Band 9, Heft 3

The field of self-assembled monolayers (SAMs) of organic compounds on different substrates is of importance because it provides a suitable and efficient method of surface modification. The formation of robust, stable monolayers from carboxylic acids on two and three dimensional surfaces of different substrates have been reported. Carboxylic acids are promising class of organic compounds for monolayer formations where traditional alkanethiols or alkoxysilanes show limitations.

This report investigated nonlinear spatiotemporal behavior in the ferroin-bromate-pyrocatechol reaction, in which two stages of wave formation, separated by several hours of quiescent period, were observed. In addition to its great photosensitivity, the second stage wave activity could undergo spontaneous breakups at broad reaction conditions. Analysis based on one-dimensional space-time plot suggests that the breakup was caused by propagation slowdown of the leading wave. Due to the presence of coupled autocatalytic reactions, the propagation of the initial and the second stage waves exhibited different and subtle responses to the variation of the concentration of each reagent.

The compound barium bis{bis-(4,6-di-tert-butyl[1,2-benzenediolato(2-)-O,O′]borate)} has been prepared by the addition of 3,5-di-tert-butylcatechol to a solution of boric acid and Ba(OH)2 and characterized by a single crystal X-ray diffraction study. The title compound crystallized in the triclinic space group P-1, with cell parameters a = 13.280(2) Å, b = 15.755(3) Å, and c = 16.980(3) Å, α = 71.691(2)o, β = 79.528(3)o, γ = 80.741(3)o, Z = 1, and V = 3296.1(10) Å3. The structure was solved by direct methods and refined to a final R = 0.0459 for 14370 reflections with I > 2σ(I). One of the arylspiroboronate ester counterions is bound to the barium atom in a rare example of the η1 bonding mode via a single oxygen of one of the catecholato groups. The coordination sphere around the barium is complemented by four molecules of water, one molecule of acetone and two bridging water molecules, connecting to an adjacent barium atom.

The formation of aqueous bridges containing phenol and ethylene glycol as well as bisphenol-A, hydrochinone and p-cresol under the application of high voltage DC (“liquid bridges”) is reported. Detailed studies were made for phenol and glycol with concentrations from 0.005 to 0.531 mol L−1. Conductivity as well as substance and mass transfers through these aqueous bridges are discussed and compared with pure water bridges. Previously suggested bidirectional mass transport is confirmed for the substances tested. Anodic oxidation happens more efficiently when phenol or glycol are transported from the cathode to the anode since in this case the formation of a passivation layer or electrode poisoning are retarded by the electrohydrodynamic (EHD) flow. The conductivity in the cathode beaker decreases in all experiments due to electrophoretic transport of naturally dissolved carbonate and bicarbonate to the anode. The observed electrochemical behavior is shortly discussed and compared to known mechanisms.

The removal of indoor air contaminants by reactivity with air filters coated with reagents has been found to be effective for aldehydes, acidic and basic vapours as well as isocyanates Coatings of polymeric amines were used for formaldehyde trapping as well as for the removal of acidic vapours and for the removal of isocyanates. The addition of glycerol as a plasticizer for the coating can also be an effective reagent.

Soil contamination by metals is a common problem encountered in many industrialized countries. In this work we present a new approach for heavy metals detection by using surface-enhanced Raman scattering (SERS) spectroscopy. Zn(II) can be clearly determined by SERS in contaminated soil by using 4-(2-pyridylazo) resorcinol (PAR) as chelating molecule for the metal ion. The SERS spectra of PAR, of its metal chelates and of the soil extract-PAR mixture were recorded using a hydroxylamine reduced silver colloid. An excellent match of the PAR-contaminated soil extracts SERS spectrum to the Zn(PAR)2 SERS spectrum can be observed, demonstrating the presence of Zn(II) in the soil probes. Density functional theory (DFT) based calculations were also performed for a reliable assignment of SERS spectra.

Nax−yHyTi2−xFexO4·nH2O nanosheets with lepidocrocite-like layered structure were produced through alkaline hydrothermal treatment at very low temperatures (130°C) from ilmenite sand. The crystal structure, morphology and optical properties were investigated by X-Ray diffraction, transmission electron microscopy, selected area electron diffraction, energy dispersive spectroscopy and UV-Vis spectroscopy. The product shows leaf-like nanosheet morphology with thickness <30 nm and lengths <1 µm. Three lepidocrocite-like titanates (Imm2 space group) with similar a and c lattice parameters but different interlayer distances (b/2) were identified. This appears to be the first preparation of lepidocrocite-like layered nanosheets by a simple, energy efficient (low temperature) and low cost (starting from mineral sand) procedure.

