Band 9, Heft 4

This review covers almost 290 heterobinuclear Pt derivatives. When the heterometals (M) are non transition and the binuclear are found both with and without a metal to metal bond. Where M is a transition metal or actinide, only those with a metal-metal bond have been included here. There are thirteen non-transition metals (Sn, Hg, Ge, Sb, Tl, Zn, Pb, Cd, Na, K, Ga, Ca and In). The shortest Pt-M bond distance is 235.2(1) (Pt-Ge). There are eighteen transition metals (Fe, W, Rh, Re, Pd, Ag, Ir, Mo, Mn, Re, Co, Cu, Cr, Au, Ni, Ti, Ta and V). The shortest Pt-M bond distance is 249.5(2) pm (Pt-Cr). There is one example of an actinide, Pt-Th at 298.4(1) pm. The Pt atom has oxidation numbers 0, +2 and +4. The Pt coordination geometries include square planar (most common), trigonal bipyramidal, pseudo octahedral (Pt(IV)) and a few prevalently capped trigonal prismatic seven coordinate species. There are at least two types of isomerism distortion and polymerisation. Factors affecting bond lengths and angles are discussed and some ambiguities in coordination polyhedra are outlined.

An alternative procedure for the calculation of highly excited vibrational levels in S0 formaldehyde was developed to apply to larger molecules. It is based on a new set of symmetrized vibrational valence coordinates. The fully symmetrized vibrational kinetic energy operator is derived in these coordinates using the Handy expression [Molec. Phys. 61, 207 (1987)]. The potential energy surface is expressed as a fully symmetrized quartic expansion in the coordinates. We have performed ab initio electronic computations using GAMESS to obtain all force constants of the S0 formaldehyde quartic force field. Our large scale vibrational calculations are based on a fully symmetrized vibrational basis set, in product form. The vibrational levels are calculated one by one using an artificial intelligence search/selection procedure and subsequent Lanczos iteration, providing access to extremely high vibrational energies. In this work special attention has been given to the CH stretch system by calculating the energies up to the fifth CH stretch overtone at ∼16000 cm−1, but the method has also been tested on two highly excited combination levels including other lower frequency modes.

It has been reported that the length of the molecular chain and the rigidity of molecules influence the structure of the polymer network in PDLC films and hence the electro-optical properties of the composites. Herein, a series of new aromatic monomeric monomethacrylates, bismethacrylates and monovinylbenzene derivatives with a mesogenic core were successfully synthesized under microwave irradiation. The microwave assisted synthesis resulted in decreased reaction times, reduced solvent requirement, increased operational simplicity, and in most cases, improved yields and selectivity.

A geometry and SCF convergence study of Hartree-Fock calculations using the 6-31G* basis set is carried out on the set of all possible diatomic molecules formed from atoms with Z≤36. The utility of Hartree-Fock calculations using the smaller STO-3G basis set to improve the convergence behavior is demonstrated.

The CdSe quantum dots (QDs) with bidentate ligands: a-diimine (NN) and dihydrolipoic acid (DHLA) were synthesized and characterized by UV-Vis, particle size and capillary electrophoretic techniques. Two systems were analyzed: CdSe with one ligand (CdSe/ligand) and CdSe with two different ligands (CdSe//ligand1/ligand2), where ligand = α-diimine or DHLA. Hydrodynamic features of functionalized QDs were characterized by zone capillary electrophoretic (CZE), and particle size techniques and these methods were consistent. It was established that CZE, micellar (MEKC) and microemulsion (MEEKC) modes were suitable for separating charged CdSe QDs and that no peaks were obtained for QDs passivated with electrically neutral ligands. For CdSe QDs with neutral (NN) ligands, a preconcentration method with the use of a micellar plug was introduced for visualizing these QDs. A sharp peak representing neutral QDs was obtained within the zone of micellar plug of a non-ionic surfactant, Here, a ligand character used for CdSe modification and the type of the electrophoretic method applied were the determining factors for the QDs peak visualization. Moreover, examples of visualization of charged and neutral QDs on the same run were presented, and for this purpose, dual mechanism (separation/preconcentration) was proposed.

