. The Pt atom has oxidation numbers 0, +2 and +4. The Pt coordination geometries include trigonal planar Pt(0); square planar Pt(II); trigonal bipyramidal, and pseudo octahedral Pt(IV), with the most frequent being square planar. The most common ligands for Pt are P and C donor atoms, as well as a chlorine atom. The Pt — Ag distance of 3.002(1) Å is the shortest found in this series. There are examples which contain two crystallographically independent molecules, which differ mostly by degree of distortion and even one unique example, which contains eight such molecules. These are examples of distortion isomerism. Factors affecting bond lengths and angles are discussed and some ambiguities in coordination polyhedral are outlined.

Chiral effects for the inhibition of acetylcholinesterase by organophosphorus pesticides were investigated for insecticide malathion and malaoxon, which is a metabolic product of malathion in living organisms. Studies were carried out using a bienzymatic biosensor with immobilized acetylcholinesterase, choline oxidase, and with Prussian Blue used as a mediator. In both cases the R enantiomers accelerate acetylocholinesterase inhibition. The chiral effect in inhibition was much more pronounced in fast flow measurements than in batch measurements.

A stable superhydrophobic surface of stearic acid grafted zinc was fabricated with two steps, that is, the zinc surface was firstly treated with glow discharge electrolysis plasma (GDEP) and then followed by a grafted reaction of stearic acid onto the treated zinc surface. Results indicated that the wettability of zinc substrate changed from superhydrophily to superhyphodrobicity with a water contact angle (CA) up to 158° and a water sliding angle (SA) less than 5°. The surface morphology and composition were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively.

The purpose of this study was to evaluate the decay of squalene and the formation of trans fatty acids (TFAs) in the amaranth oil extracted with hexane with and without heat. Oils were analyzed by determining their chemical values, and the fatty acids were identified and quantified by using Fourier-transform infrared (FTIR) spectroscopy, in the mid-region of 400–4000 cm−1, and gas chromatography. The FTIR analysis shows that two oil extracts (with and without heat) present a well-defined peak at 968 cm−1, which represents the trans double bonds. The quantified TFAs are

Polybenzene unit BT_48 can dimerize either by identification of 8-membered rings to provide a diamond-like fcc net or by identifying the opening 12-membered rings to form intercalated dendrimer-dimers which can further grow and rather quickly superimpose over the diamond-like network. The third hypothetical moiety we consider here is an eclipsed isomer, that can form multitori as negatively curved structures of various complexity. Multitori can evolve spherically or show a linear periodicity, as in rods. The polybenzene (“armchair”) multitori BTA are compared to the (“zig-zag”) BTZ ones, proposed earlier by us. A graph-theoretical study related the structure of multitori to the genus of their embedding surface and established the lower and upper bound values of genus. The total energy per carbon atom, HOMO-LUMO gap and strain energy of BTA and BTZ multitori have been computed and the results obtained point to BTZ multitori to be at least as stable as C60 what suggests BTZ multitori can be eventually synthesized in laboratory.

HPLC has been already used for the TAP estimation. Phenylalanine, salicylic, p-hydroxybenzoic (pHBA) or terephthalic (TPA) acids have been used as sensor compounds. Products of their reaction with the hydroxyl radicals, generated in the Fenton-like reaction, were analyzed using electrochemical or fluorescence detection. This paper describes the TAP assay based on the hydroxyl radicals reaction with pHBA, reversed-phase-HPLC separation and UV photometric detection. The elaborated assay has been used to evaluate TAP values of some apiculture products.

The spatial relationships between the pharmacophore elements were investigated in the case of four different stereoisomeric forms of opioid tetrapeptide, endomorphin-2, taking into account the L-D and cis-trans isomerisms. On the basis of distances and angles measured between the pharmacophoric points, a comparative analysis of conformational distributions was performed, applying a variety of distance-angle maps. The results obtained by this theoretical study indicated that the stereoisomers of endomorphin-2 could be distinguished from one another, based on the comparative analysis of distance-angle maps. Nevertheless, it could be concluded that this method proved to be suitable to examine the effects of L-D and cis-trans isomerisms on the spatial relationships of the pharmacophores of tetrapeptide.

