Band 6, Heft 2

Textured Ni tapes were fabricated from commercially available nickel pellets (98.5% Ni). Ingots produced by a melt process were cold rolled to 150–400 μm thick tapes. Texturing was achieved by annealing in a reducing atmosphere (Ar + 6.5% v/v H2). Sharp cubic biaxial textured Ni tapes were obtained by thermal treatment at 1000°C for 2 hours in a reducing atmosphere. The tapes were characterized by scanning electron microscopy, X-ray diffraction and by electron backscattering diffraction. The tensile strength, the thermal expansion behavior and the Vickers hardness for the cold rolled tapes and for the heat-treated tapes were measured.

Three simple protocols for the extraction of acyclovir from its pharmaceutical creams based on ultrasonication, ultrasonication with heating and magnetic stirring were evaluated and compared. Extraction kinetics were studied at different time intervals (5, 10, 15, 30 and 60 min) and the extraction efficiency was determined by HPLC. The effect of concentration of aqueous NaOH as the extraction medium and the stirring speed were also studied and optimized. Best results were obtained with 50 mL of 0.01 mol L−1 aqueous NaOH with magnetic stirring speed of 500 r.p.m. HPLC analysis involved rapid separation of acyclovir from the cream matrix using a 100 × 4.6 mm i.d. monolithic column and UV detection at 254 nm. Magnetic stirring produced the best results in terms of extraction efficiency with an average extraction yield of 100.8%, n = 16 at an optimum extraction time of 15 min. The selected protocol was validated for within and day-to-day precision and ruggedness.

The mechanisms of oxidation of a series of a-alkyl substituted mono and dimethoxylated benzyl alcohols catalysed by mesotetrakis(4-N-methylpyridynium)porphyrin iron (III) chloride (FeTMPyPCl) and meso-tetrakis(4-sulfonatophenyl)porphyrin iron (III) chloride (FeTSPPCl) in aqueous solution with KHSO5 as oxygen atom donor and by meso-tetrakis(pentafluorophenyl)-porphyrin iron (III) chloride (FeTPFPPCl) in dichloromethane employing iodosylbenzene as oxidant have been investigated. In the highly polar aqueous medium an electron transfer mechanism is operating. With FeTMPyPCl, which is a much more efficient catalyst than FeTSPPCl due to the presence of stronger electron withdrawing substituents, formation of side-chain oxidation products accompanies generation of nuclear oxidation products. In the low polar solvent dichloromethane, two competing mechanism have been suggested: hydrogen atom transfer and formation of a complex between the active species iron-oxo porphyrin radical cation and the substrate.

Derivatives of purine, adenine, guanine, and 2,6-diaminopurine linked to the azanonaborane (B8N cluster) have been prepared, for possible use as powerful agents for boron neutron capture therapy (BNCT). The synthesis was carried out via a ligand exchange reaction. The exo-NH2R group of the azanonaborane of the type [(RH2N)B8H11NHR] can be exchanged by one hetero-nitrogen atom of the pyrimidine ring, and except for guanine, also by an N atom of the imidazole ring. The identity of the products was confirmed by NMR, elemental analysis, IR, and mass spectrometry. No reaction was found to occur with caffeine and theophylline under the same reaction conditions.

A number of stereoisomeric ureas (N-[aryl(benzyl, or cycloalkyl)carbamoyl]-exo(endo)-5-aminomethylbicyclo[2.2.1]hept-2-enes) have been synthesized from bicyclo[2.2.1]hept-2-en-exo(endo)-5-carbonitrile by reduction with lithium aluminum hydride and subsequent reaction of the resulting amines with aryl (benzyl, or cycloalkyl) isocyanates. Regioselective alkylation of stereoisomeric ureas has been performed with benzyl chloride under liquid/solid phase-transfer catalysis. The outcome of the reactions of ureas with peroxy acids is dependent upon the orientation of substituents in the bicyclic fragment. Exo-isomeric ureas are transformed into corresponding epoxy-derivatives, while reactions of the endo-isomers are accompanied by intramolecular cyclization, resulting in the formation of azatricyclononane derivatives. Quantum-chemical calculations have established a decisive role for additional hydrogen bonding in the stabilization of transition states in these heterocyclization reactions of ureas. The structures and stereochemical homogeneity of the products have been confirmed by the analysis of 1H and 13C NMR spectra and correlation spectroscopy. The mechanism of the intramolecular heterocyclization reaction of ureas and carboxamide of endo-5-aminomethyl-exo-2,3-epoxybicyclo[2.2.1]heptane series has been studied at the BHandHLYP/6-31G(d) level of theory.