A novel oxo-centered trinuclear mixed-metal carboxylate complex with unsaturated bridging ligands [Fe2Cr(µ3-O)(C3H3O2)6(H2O)3]·NO3·4H2O has been synthesized and characterized by means of Elemental analyses, Infrared spectroscopy and Crystal structure analysis. The compound crystallizes isotypically in the monoclinic space group type P21/c. In the compound, each M(III) cation is coordinated by six O atoms from four unsaturated carboxylate groups as bridging ligands, one water molecule as the terminal ligand, and a µ3-oxygen atom in the center of an equilateral triangle. The infrared spectra show resolved bands arising from νasym(COO) and νsym(COO) vibration of bridging carboxylate ligands along with those of νasym(M2M′O) vibration in the complex. The difference between symmetrical and asymmetrical (COO) ligands indicate that the acrylate bridge is present in the structure of complex.

This article describes the simple hydrodehalogenation of halogenated anilines and their derivatives by the action of Raney aluminium-nickel alloy in aqueous alkaline solution at room temperature. The reaction course was monitored by means of 1H nuclear magnetic resonance (NMR) spectroscopy and GC-MS spectra. The effect of Al and Ni and the nature and quantity of the base for effective hydrodehalogenation were studied. The possibility of lowering Al content more than 500 times and Ni content more than 10 times in the filtered mother liquor by a dehalogenation procedure was tested using precipitation. The reduction method described was satisfactorily proved for dehalogenation of polyhalogenated anilines in the multiphase dimethoxymethane/aqueous NaOH/Al-Ni reaction mixture. Dehalogenation under multi-phase conditions was demonstrated for the preparation of ortho-alkylated anilines from simply available 2-substituted-4-chloroanilines.

In the present study, a simple procedure for the isolation by solid-phase extraction (SPE) and quantification by UV-Vis spectrometry (400 nm) of the humic acids (HAs) in the natural waters was developed. Seven different sorbents: Porapak P (polystyrene-divinylbenzene copolymer), Florisil (chemical composition: 84.0% SiO2, 15.5% MgO and 0.5% Na2SO4), Silica gel C18 (octadecyl silane), Strata X (surface modified polystyrene-divinylbenzene), Strata NH2 (silica-based trifunctional amino ligand), Strata SAX (silica-based trifunctional quaternary amine) and Strata C18-E (silica-based trifunctional C18 with hydrophobic end-capping of silanols) were tested. The HAs, adsorbed on SPE cartridges, were eluted using: NaOH (0.1 M), sodium dodecyl sulphate (SDS) (20 g L−1), and a 1:1 v/v mixture of SDS (20 g L−1) and NaOH (0.1 M). The extraction efficiency was evaluated by comparing the HAs recovery levels. The repeatability of results was estimated by the relative standard deviation (RSD). The data confirmed that Porapak P, Silica gel C18, Florisil, Strata NH2 and Strata X could be good alternatives for the traditional isolation of the aquatic HAs with XAD resin. The proposed method was applied for the determination of HAs in some waters sampled from the Western Romanian Plain. The content of HAs was correlated with the arsenic concentration and total organic carbon (TOC) level.

Grubbs II generation catalyst (3), bearing a fluorinated imidazolinium ligand, was investigated in cross metathesis (CM), ring closing metathesis (RCM) and ring opening polymerization metathesis (ROMP) for a variety of substrates. Kinetic studies showed reduced stability of the catalyst in methylene chloride following the first 15 minutes of reaction preventing a higher efficiency despite the very high activity. Beneficial solvent effects on the catalyst stability were observed by performing RCM in C6F6.

Two series of substituted ferrocenes were synthesised using either the Horner-Wadsworth-Emmons reaction or monolithiation of ferrocene. The series consist of arylthio- and styryl-ferrocenes with different substituents in the para position of the aryl rings of the systems. The electronic communication was investigated by comparing the substituent effects in absorption spectroscopy and in cyclic voltammetry. A small substituent effect was found in the electronic transitions of the styryl substituted ferrocenes. The oxidation of the ferrocene derivatives showed clear substituent effects as illustrated by the linear Hammett plots. The effect was shown to be an order of magnitude larger in the arylthio-systems than in the styryl systems. It is suggested that the reason behind the large effect is a direct sulfur-iron orbital overlap.