The present study is reporting the influence of the chelating/combustion agents on the magnetic properties of Zn ferrite. Six chelating/combustion agents, citric acid, egg white, tartaric acid, glycine, glucose and urea, were used to obtain monophase zinc nanoferrite via a sol-gel auto-combustion method. The samples were subjected to a comparative study of structural features and magnetic properties by means of infrared spectroscopy, X-ray diffractometry, scanning electron microscopy and vibrating sample magnetometry. Significant influence of fuel and combustion mode was observed in the magnetic behavior of as-obtained samples. Values of the structural parameters were discovered to vary as a function of fuel choice, and to obtain crystallite size between 38 and 62 nm, inversion degree between 0.239 and 0.807, lattice parameter between 8.4125 and 8.4432 Å. The optimization of sol-gel method synthesis of zinc ferrite nanoparticles by chosing the appropriate fuel is providing structural and magnetic properties of zinc nanoferrite as potential materials to be used in biomedical applications.

The development and optimization of a novel UV spectrophotometric methodology was proposed for simultaneous analysis of ethambutol (ETB), isoniazid (ISO), rifampicin (RIF) and pyrazinamide (PYR), using multivariate calibration based on the partial least squares method (PLS). The methodology was successfully applied for analysis of four-drug fixed dose combination (4-FDC) tablets used for tuberculosis treatment. A 34 Box-Behnken design, with triplicate in central point, was used for sample preparation in the calibration step. In the present case, nine latent variables were chosen for the model development that presented the smallest RMSECV and explain 98.76% of data variance in Y block (concentrations of ETB ISO, RIF and PYR) and 99.93% of data variance in X block (spectral data). PLS models for ETB, ISO, RIF and PYR presented RMSEP and R2 values of 0.23 mg L−1 and 0.971; 0.14 mg L−1 and 0.731; 0.11 mg L−1 and 0.990 and 0.57 mg L−1 and 0.972, respectively. A validation step was performed based on the comparison between the UV spectrophotometric proposed methodology and capillary zone electrophoresis (CZE) in 4-FDC real samples and no significant difference was found between two methodologies at 95% of confidence level.

The reduction of H2SO4 to SO2 occurs with a relatively good efficiency only at high temperatures, in the presence of catalysts. Some experimental results, regarding conversion of sulfuric acid (96 wt.%) to sulfur dioxide and oxygen, are reported. The reduction has been performed at 800 – 900°C and atmospheric pressure, in a tubular quartz reactor. The following commercial catalysts were tested: Pd/Al2O3 (5 wt.% and 0.5 wt.% Pd), Pt/Al2O3 (0.1 wt.% Pt) and α-Fe2O3. The fresh and spent catalysts were characterized by X-Ray diffraction and BET method. The highest catalytic activity was determined for 5 wt.% Pd/Al2O3, a conversion of 80% being obtained for 5 hours time on stream, at 9 mL h−1 flow rate of 96 wt.% H2SO4. A conversion of 64% was determined for 0.5 wt.% Pd/Al2O3 and 0.1 wt.% Pt/Al2O3. For α-Fe2O3, a less expensive catalyst, a conversion of 61% for about 60 hours was obtained.

Tyrosine (Tyr) was quantitated with high sensitivity and selectivity in the presence of uric acid (UA) using a carbon paste electrode modified with multi-walled carbon nanotubes. Tyr and UA were catalytically oxidized with diffusion-controlled characteristics. They were determined simultaneously by differential pulse voltammetry with a potential difference of 350 mV. The electrocatalytic currents increase linearly with Tyr and UA concentrations 4×10−7−1×10−4 M and 3×10−7−2×10−4 M. Their detection limits were 1×10−7 and 5.1×10−8 M respectively. In the presence of sodium dodecyl sulfate the Tyr detection limit improved from 1×10−7 to 6.9×10−8 M. The electrode was successfully used to quantitate Tyr and UA in serum.

A number of heterogeneous acid type catalysts of silica-alumina nature, which are proposed to be used for petrochemistry by-product oligomerization, have been investigated. Particularly, such key indicators as active site concentration and strength have been determined. These parameters have been determined by the method based on potentiometric titration that is relatively seldom used in heterogeneous catalysis. The number of active site types present in investigated catalysts, as well as concentrations of each type of site, has been determined by mathematical processing of potentiometric titration data. The sequence of mathematical processing of titration data is described. The relationship between the properties of the investigated catalysts and their effectiveness in heterogeneous catalytic cooligomerization of the C9 fraction of liquid products of diesel fuel pyrolysis has been analyzed. The relationships between yields achieved in the presence of various catalysts and the properties of these catalysts have been defined. Namely, it was determined that the product yield is almost proportional to the active site’s concentration of the catalysts (activated clay materials). The relationship between the strength of active sites and average molecular weight of the cooligomers has been found. The causes of obtained regularities have been analyzed and explained.