Kinetic study on the decomposition of Prussian Blue electrocatalytic layer during electrochemical reduction of hydrogen peroxide has been studied in relation to biosensor application of this electrocatalyst. The decomposition has been shown to proceed as a nearly exponential decay process and the corresponding first-order rate coefficients were determined. It has been shown that the decomposition proceeds about 10 times faster in pH 7.3 buffer solution as compared to pH 5.5 buffer. A linear dependence of the decomposition rate on the concentration of hydrogen peroxide has been found.

The effect of microwave irradiation on the reactions of 2-[3-(trifluoromethyl)phenyl]-4-R1-furo[3,2-b]pyrrole-5-carboxhydrazides 1 with 5-arylfuran-2-carboxaldehydes 2, thiophene-2-carboxaldehyde (3) and methyl 2-formylfuro[3,2-b]pyrrole-5-carboxylates 4 has been studied. Reactions of 1 with formic and acetic acid, respectively, led to acylhydrazides 9a–c. Reaction of 1a with 4-substituted 1,3-oxazol-5(4H)-one 10 led to imidazole derivative 13. 1,2,4-Triazole-3-thiones 15a,b were synthesized by two-step reaction of 1a with potassium isothiocyanate and phenyl isothiocyanate, respectively, and subsequent base-catalyzed cyclization of thiosemicarbazides 14a,b. Pyrazole 16 was prepared by reaction of 1a with pentane-2,4-dione.

An one-pot approach was developed for the synthesis of substituted 5,7-dihydro-1,6-naphthyridines and 5,6,7,8-tetrahydroquinolines with moderate to good yields. This pathway is a modified two-step synthesis of Kröhnke pyridine and involves a four-component tandem reaction of N-phenacylpyridinium bromide, aromatic aldehydes, substituted or nitrogen-containing cyclic ketones and a nitrogen source. This multi-component reaction is performed using microwave irradiation heating of the reaction substrates under an environment of NH4OAc/HOAc.

A Electrosynthesis of conducting poly(3-methylpyrrole) (P3MPy) and poly(3-methylpyrrole-2,6-dimethyl-β-cyclodextrin) (poly(3MPy-β-DMCD)) films on a gold electrode in acetonitrile electrolyte solution containing lithium perchlorate has been carried out by potential cycling. Products were characterized with cyclic voltammetry CV, in situ UV-Vis spectroscopy, and in situ resistance measurements. Electrosynthesis of poly(3MPy-β-DMCD) started with a (1:1) (3MPy-β-DMCD) supramolecular cyclodextrin CD complex of 3-methylpyrrole characterized with proton NMR spectroscopy. The oxidation peak of poly(3MPy-β-DMCD) in CVs is shifted to more positive values than P3MPy. In situ resistance measurements show that the resistance of poly(3MPy-β-DMCD) is higher than of P3MPy by approximately an order of magnitude. Minimum resistance can be observed for P3MPy and poly(3MPy-β-DMCD) at 0.40 E Ag/AgClE Ag/AgClIn situ UV-Vis spectroelectrochemical data for both films prepared potentiodynamically by cycling the potential in the range −0.20 E Ag/AgCl

The main objective of this paper is to introduce principal component analysis and two robust fuzzy principal component algorithms as useful tools in characterizing and comparing rime samples collected in different locations in Poland (2004–2007). The efficiency of the applied procedures was illustrated on a data set containing 108 rime samples and concentration of anions, cations, HCHO, as well as pH and conductivity. The fuzzy principal component algorithms achieved better results mainly because they are more compressible than classical PCA and very robust to outliers. For example, a three component model, fuzzy principal component analysis-first component (FPCA-1) accounts for 62.37% of the total variance and fuzzy principal component analysis-orthogonal (FPCA-o) 90.11%; PCA accounts only for 58.30%. The first two principal components explain 51.41% of the total variance in the case of FPCA-1 and 79.59% in the case of FPCA-o as compared to only 47.55% for PCA. As a direct consequence, PCA showed only a partial differentiation of rime samples onto the plane or in the space described by different combination of two or three principal components, whereas a much sharper differentiation of the samples, regarding their origin and location, is observed when FPCAs are applied.