In the present study newly produced semiconductor ceramic nanopowder materials made of CdTe and Cd1−xZnxTe (CZT) are considered. Common features and differences in microstructures, phase transformations, grain growth and properties of the ceramic materials of the binary and ternary compositions are studied.

Fluorescence spectroscopy and circular dichroism (CD) spectroscopy were used to investigate the interaction of coumarin-3-carboxylic acid with human serum albumin (HSA) and bovine serum albumin (BSA) under physiological conditions in a buffer solution of pH 7.4. Quenching constants were determined using the Lineweaver-Burk equation to provide a measure of the binding affinity of coumarin-3-carboxylic acid to HSA/BSA. Binding studies concerning the number of binding sites, n, and apparent binding constant, K, were performed by a fluorescence quenching method at different temperatures (298, 303 and 310 K). The thermodynamic parameters, enthalpy change (ΔH0) and entropy change (ΔS0) as calculated according to the van’t Hoff equation, indicated that hydrogen bonding and van der Waals forces play a major role in coumarin-3-carboxylic acid-HSA association whereas electrostatic interactions dominate in coumarin-3-carboxylic acid-BSA association. The distance, r, between the donor (HSA/BSA) and acceptor (coumarin-3-carboxylic acid) has been estimated using Förster’s equation, on the basis of resonance energy transfer. Furthermore, CD spectra were used to investigate the α-helix changes of the HSA and BSA molecules upon addition of coumarin-3-carboxylic acid.

A new series of twenty four derivatives of pyrano[3,2-c]chromene IVa-x bearing 1H-pyrazole were synthesized by a one pot, base-catalyzed cyclocondensation reaction of 1H-pyrazole-4-carbaldehyde Ia-l, malononitrile II and 4-hydroxycoumarin IIIa-b. All the synthesized compounds were characterized by elemental analysis, FT-IR, 1H NMR and 13C NMR spectral data. All the synthesized compounds were screened against six bacterial pathogens, namely B. subtilis, C. tetani, S. pneumoniae, S. typhi, V. cholerae, E. coli and for antifungal activity against two fungal pathogens, A. fumigatus and C. albicans using the broth microdilution MIC method. Some of the compounds were found to be equipotent or more potent than commercial drugs against most of employed strains, as evident from the screening data.

The analytical performances of coupled chemical vapor generation, integrated atom trap (CVG-IAT) atomizer flame atomic absorption spectrometry (FAAS) system were evaluated for determination of nickel in environmental samples. Nickel chemical vapors are atomized in an air-acetylene flame-heated IAT. A new design of CVG-IAT-FAAS hyphenated technique that would exceed the operational capabilities of existing arrangements (a water-cooled single silica tube, double-slotted quartz tube) permitting construction of an “integrated trap” was investigated. An improvement in limit of detection was achieved compared with that obtained using any of the above atom trapping techniques separately. The concentration limit of detection was 1 ng mL−1 for Ni. The overall efficiencies of the vapor generation process was estimated to be ca. 50%. For a 2 min in situ pre-concentration time, sensitivity enhancement, compared to FAAS, was 200 folds for Ni, using vapor generation atom trapping technique. The sensitivity can be further improved by increasing the collection time. The precision of the measurements for 25 ng mL−1 of Ni was 9% RSD. The accuracy of this method was tested by analyses of NIST SRM 2704 (Buffalo River Sediment), NIST SRM 1648 (Urban Particulate Matter), NIST SRM 2710 (Montana Soil), NBS SRM 1633a (Coal Fly Ash) and NIST SRM 1643e (Trace Element in Water) certified reference materials. The measured Ni content in five reference materials was in satisfactory agreement with the certified values (in the range of 14.3–98 μg g−1). The hyphenated technique was applied for nickel determination in coal fly ash, soil, sediment, sewage and river water.