Losartan is an antihypertensive agent that lost its patent protection in 2010, and, consequently, it has been available in generic form. The latter motivated the search for a rapid and precise alternative method. Here, a simple conductometric titration in aqueous medium is described for the losartan analysis in pharmaceutical formulations. The first step of the titration occurs with the protonation of losartan producing a white precipitate and resulting in a slow increase in conductivity. When the protonation stage is complete, a sharp increase in conductivity occurs which was determined to be due to the presence of excess of acid. The titrimetric method was applied to the determination of losartan in pharmaceutical products and the results are comparable with values obtained using a chromatographic method recommended by the United States Pharmacopoeia. The relative standard deviation for successive measurements of a 125 mg L−1 (2.71×10−4 mol L−1) losartan solution was approximately 2%. Recovery study in tablet samples ranged between 99 and 102.4%. The procedure is fast, simple, and represents an attractive alternative for losartan quantification in routine analysis. In addition, it avoids organic solvents, minimizes the risk of exposure to the operator, and the waste treatment is easier compared to classical chromatographic methods.

Microcomposites consisting of TiO2 and ThF4 or UO3 (0.5–2% of the TiO2 mass) are produced by sol-gel synthesis of TiO2 in presence of the respective additives. X-ray diffraction study reveals small effect of the latter on TiO2 phase composition and cell parameters and significant influence on the crystallite size and UV/Vis reflectance spectra. The photocatalytic tests in presence of TiO2-ThF4 microcomposites under UV and solar irradiation show a non-monotonic increase of the Malachite Green degradation rate constant with the increase of ThF4-content. No changes in the photocatalytic activity are observed in the presence of UO3 but the latter composites exhibit activity in darkness. The results are compared with previously reported data on the performance of TiO2-ThO2 photocatalyst with the same radioactivity and suggest that both radioactivity and the chemical nature of the dopants are responsible for the photocatalytic performance of TiO2-based composites containing radioactive substances.

Polyurethanes based on poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer, succinic or citric acid, and ethyl ester L-lysine diisocyanate were synthesized and characterized by FT-IR and GPC. Wetting properties were evaluated by contact angle determinations. The critical micelle concentration was determined from surface tension measurements. Their abillity to undergo self-aggregation and temperature induced gelation was investigated through dynamic oscillatory measurements. The gelation point, sol-gel transitions, and gel structure are influenced by polymer structure, composition, molecular weight, concentration, and heating rate.

Carbon xerogels (CXs) synthesized from resorcinol and formaldehyde under different pH conditions were investigated. Both the textural and surface properties of the CXs depend closely on the pH used in the synthesis procedure. Concerning the texture, the mesoporous surface area (Smeso) increases and the micropore volume (Vmicro) decreases as the pH increases; concerning the surface chemistry, surface oxygen functional groups were easier to be created (by O2) on CX synthesized at lower pH. Application of these CXs as support of gold catalysts was also studied. Results showed that the oxygen activated CX that was synthesized at moderate pH (i.e., pH 6.0) was the most favorable support for gold catalysts used in selective oxidation of benzyl alcohol by molecular oxygen in liquid phase, due to the adequate amounts of surface oxygen functional groups created on the surface.

Spectrophotometric study of competitive complex formation equilibria involving overlapped spectral responding species applying a simple and versatile algorithm was carried out. The algorithm involves multivariable regression for calculation of equilibrium concentrations from multiwavelength data and mass action law for the stability constant calculation. The used regression functions are part of common statistical software. Stability constants and complex stoichiometry of competing equilibria were simultaneously determined. The species concentration profiles at several spectral overlapping and α-coefficient of competing reaction were obtained. Non-absorbing bismuth — pyrophosphate (PPh) system was studied as a competitive reaction of bismuth — 4-(2-Pyridylazo) resorcinol (PAR) complex. The formation of Bi-PPh complex with 1:1 stoichiometry was proved in the studied concentration region (CBi = 1×10−5 mol L−1; CPPh = 5×10−6 − 1×10−4 mol L−1). The stability constant of the complex at pH 1 and µ = 1.0 have been determined: logβ = 4.2±0.2.

This work focuses on using analytical methods, such as Fourier transform Infrared spectroscopy (FTIR) and high performance liquid chromatography (HPLC) with mass spectrometry (MS) detection to assess archaeological and geological amber. The main goal of this study is to apply the previously developed and optimized analytical methods in verifying criteria to ascribe and characterize the origin of materials found in archaeological sites. The proposed LC-MS method was successfully applied for the quantification of succinic acid content both in geological and archaeological samples of amber and offers excellent linearity between 0.1 and 5µg mL−1. The developed FTIR method provided some criteria which is able to differentiate between Baltic and Romanian amber (Romanite) that furthermore validates on archaeological amber artefacts.