The influence of EDTA, carboxylic acids, amino-and hydroxocarboxylic acids, monosaccharides and humic substances on the generation of arsines in hydride generation atomic absorption spectrometry (HGAAS) was investigated. EDTA (0.02 mol L−1), ascorbic acid (0.02 mol L−1) and glucose or fructose (0.2 mol L−1) are useful additives for levelling sensitivities for As(III), monomethylarsonate (MMA) and dimethylarsinate (DMA). The presence of glycine, malonic, tartaric acids, BICIN and soil humin extracts leads to differences in analytical signal response between these arsenic species. An analytical application to the determination of the sum of As(III), monomethylarsonate (MMA) and dimethylarsinate (DMA) as well as the sum of toxicologically relevant hydride forming arsenic fraction As(III) + As(V) + MMA + DMA in EDTA soil/sediment extracts using continuous flow HGAAS was demonstrated. The limit of detection was 0.2 mg kg−1 As. Within-day and between-day precision were in the range 3–7% and 4–10%, respectively, for arsenic contents of 0.7–25 mg kg−1, with recoveries 95–103%.

A simple and highly sensitive spectrofluorometric method was developed for the determination of some 1,4-dihydropyridine compounds namely, nicardipine, nifedipine and isradipine in pharmaceutical preparations and biological fluids. The method is based on the reduction of nicardipine, nifedipine and isradipine with Zn/HCl and measuring the fluorescence intensity obtained (λem/λex) at 460/364, 450/393 and 446/360 nm, respectively. The factors affecting the development of the fluorophore and its stability were studied and optimized. The effect of some surfactants such as β-cyclodextrin (βCD), carboxymethylcelullose (CMC), sodium dodecyl sulphate (SDS) and triton X-100, on the fluorescence intensity was studied. The fluorescence intensity-concentration plots of nicardipine, nifedipine and isradipine were rectilinear over the ranges 0.4–6.0, 0.2–4.0 and 0.1–9.0 μg ml−1 with detection limits of 0.0028, 0.017 and 0.016 μg ml−1, respectively. The proposed method was successfully applied to commercial tablets containing the compounds; the percentage recovery agreed well with those obtained using the official methods. The method was further extended to the in vitro determination of the compounds in spiked human plasma and urine samples. A proposal of the reduction reaction pathway was postulated.

A single step derivatisation for the determination of putrescine and cadaverine by gas chromatography using trifluoroacetylacetone (TFAA) in methanol or ethanol was studied and optimised. The derivatives were analysed by an iontrap gas chromatograph-mass spectrometer (GC-MS) operating with electron impact ionisation with selective ion storage (EI-SIS) mode. The optimised mole ratios for TFAA/putrescine and TFAA/cadaverine reactions were 5/1 and 5.8/1 respectively with a reaction time of 15 minutes at 95oC. The retention times for the derivatised putrescine and cadaverine were 11.3 and 12.2 minutes respectively using the capillary column, CP-Sil 8CB; 30 m length x 0.25 mm i.d. x 0.25 mm film. The correlation coefficients (R2) of calibration curves for putrescine and cadaverine were 0.991 and 0.990 respectively over a concentration range of 100 ng cm−3 to 1500 ng cm−3. The method developed was found to be simple (single-stage derivatisation), rapid (15 minutes derivatisation & 14 minutes GC/MS run) and accurate (putrescine and cadaverine recoveries 94.8%–97.7%).

The kinetics of the C-S coupling of arylmagnesium bromides with phenyl tosylate has been studied in THF: toluene at 90°C. The reaction is first order in Grignard reagent and first order in phenyl tosylate. Kinetic data, Hammett relationship and activation parameters are consistent with a nucleophilic addition mechanism involving rate determining attack of carbanion to sulfonyl group followed by a fast phenoxide group leaving.

Increasing environmental pollution caused by toxic dyes due to their hazardous nature is a matter of great concern. It has been generally agreed that methyl orange (MO) can be effectively degraded in aerated K2S2O8 homogeneous reaction system using near-UV irradiation. In this paper photocatalytic degradation of MO solutions with K2S2O8 was investigated, with particular attention on the possible underlying mechanisms. This report has shown decolorization efficiency of MO increases with the increasing of the dosage of the catalyst. There is no optimal amount of catalyst in our case, where special attention was paid on the nature of the photocatalyst itself. The current research revealed that the decolorization reaction is a pseudo first-order reaction when the concentration of MO is below 20 mg L−1 and the decolorization reaction is zero-order reaction when the concentration of MO is above 100 mg L−1, but the Langmuir-Hinshewood kinetic model does not describe this. The influence of IO 4−, BrO 3− and H2O2 were investigated in detailed. Several observations indicate that the mechanism is not involved in hydroxyl radical attacks in MO degradation with K2S2O8 by UV irradiation. The possible underlying mechanisms are direct oxidation of the MO by S2O 82− and hydrogen attraction by SO 4•−.

