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121.
Abstract The kinetics of polymerization of 3,6-dibromo-9-(2,3-epoxypro-pyl) carbazole with stannic chloride and boron trifluoride etherate were studied by a microcalorimetric technique. Complex kinetics of the polymerization rate were observed. A spontaneous increase of the reaction rate was recorded after it decreased and after polymerization for some time at the minimal rate. This effect is explained by a change in the mechanism of polymerization. At the high enough degree of conversion, transition from an active chain end mechanism to an activated monomer mechanism takes place. 相似文献
122.
A study of crystal structures from the Cambridge Structural Database (CSD) and DFT calculations reveals that parallel pyridine–pyridine and benzene–pyridine interactions at large horizontal displacements (offsets) can be important, similar to parallel benzene–benzene interactions. In the crystal structures from the CSD preferred parallel pyridine–pyridine interactions were observed at a large horizontal displacement (4.0–6.0 Å) and not at an offset of 1.5 Å with the lowest calculated energy. The calculated interaction energies for pyridine–pyridine and benzene–pyridine dimers at a large offset (4.5 Å) are about 2.2 and 2.1 kcal mol?1, respectively. Substantial attraction at large offset values is a consequence of the balance between repulsion and dispersion. That is, dispersion at large offsets is reduced, however, repulsion is also reduced at large offsets, resulting in attractive interactions. 相似文献
123.
Violeta Marković Svetlana Marković Ana Janićijević Marko V. Rodić Vukadin M. Leovac Nina Todorović Snežana Trifunović Milan D. Joksović 《Structural chemistry》2013,24(6):2127-2136
A study on the synthesis and mechanistical aspects of formation of 3-methyl-5-oxo-3-pyrazolin-1-carboxamide (MOPC) starting from S-methylisothiosemicarbazide hydrogen iodide and methyl acetoacetate was performed. In the alkaline aqueous solution, the intermediate methyl acetoacetate S-methylisothiosemicarbazone undergoes substitution of CH3S? anion by hydroxide anion, cyclization, carbanion formation, and elimination of methanol, thus yielding corresponding Na-enolate salt of pyrazol-5-one derivative. The structure of the compound obtained after protonation of the formed enolate salt was determined by means of spectroscopic techniques and single-crystal X-ray diffraction analysis. The mechanism of conversion of methyl acetoacetate S-methylisothiosemicarbazone into MOPC was investigated by means of the B3LYP functional, and it was found that the reaction is thermodynamically controlled. 相似文献
124.
K. Sunjog S. Kolarević K. Héberger Z. Gačić J. Knežević-Vukčević B. Vuković-Gačić M. Lenhardt 《Analytical and bioanalytical chemistry》2013,405(14):4879-4885
The genotoxic potential of waters in six rivers and reservoirs from Serbia was monitored in different tissues of chub (Squalius cephalus L. 1758) with the alkaline comet assay. The comet assay, or single-cell gel electrophoresis, has a wide application as a simple and sensitive method for evaluating DNA damage in fish exposed to various xenobiotics in the aquatic environment. Three types of cells, erythrocytes, gill cells, and liver cells, were used for assessing DNA damage. Images of randomly selected cells were analyzed with a Leica fluorescence microscope and image analysis by software (Comet Assay IV Image analysis system, PI, UK). Three parameters (tail length—l, tail intensity—i, and Olive tail moment—m) were analyzed on 1,700 nuclei per cell type. The procedure for sum of ranking differences (SRD) was implemented to compare different types of cells and different parameters for estimation of DNA damage. Regarding our nine different estimations of genotoxicity: tail length, intensity, and moment in erythrocytes (rel, rei, rem), liver cells (rll, rli, rlm), and gill cells (rgl, rgi, rgm), the SRD procedure has shown that the Olive tail moment and tail intensity are (almost) equally good parameters; the SRD value was lower for the tail moment and tail intensity than for tail length in the case of all types of cells. The least reliable parameter was rel; close to the borderline case were rei, rll, and rgl (~5 % probability of random ranking). Figure
Comparison of comet assay parameters 相似文献
125.
Dragana Mutavdžić Pavlović Danijela Ašperger Dijana Tolić Sandra Babić 《Journal of separation science》2013,36(18):3042-3049
This paper describes the development, optimization, and validation of a method for the determination of five pharmaceuticals from different therapeutic classes (antibiotics, anthelmintics, glucocorticoides) in water samples. Water samples were prepared using SPE and extracts were analyzed by HPLC with diode‐array detection. The efficiency of 11 different SPE cartridges to extract the investigated compounds from water was tested in preliminary experiments. Then, the pH of the water sample, elution solvent, and sorbent mass were optimized. Except for optimization of the SPE procedure, selection of the optimal HPLC column with different stationary phases from different manufacturers has been performed. The developed method was validated using spring water samples spiked with appropriate concentrations of pharmaceuticals. Good linearity was obtained in the range of 2.4–200 μg/L, depending on the pharmaceutical with the correlation coefficients >0.9930 in all cases, except for ciprofloxacin (0.9866). Also, the method has revealed that low LODs (0.7–3.9 μg/L), good precision (intra‐ and interday) with RSD below 17% and recoveries above 98% for all pharmaceuticals. The method has been successfully applied to the analysis of production wastewater samples from the pharmaceutical industry. 相似文献
126.