The present paper reports the results of the relationship between the surface topography, microstructure and the in vitro bioactivity of samples with and without fluorapatite content in simulated body fluid. Glasses and glass ceramics belonging to the Li2O-SiO2-CaO-P2O5-CaF2 system were prepared by using conventional melting technique following by heat treatment to obtain glass ceramics. This current study demonstrates the benefits of combining two microscopic methods for better investigation of the surface structure. The formation of apatite layer on the surface and the increase in surface roughness proved that the glasses and glass ceramics with bioactive fluorapatite content could satisfy to the requirements for biomaterial applications. The results also showed that the roughness of apatite layer formed after immersion in body fluid on the surface of glasses with fluorapatite was more pronounced than that of equivalent glass ceramic samples cured under the same conditions.

In this study, forty-seven plant species belonging to seven families were analysed by GC and GC-MS for the contents of pharmacologically effective quinones: dithymoquinone (DTQ), thymohydroquinone (THQ), and thymoquinone (TQ). The results showed that detectable amounts (≥1 mg kg−1) of at least one of these compounds have been found in three species of both Monarda (M. didyma, M. media, and M. menthifolia) and Thymus (T. pulegioides, T. serpyllum, and T. vulgaris) genera, two Satureja (S. hortensis and S. montana) species, and in single representatives of Eupatorium (E. cannabinum), Juniperus (J. communis), and Nigella (N. sativa) genera. The maximum contents of THQ and TQ were found in M. media aerial parts and M. didyma inflorescences (2674 and 3564 mg kg−1 of dried weight, respectively) in amounts significantly exceeding their maximum contents in N. sativa seeds (THQ = 530 mg kg−1 and TQ = 1881 mg kg−1), which are generally considered as the main natural source of both of these compounds. As a conclusion, M. didyma (bergamot) and M. media (purple bergamot) can be recommended as new prospective natural sources of THQ and TQ for pharmaceutical or food industries.

The paper considers the possibilities for mechanochemical synthesis of rare earth complexes. The complex Eu(TTA)3·phen (HTTA — 2-thenoyltrifluoroacetone, phen — 1,10-phenanthroline) is synthesized by mechanical treatment of a mixture of EuCl3.6H2O, HTTA, phen and NaOH in planetary ball mill Pulverisette 7 for 30 min at 800 min−1. The non reacted starting reagents and reaction side products are separated by treating activated mixture with water-ethanol solution following a procedure proposed in the literature. The elemental composition, X-ray diffraction pattern, IR spectra, optical properties (excitation and emission spectra, luminescence lifetime) and morphology of the mechanochemically synthesized complex are compared with those of the complex prepared from solution by the conventional method. The results confirm close similarity in the molecular structure and identity of the elemental composition, X-ray diffractograms and fluorescence properties of the compounds prepared by both methods.

The sorptive potential of some lignocellulosic agro-industrial wastes (sunflower seed shells and corn cob) for Basic Blue 9 cationic dye removal from aqueous solutions was examined using the batch technique. The Freundlich, Langmuir, and Dubinin-Radushkevich isotherm models were used in order to determine the quantitative parameters of sorption. The Langmuir isotherm model indicated a maximum sorption capacity for these materials in the range of 40–50 mg dye per g (25°C), slightly higher for corn cob than for sunflower seed shells. The values of the thermodynamic parameters showed that the retention of cationic dye is a spontaneous and endothermic process. The application of pseudo-first order and pseudo-second order intraparticle diffusion models, and a Boyd — Reichenberg model for kinetic data interpretation suggested that sorption of Basic Blue 9 dye onto the studied materials is a process where both surface sorption and intraparticle diffusion contributed to the rate-limiting step. These lignocellulosic wastes can be used with good efficiency for dye removal from aqueous effluents.

A thermodynamic equation relating the change of interfacial excess (Gibbs) energy in the solid/aqueous salt solution system, caused by a variation of concentration of inorganic salt at a constant charge-determining ion activity, temperature and pressure, is derived. The equation is based on the Gibbs equation and ionic components of charge parameters. On the basis of literature experimental data for the AgI/aqueous KNO3 and TiO2/aqueous NaCl systems it was shown that the interfacial excess energy decreases with increasing salt concentration due to variation of the ionic components of charge of the interface.