Six complexes of vancomycin and peptidoglycan precursors were studied via molecular dynamics simulations. The interactions between the antibiotic and peptidoglycan fragments were identified and described in detail. All six studied modifications of the peptidoglycan precursor resulted in a weakening of the interaction with vancomycin when comparing to the native D-Ala-D-Ala-terminated fragment. It was confirmed that the N-terminus of the vancomycin is directly responsible for peptidoglycan recognition and antimicrobial activity. In simulated systems, the saccharide part of the antibiotic interacts with peptide precursors, thus it could also be important for antimicrobial activity. The complex terminated with D-Lac is the only one in which there is a weak interaction with the sugar moiety in the simulated systems. Analysis of conformational changes is a major scope of this work. The lack of interactions resulting from modification of the peptidoglycan precursors (D-Lac, D-Ser or other substitution) would be counterbalanced by proper modifications of the vancomycin moiety, especially the saccharide part of vancomycin.

A combined method involving electrochemical oxidation of iodide to iodate at a platinum electrode followed by extraction in CCl4 of ionic associates of iodine-iodide complexes with brilliant green, formed in excess of iodide, was developed for the spectrophotometric quantification of iodide. The slope of the calibration curve yields a molar extinction coefficient of ɛ = 3·105 L mol−1cm−1. This method can be used for the quantification of iodide in the concentration range of 3·10−7 − 3·10−6 mol L−1 with a detection limit of 5·10−8 mol L−1. The interfering effect of other ions on the determination of the iodide concentration was also investigated. The method was successfully applied for the determination of iodide in real samples of NaCl and spring water. Relative standard deviation is 1–2%.

Competitive adsorption of zinc and copper on activated carbon is studied in this article. Main aim was to suggest an advanced model for competitive adsorption of both metals considering pH influence and precipitation. A surface-complexation approach was employed for the modeling. Two models were considered: simple adsorption and ion exchange. System “The Geochemists Workbench” was used for calculation of both static and dynamic adsorption tasks. From the batch experiments, concentration of four types of sorbing sites on the carbon surface and its protonation and sorption constants were deduced. Then, batch competitive adsorption experiments were compared with the models’ results. Finally, a column experiment (fixed bed adsorption) was carried out. It was observed that the model of ion exchange can satisfyingly predict both chromatographic effect and increase of zinc concentration in effluent over its initial value, although a quantitative agreement between the model and the experiment was not totally precise.

An HPLC method for the quality control of famotidine (FMT) containing formulations has been developed and validated. The combination of a short monolithic column (Chromolith® RP-18e 50 × 4.6 mm i.d.) and an elevated flow rate (3.0 mL min−1) enabled the proposal of a high-throughput analytical scheme capable of reliable operation in a demanding industrial environment. Detection was carried out at 265 nm. Thorough validation of the method included linearity (5–150%), limits of detection (0.13%) and quantification (0.41%), selectivity, precision (within- and day-to-day), accuracy and ruggedness. The new method was applied successfully to the analysis of samples (assay, dissolution, dosage & blending uniformity) during the production of four validation batches of FMT-containing tablets.

The crystal and molecular structure of [Cu(nif)2(4-PM)2]·CH3OH (1) and [Cu(2-Clbz)2(4-PM)2(H2O)] (2), (where nif = niflumate anion, 2-Clbz = 2-chlorobenzoate anion and 4-PM is the 4-pyridylmethanol), have been determinated by X-ray crystallography. The Cu2+ cation in (1), is coordinated by two pairs of oxygen atoms from asymmetric bidentate niflumate anions and by a pair of pyridine nitrogen atoms from monodentate 4-pyridylmethanol ligands in trans position forming an extremely elongated bipyramid. The Cu2+ cation in (2), is coordinated by a pair of oxygen atoms from monodentate 2-chlorobenzoate anions, further by a pair of pyridine nitrogen atoms from monodentate 4-pyridylmethanol ligands and finally by a water oxygen atom forming a tetragonal-pyramidal coordination polyhedron. The molecules of both complexes in crystal structures are linked by O-H…O hydrogen bonds, which created a three-dimensional hydrogen-bonding networks. The Π-Π stacking interactions are also observed in crystal structures of complex 2. The spectral properties (IR and electronic spectra) of both complexes were also investigated.