Sub-micrometer nickel powders of controlled size and morphology were produced by a surfactant-assisted polyol method, using ethylene glycol (EG) as solvent and reductant in the presence of sodium dodecyl sulfate (SDS) surfactant and NaOH. The resultant Ni powders were characterized by XRD, SEM, EDS, and FTIR. Spherical, hexagonal, and triangular fcc Ni powders from 0.30 to 0.60 μm were obtained in the presence of SDS; irregular spherical fcc Ni powders were obtained in its absence. The concentrations of SDS, NaOH and Ni(CH3COO)2·4H2O greatly influence the product morphology and size.

A cheap and efficient fibrous hydrolyzed polyacrylonitrile (HPAN) sorbent was obtained by alkaline hydrolysis of Romanian polyacrylonitrile fibres. Scanning electronic microscopy and infrared spectroscopy were used to characterize the hydrolyzed product and to confirm its functionalization. The adsorptive potential of the proposed sorbent for reactive dye Brilliant Red HE-3B removal from aqueous solutions of pH=2 was examined by the batch technique as a function of dye concentration, temperature solution and contact time. The Freundlich, Langmuir and Dubinin-Radushkevich adsorption models were applied to describe equilibrium sorption data and to determine the corresponding isotherm constants. The thermodynamic parameters ΔG, ΔH and ΔS were also determined; the values obtained show that sorption of reactive dye on HPAN fibres is a spontaneous, endothermic and entropy-driven process. The kinetics of sorption of the reactive dye were analyzed using pseudo-first order and pseudo-second order kinetic models. The kinetic data fitted well to pseudo-second order kinetics, indicating the chemisorption of reactive dye onto the fibrous sorbent. The sorption mechanism of the dye onto hydrolyzed fibres was confirmed by FTIR spectroscopy. The dye-loaded HPAN sorbent can be regenerated by treatment with 0.1M NaOH and the regenerated sorbent may be reused in several adsorption-desorption cycles. The results of this study provided evidence that the HPAN fibres are effective for removing reactive dye Brilliant Red HE-3B from aqueous effluents.

In the present study, Quantitative Structure-Activity Relationship (QSAR) modeling has been carried out for lipid peroxidation (LPO)-inhibition potential of a set of 27 flavonoids, using structural and topological parameters. For the development of models, three methods were used: (1) stepwise regression, (2) factor analysis followed by multiple linear regressions (FA-MLR) and (3) partial least squares (PLS) analysis. The best equation was obtained from stepwise regression analysis (Q2 = 0.626) considering the leave-oneout prediction statistics.

Membrane separations are finding greater use in wastewater treatment because of their efficiency. In order to prove the effectiveness of membrane filtration an applicability study is carried out. Nanofiltration and reverse osmosis membranes are tested under quite different conditions to reduce the chemical oxygen demands (COD) of wastewaters to meet the Council Directive 76/464/EEC release limit. Two kinds of real wastewaters were selected for the investigation. The wastewaters represent extreme different circumstances since the difference between their COD is two orders of magnitude. All of the membranes tested can be applied either to the treatment of wastewater of high COD (pharmaceutical wastewater) or wastewater of low COD (dumpsite leachate), since the different conditions do not change the membrane characteristics. The experimental data show that none of the membranes can decrease the COD to the release limit in one step. However, if two-stage filtrations (nanofiltration followed by reverse osmosis) are accomplished for both of the wastewaters, a total COD reduction of 94% can be achieved. With the application of the two-stage filtration the COD of the wastewater of low COD can be decreased below the release limit but in case of wastewater of the high COD further treatment will be required.

Adsorption characteristics of herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA) have been evaluated using bituminous shale (BS) as a model adsorbent-containing solid organic matter in a mineral matrix. The adsorption of MCPA on BS has been studied with varying concentration, temperature, pH and contact time, using batch technique. Adsorption ability of BS increases with increasing temperature and decreasing pH in the studied concentration range of (0.6–4.0) × 10−4 M. Theoretical curves calculated from Freundlich, Dubinin-Radushkevich (D-R), Langmuir and Temkin isotherm equations show a two-step isotherm shape. The results could be explained by assuming the presence of two-type sites with different affinity on adsorbent surface. Adsorption process is endothermic and entropy controlled at the first stage, and exothermic and enthalpy controlled at the second stage. The mechanism proposed based on surface ionization and complexation model is consistent with the pH dependent experimental results. Kinetic data fit well to both Paterson’s and Nernst Planck model based on homogeneous solid phase diffusion (HSPD). The values of particle diffusion coefficients (D p ) predicted from both models are comparable each other and independent of temperature and concentration.