Tomáš Křížek Veronika Doubnerová Helena Ryšlavá Pavel Coufal Zuzana Bosáková 《Analytical and bioanalytical chemistry》2013,405(8):2425-2434
Enzyme assays of β-N-acetylhexosaminidase from Aspergillus oryzae using capillary electrophoresis in the offline and online setup have been developed. The pH value and concentration of the borate-based background electrolyte were optimized in order to achieve baseline separation of N,N′,N″-triacetylchitotriose, N,N′-diacetylchitobiose, and N-acetyl-d-glucosamine. The optimized method using 25 mM tetraborate buffer, pH 10.0, was evaluated in terms of repeatability, limits of detection, quantification, and linearity. The method was successfully applied to the offline enzyme assay of β-N-acetylhexosaminidase, which was demonstrated by monitoring the hydrolysis of N,N′,N″-triacetylchitotriose. The presented method was also utilized to study the pH dependence of enzyme activity. An online assay with N,N′-diacetylchitobiose as a substrate was developed using the Transverse Diffusion of Laminar Flow Profiles model to optimize the injection sequence and in-capillary mixing of substrate and enzyme plugs. The experimental results were in good agreement with predictions of the model. The online assay was successfully used to observe the inhibition effect of N,N′-dimethylformamide on the activity of β-N-acetylhexosaminidase with nanoliter volumes of reagents used per run and a high degree of automation. After adjustment of background electrolyte pH, an online assay with N,N′,N″-triacetylchitotriose as a substrate was also performed. Figure
Electropherograms resulting from online enzyme assays of β-N-acetylhexosaminidase for chitobiose as a substrate with 10-min (red line), 5-min (blue line) and 0-min (black line) reaction time. Peak identification: 1 chitobiose, 2 N-acetylglucosamine 相似文献
127.
Thallium sulfide layers of varying composition form on the surface of low-density polyethylene (PE) when the PE films have been sulfurized in a solution of higher polythionic acid H2S33O6, and then immersed in the alkaline solution of thallium (I) sulfate. The concentration of sulfur sorbed-diffused into PE surface increases with the increase of the sulfurization time and concentration of higher polythionic acid solution. The concentration of thallium in the Tl x S y layers depends on the sulfur concentration sorbed-diffused into PE, the concentration, and temperature of thallium (I) sulfate solutions. By chemical analysis of the obtained sulfide layers it was determined that the values of x and y in the TlxSy layers varies in the intervals: 1<x<3, 1<y<6. Two phases TlS, Tl2S2 were identified by X-ray diffraction analysis in thallium sulfide layers. Scanning Electron (SEM) and Atomic Force (AFM) microscopies were used to characterize surface morphology of thallium sulfide layers. The films deposited on the PE surface have a non-homogeneous structure, and consist of separated islands. 相似文献
128.
Zdravko Džambaski Đorđe Toljić Bojan Bondžić Rade Marković Marija Baranac-Stojanović 《Tetrahedron》2013
The reactivity of 2-alkylidene-4-oxothiazolidine S-oxides under the Pummerer reaction conditions, using Ac2O, TFAA, SOCl2 and SOBr2 as initiators, has been examined. Almost all reactions proceeded with absolute regioselectivity yielding α-substituted sulfides or vinyl-chloro derivatives. The mechanism for the formation of the latter products was postulated and proved experimentally. 相似文献
129.
Vladimíra Novotná Věra Hamplová Miroslav Kašpar Milada Glogarová Karel Knížek Siegmar Diele 《Liquid crystals》2013,40(8):967-975
New mesogens composed of achiral bent molecules with thermally stable ester linkages, and laterally substituted by a methoxy group symmetrically near the central benzene ring, were synthesized. Texture, calorimetric, electro‐optical, X‐ray and dielectric measurements were performed. In most of studied compounds the antiferroelectric B2 phase was found on cooling from the isotropic phase, followed by the B7 phase at lower temperatures. Undulation of layers in the B7 phase was confirmed by precise synchrotron studies. 相似文献
130.
George Cordoyiannis Patricia Losada-Pérez Chandra Shekhar Pati Tripathi Brigita Rožič Uroš Tkalec Vassilios Tzitzios 《Liquid crystals》2013,40(11):1419-1426
The phase transition behaviour of the chiral liquid crystal CE6 doped with spherical surface-functionalised CdSe nanoparticles has been examined by means of high-resolution adiabatic scanning calorimetry and polarising microscopy. The addition of nanoparticles results in an essentially stabilised blue phase III. The phase diagram is displayed upon heating and cooling and the enthalpy changes involved in the conversion between the blue phases are determined. The dispersion of functionalised nanoparticles is prominent for the stabilisation of blue phase III, which is potentially useful for applications, especially if applied on liquid crystals that exhibit blue phases close to room temperature. 相似文献