ZrMo2O7(OH)2·2H2O was obtained from ZrOCl2·2H2O and Na2MoO4·2H2O by a coprecipitation method. The phase and structural changes occurred during the heat-treatment of ZrMo2O7(OH)2·2H2O were investigated by XRD, IR and XPS analysis. The sequence of phase transformation can be divided into three stages: (1) transformation of ZrMo2O7(OH)2·2H2O to orthorhombic LT-ZrMo2O8 up to 300°C; (2) obtaining of mixture of both polymorphs of ZrMo2O8: cubic and trigonal at 400°C; (3) conversion to single trigonal (α) ZrMo2O8 above 450°C. The microstructure of the obtained trigonal (α) ZrMo2O8 was observed by scanning electron microscopy (SEM). The particle sizes were below 0.5 µm. The specific surface area was measured by modified BET method. The photocatalytic activity of the obtained trigonal (α) ZrMo2O8 powders was investigated by degradation of a model aqueous solution of Malachite Green (MG) upon UV-light irradiation.

The electrochemical behaviour of three purine derivatives was investigated by cyclic voltammetry on different electrode materials: glassy carbon in native form and electrochemically activated, carbon paste electrode unmodified or modified with 1, 4-benzoquinone. The preliminary study obtained on solid electrodes was extended to graphite based planar screen-printed electrodes, unmodified and modified with multi-wall carbon nanotubes, or cobalt phthalocyanine. The influence of some experimental parameters (pH, scan rate, concentration and electrolytic medium) on the electrochemical behaviour of these alkaloids was also examined. The electrochemical oxidation of purine derivatives is an irreversible and diffusion controlled process, proved by the linear dependence between the peak potentials and the logarithm of scan rates and between the anodic peak current and the square root of scan rate.

The effect of alloying on the adsorption of atomic hydrogen was studied using density functional theory (DFT). In the study the (100) surfaces of Pd-Ag, Pd-Pt, Pd-Au, Pt-Ag, and Pt-Au alloys were considered by means of a cluster model. The structural and energetic properties of the H atom adsorbed on the Pd4Me (Me = Ag, Pt, Au) and Pt4Me (Me = Pd, Ag, Au) clusters were calculated and compared with the H-atom adsorption on monometallic clusters. The effect of alloying on the H-atom adsorption is evident for all the investigated bimetallic systems. However, it strongly depends on the second metal atom, Me, is placed in the surface layer or in the subsurface one. In general, the H atom adsorbed in a site containing the second metal exhibits different properties from those characteristic of its adsorption on Pd(100) and Pt(100). Hence, the modified interaction between atomic hydrogen and the alloyed surfaces may increase the selectivity of the catalytic hydrogenation reactions on such surfaces.

This paper presents the extraction of cations from a soil sample, type ranker on serpentinite, in deionized water, by use of three different extraction techniques. The first extraction technique included the use of a rotary mixer, the second technique involved the use of a microwave digestion system with different extraction temperatures, and the third technique employed an ultrasonic bath with different extraction times. Ion chromatography was used for determining the concentration of Li, Na, K, Ca, Mg and ammonium ions in soil extracts with subsequent determination of concentrations for all cations, except for ammonium ion extraction, conducted by Inductively Coupled Plasma-Atomic Emission Spectrometry. The results of cation extractions showed that microwave assisted extraction was most efficient for the Li, Na, K, Ca, Mg, Co, Mn, Ni, Pb and ammonium ions. Use of a rotary mixer for extraction was most efficient for Cd and Zn ions, while use of ultrasound bath was most efficient for Cr, Cu, Fe and Al ions. Several times higher amount of cations extracted by the most efficient, compared to the second best technique, under optimal conditions, were noticed in the case of: Ca, Mg, Co, Mn, Fe, Al, and Zn ions.

Dihydroquercetin (dhq) and its 3-acetate react with acetic anhydride in the absence of a base catalyst to yield mixtures of partially acetylated products. Three new esters were characterized by NMR spectroscopy as dhq 3,7,3′-triacetate, 3,7,4′-triacetate and 5,7,3′,4′-tetraacetate. At its melting point neat dhq 3,7,3′,4′-tetraacetate is partially converted to dhq 3,3′,4′-triacetate and dhq pentaacetate by intermolecular acetyl transfer. Dhq 7,3′,4′-triacetate yields exclusively dhq 3′,4′-di- and 3,7,3′,4′-tetraacetate under these conditions. The acetylation/deacetylation reactions are accompanied by partial epimerization: 3 new acetates with 2,3-cis stereochemistry (dhq 3-, 3,7,3′,4′-tetra- and penta-) were identified. Dhq and its 3,7,3′,4′-tetraacetate undergo regiospecific dibromination at C-6 and C-8 with excess N-bromosuccinimide in polar solvents, and 6,8-dibromo-dhq can be regioselectively debrominated to 8-bromo-dhq with sodium sulfite.

The original version of the article was published in Cent. Eur. J. Chem., Vol. 8(3), (2010), pp. 687–695. Unfortunately, the original version of this article contains mistakes in the Authors names section. There should be: Saman Azodi-Deilami1, Majid Abdouss1 and S. Rezvaneh Seyedi2.