A novel method for the preparation of biaxial textured nickel oxide on commercially available nickel via a modified surface oxidation epitaxy (SOE) process has been developed. Following studies of different heat-treatment procedures for both texturing of nickel and for the fabrication of nickel oxide the following method was found to yield the best results. Nickel was first textured under an argon — hydrogen atmosphere at 1000°C for 120 min, then the temperature was lowered to 800°C and the atmosphere was changed to argon with 3 ppm oxygen. Smooth and crack free c-axis textured and a–b aligned NiO buffer layers with an out-of-plane texture of 7.8° and an in-plane texture of 9.4° were successfully produced. Higher oxygen partial pressure and temperatures resulted in increased surface roughness and excessive grain growth.

The relative enthalpies of melts in the system KF - K2NbF7 were measured by drop-calorimetry at the temperatures 1058, 1140 and 1208 K as a function of composition. Heat capacities of melted mixtures and enthalpies of mixing were determined using the experimental data. The molar heat capacity of melts diverges slightly from additivity. The molar enthalpy of mixing of melts shows small negative deviation from ideality which decreases with decreasing temperature. The thermal effect at mixing was assigned predominantly to association reactions producing more complex fluoroniobate anions.

The The mechanism of reaction between 3-hydroxy-3-methyl-2-butanone and malononitrile for the synthesis of 2-dicyanomethylene-4, 5, 5-trimethyl-2,5-dihydrofuran-3-carbonitrile catalyzed by lithium ethoxide was investigated by density functional theory (DFT). The geometries and the frequencies of reactants, intermediates, transition states and products were calculated at the B3LYP/6-31G(d) level. The vibration analysis and the IRC analysis verified the authenticity of transition states. The reaction processes were confirmed by the changes of charge density at the bond-forming critical point. The results indicated that lithium ethoxide is an effective catalyst in the synthesis of 2-dicyanomethylene-4, 5, 5-trimethyl-2, 5-dihydrofuran-3-carbonitrile from malononi-trile and 3-hydroxy-3-methyl-2-butanone. The activation energy of the reaction with lithium ethoxide was 115.86 kJ·mol−1 less than the uncatalyzed reaction. The mechanism of the lithium ethoxide catalyzed reaction differed from the mechanism of the uncatalyzed reaction.

Quantitative structure-property relationship (QSPR) modeling is a powerful approach for predicting environmental behavior of organic pollutants with their structure descriptors. This study reports an optimal QSPR model for estimating logarithmic n-octanol/water partition coefficients (log K OW) of polycyclic aromatic hydrocarbons (PAHs). Quantum chemical descriptors computed with density functional theory at B3LYP/6-31G(d) level and partial least squares (PLS) analysis with optimizing procedure were used for generating QSPR models for log K OW of PAHs. The squared correlation coefficient (R 2) of the optimal model was 0.990, and the results of crossvalidation test (Q 2cum=0.976) showed this optimal model had high fitting precision and good predictability. The log K OW values predicted by the optimal model are very close to those observed. The PLS analysis indicated that PAHs with larger electronic spatial extent and lower total energy values tend to be more hydrophobic and lipophilic.

A binuclear copper complex [{Cu(L)2}2], C68H48Cu2N4O12C (where L is 4-methyl-7-(salicylideneamino)coumarin), has been synthesized and characterized using elemental analysis, molar conductance measurements, and infrared, ultraviolet and ESR spectrosopy. The molecular structure of title compound, determined by single-crystal X-ray diffraction studies, reveals that the two symmetric Cu(L)2 units are associated into a dimer by rather long Cu...O bonds. The Cu(II) ions are bridged via the phenolic oxygen of one of the monomers and have distorted trigonal bipyramidal conformation geometry. Within each monomer the two methylsubstituted coumarin skeletons are trans to one another, but adopt a parallel arrangement with respect to the other monomer. Only half of the complex molecule can be found in the asymmetric unit, Z′ = 0.5, the other half is generated by the symmetry centre.