In the present paper, hydroxyapatite and structurally modified hydroxyapatite were investigated to establish the best material for nicotinic acid adsorption. Structurally modified hydroxyapatite wa prepared by adding sodium silicate in the reaction medium. The influence of silica concentration, presence of small amounts of metal ions, temperature and initial concentrations of nicotinic acid solutions on the adsorption capacity, were studied. Results indicated that structurally modified hydroxyapatite doped with copper adsorbed the highest amount of nicotinic acid. For this material the adsorption capacity was 0.232 mg nicotinic acid / g material, at an initial concentration of 10−4 M nicotinic acid. For all types of materials, best results were obtained at 15°C. The amount of nicotinic acid adsorbed increases with the decrease in temperature and with the increase in the initial concentration of nicotinic acid. Adsorption kinetics data were modeled using pseudo-first and pseudo-second order models while the interference due to diffusion was analyzed with intraparticle diffusion model. The results indicate that pseudo-second order model best describes the adsorption kinetics data, indicating the formation of chemical bonding. The materials used in this study were characterized by the following methods: IR, Coulter Counter analyzer, Scanning Electron Microscope and BET

The oxidation process of 1-methoxy-4-(1-methylethyl)benzene catalysed by N-hydroxyphthalimide (NHPI) or NHPI in combination with Cu(II), Co(II), Mn(II) and Fe(II) salts was studied. The effects of the amount of catalyst and the temperature were determined. 1-Methyl-1-(4-methoxyphenyl)ethyl hydroperoxide was obtained in a yield of 73 mol% when 1-methoxy-4-(1-methylethyl)benzene was oxidised for 3 h at 60°C in acetonitrile as a solvent in the presence of NHPI. 1-(4-Methoxyphenyl)ethanone with high selectivity up to 68–75 mol%, but low yield amounting to 11 mol% was obtained when 1-methoxy-4-(1-methylethyl)benzene was oxidised in the presence of the NHPI/Cu(II) system at 120°C.

Wine samples (Grüner Veltliner (GV) and Zweigelt (ZW) from four different geographical regions of Austria and Czech Republic) were analyzed to determine their total phenolic content (TPC) by applying the Folin-Ciocalteau method, total antioxidant activity (TAA) by FRAP (ferric reducing antioxidant power) and DPPH (1,1-diphenyl-2-picryl-hydrazyl) assays, and to identify and quantify eleven phenolic compounds using a HPLC/UV-VIS method.

Electrochemical behaviour of some alkaloids, namely: caffeine, aminophylline, theophylline, codeine phosphate and papaverine hydrochloride, that are in solution in various combinations or in the presence of other compounds contained in pharmaceuticals or in real samples (urine) was investigated using cyclic voltammetry (CV), square-wave voltammetry (SWV) and differential pulse voltammetry (DPV) on electrochemically activated glassy carbon electrode. The proposed electroanalytical methods were successfully applied in the simultaneous determination of these alkaloids in different combination or in the presence of other compounds. The great part of these combinations can be analyzed simultaneously because they practically do not interfere. The electrochemical test methods attempted to detect the presence of alkaloids in urine samples collected from subjects who consumed coffee (caffeine), and from a patient under treatment with Miofilin® (aminophylline). Urine samples were determined after filtration, without prior dilution and after dilutiion with acetate buffer at pH 4.5. Best results were obtained using DPV performed on electrochemically activated glassy carbon electrode. Thus in samples taken from subjects who drink coffee the caffeine concentration detected was 6.21×10−7 mol L−1 in the first sample and 7.77×10−7 mol L−1 in the second sample, while aminophylline concentration detected was 1.15×10−7 mol L−1.