The investigation of the extraction properties of a series of polyoligodentate β-aminophosphine oxides 1–8 bearing from one to six phosphine oxide groups in a molecule towards Ln(III) and alkaline earth metals ions from neutral media has revealed that, using common diluents, the extraction efficiency increases with an increase of a number of P=O functions in a ligand. The addition of ionic liquid, namely 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([bmim][NTf2]), significantly increasing the extraction efficiency and application of IL concentration of 0.05 M (in 1,2-dichloroethane) providing the maximum recovery of metal ions with Lu/La separation factor reaching up to 91. Hexapodal tris[bis(2-diphenylphosphorylethyl)aminoethyl]amine 8 demonstrates the highest extraction under all conditions applied and the separation factor for U and Eu of this compound exceeded 103.

Multivariate curve resolution — alternating least squares (MCR-ALS) has been applied to data collected from UV/Vis spectrophotometric analysis of the autoxidation process of pyrogallol in weakly alkaline aqueous solutions. The MCR-ALS analysis was able to explain the autoxidation kinetics of pyrogallol at pH 7.4 and 8.0, allowing deduction of the pure spectra and concentration changes of different species present throughout the entire process. The autoxidation process at pH 7.4 was found to follow a first-order reaction model, with formation of purpurogallin as the sole and terminal product. Changing the pH to 8.0 not only accelerated autoxidation of pyrogallol to purpurogallin but also introduced a further autoxidation of purpurogallin. At pH 8.0 the process fits a model of two consecutive first-order reactions. The first step is formation of purpurogallin, which reacts in a further autoxidation to form a yellow colored substance, most probably purpurogallin polymer.

The aim of this work was to mimic the stratified structure of the median region of long bones. Starting from this desideratum, more COLL/HA composite materials with different morphology were synthesized and characterized, each of these materials mimicking one layer of long bone (endo- and periosteum, compact and cancellous bony tissue). Stratified bone grafts were obtained by assembling these layers; the obtained grafts were similar to the median region of long bones. Even though, natural bones have a more complex microstructure, this is a pioneering work since for the first time a stratified COLL/HA composite material similar to bone was produced.

This work relates to the consecutive reduction of short chain carboxylic acids (volatile fatty acids, VFAs) to alcohols as main products. Acetic acid (AA) was used as a reactant to model the VFAs that can be produced by either thermochemical or biological biomass degradation. The amorphised zeolite supported copper catalysts (Cu/SiAl), especially the In-modified CuIn/SiAl catalysts, showed high hydroconversion activity and selectivity for alcohol, ester and aldehyde. Catalysts containing dispersed copper particles in amorphous aluminosilicate were obtained by dehydrating and H2-reducing Cu-forms of low-silica synthetic zeolites (A, X, P). The activity of the highly destructed Cu-aluminosilicates was found to depend on the structure of the zeolite precursor. The formation of ethyl acetate could be suppressed by adding water to the AA feed and by modifying the catalyst, e.g. by In2O3 additive. In the catalysts modified by In2O3 additive formation of copper-indium alloy phase (Cu2In intermetallic compound) was detected resulting in a different selectivity than the one recorded for the Cu/SiAl.

Magnetic resonance study of six samples consisting of carbon encapsulated nickel nanoparticles or carbon nanotubes ended with such nickel nanoparticles was carried out at room temperature. Samples of Ni/C were prepared by carburization of nanocrystalline nickel by ethylene (C2H4) and methane (CH4). Hydrocarbons decomposition on nickel nanoparticles was done at temperatures 500, 600 and 700°C. Magnetic resonance spectra of samples designated as CH4/500, CH4/600, CH4/700, C2H4/500, C2H4/600 and C2H4/700 were obtained by Bruker E 500 spectrometer. The integrated intensities of the resonance spectra were correlated with the carburization conditions (temperature, type of hydrocarbon) during samples preparation. A core-shell model of the investigated samples allowed rough estimation of appropriate shell sizes.

Biopolymeric microparticles were prepared by rapid expansion of high pressure CO2-chitosan (Chi) solution in sodium bis-(2-ethyl hexyl) sulfosuccinate (AOT) solution. At pressures higher than 2 MPa, ultrafine particles were formed while under this value, wires were obtained. The formation of Chi/AOT complex was confirmed by Fourier Transform Infrared (FTIR) Spectroscopy, whereas scanning electron microscopy was used to characterize the morphology, size and shape of the particles. The FTIR spectrum proved the interaction between the sulfonate groups of AOT and the amino groups of Chi. Microparticles are quasi-spherical in wet conditions and irregular after freeze drying, presenting a rough surface with many pores. Lyophilized hydrophobic microparticles were used to remove phenol and o-cresol from aqueous solution, and the adsorption process showed a maximum efficiency in the 7–8 pH range. The uptake of phenol and o-cresol increased with the amount of particles and decreased with increasing the pollutant concentration. The adsorption occurred rapidly in the first 60–120 minutes, and leveled off thereafter.