The hydrogenation properties of magnesium hydride mechanically milled with iron fluorides (FeF2 and FeF3), were investigated by Temperature Programmed Desorption (TPD) and volumetric methods using a Sieverts-type apparatus, as prepared upon dehydrogenation and finally upon subsequent hydrogenation. The activation energy of hydrogen desorption (Ea), calculated from the Kissinger formula using TPD measurements obtained with different heating rates, showed significant decreases of Ea in comparison to that of milled MgH2 without any dopants. Moreover, the influence of these metal fluorides on the thermodynamics of the decomposition process was also examined. In the case of the FeF2 dopant, rehydrogenation following desorption caused the complete decomposition of the iron fluoride to BCC iron and the formation of a predominant MgH2 phase. In contrast to FeF2, the addition of FeF3 led to the formation of β-MgH2 as a major phase coexisting with Mg2FeH6 and MgF2 compounds. The presence of pure Fe in the MgH2+FeF2 composite, as opposed to MgH2+FeF3 containing Mg2FeH6 and MgF2, did not cause any significant influence on the sorption properties of MgH2. Moreover, the original material doped with FeF3 predominantly showed iron in the Mg2FeH6 compound, while the FeF2 dopant iron mostly showed the nearly pure BCC metallic phase

Starting from the paddlewheel complex copper(II)acetate, the green N-methylimidazole adduct of copper(II)acetate is formed and transformed into the monomeric and dimeric N-methylimidazole adducts of copper(II)acetate [Cu(C4H6N2)2(CH3COO)2]n·xH2O (n = 1,2; x = 0, 6). The formation of the blue dimer or the purple monomer depends on the solvent and the presence or absence of water.

This paper presents mathematical and computational modelling of kinetics of a bioelectroanalytical system based on the interfacial action of hydrolytic enzyme. A system of non-linear differential equations with diffusion is used to describe the kinetics of Termomyces lanuginosa lipase (TLL) catalyzed hydrolysis of L-ascorbic acid palmitate (AAP). The system was solved numerically, and the kinetic prameters of AAP hydrolysis by the enzyme were determined. The experimental and modelling results show linear dependence of the rate of AAP hydrolysis on the TLL concentration. Complex dependence of the initial rate of bioelectrocatalytic current increase on the thickness of total diffusion layer (hydrodynamic diffusion layer plus thickness of dialysis membrane on the electrode surface) is also demonstrated and explained.

The adenine-thymine (AT), adenine-uracil (AU) and guanine-cytosine (GC) base associates in clusters containing 400 water molecules were studied using a newly implemented Metropolis Monte Carlo algorithm based on the extended cluster approach. Starting from the hydrogen-bonded Watson-Crick geometries, all three base pairs are transformed into more favorable stacked configurations during the simulation. The obtained results show, for the first time, the transition from planar base pairs to stacked base associates in the Monte Carlo framework. Analysis of the interaction energies shows that, in the water cluster, the stacked dimers are energetically preferable compared to the corresponding Watson-Crick base pairs. This is due to the larger base-water interaction in the stacked structures. The water-water interaction is one of the main factors promoting the formation of stacked dimers, and the obtained data confirm the crucial role of the water-water interactions in base stacking.

Selected β-diketones bearing unsaturated derivatives have been demonstrated to undergo homo-metathesis and cross-metathesis with selected olefins in the presence of Grubbs catalysts. The reactions led to respective homo- and cross-metathesis products mainly with good yields and selectivities.

An approximate analytical solution of the radial Schrödinger equation for the generalized Hulthén potential is obtained by applying an improved approximation of the centrifugal term. The bound state energy eigenvalues and the normalized eigenfunctions are given in terms of hypergeometric polynomials. The results for arbitrary quantum numbers n r and l with different values of the screening parameter δ are compared with those obtained by the numerical method, asymptotic iteration, the Nikiforov-Uvarov method, the exact quantization rule, and variational methods. The results obtained by the method proposed in this work are in a good agreement with those obtained by other approximate methods.

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.

The original version of the article was published in Cent. Eur. J. Chem. 9(3) (2011), pp 391–403. Unfortunately, the original version of this article contains mistakes in the caption of the y-axis of Figs. 5,6 and 10 due to a font conversion problem. The actual units on the y-axis of these figures should be µS cm−1, not mS cm−1.