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61.
V. Pažma 《Czechoslovak Journal of Physics》1979,29(5):481-486
A proposal for formulation of relativistic quantum mechanics in terms of path integrals is presented.We are deeply indebted to Dr. M.Petrá for many stimulating discussions. 相似文献
62.
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
63.
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
64.
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
65.
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
66.
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
67.
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
68.
Katarína Hroboňová Andrea Spevak Ľubica Spišská Jozef Lehotay Jozef Čižmárik 《Chemical Papers》2013,67(5):477-483
The molecularly imprinted polymers (MIPs) were synthesised and the influence of the type of porogen, the nature of sample solvent, and the binding capacity of material were tested by high-performance liquid chromatography (HPLC). Umbelliferone was used as the template for imprint formation. Methacrylic acid was used as the monomer and acetonitrile, ethanol, and chloroform as porogen. Non-imprinted polymers (NIPs) were prepared by the same procedure. The highest value of the specific binding capacity (269 μg of umbelliferone per 100 mg of polymer) was obtained for polymers prepared in chloroform as porogen and methanol/water (φ r = 1: 1) as the sample solvent. The group-selective MIP was used as sorbent for the SPE pre-treatment of umbelliferone from plant extracts prior to HPLC analysis. Analysis of the spiked samples showed good recoveries (> 77 %). The limit of detection, limit of determination, and repeatability of the method were also calculated. 相似文献
69.
Jan Jakubík Alena Randáková Vladimír Doležal 《Journal of computer-aided molecular design》2013,27(6):525-538
Twelve homology models of the human M2 muscarinic receptor using different sets of templates have been designed using the Prime program or the modeller program and compared to crystallographic structure (PDB:3UON). The best models were obtained using single template of the closest published structure, the M3 muscarinic receptor (PDB:4DAJ). Adding more (structurally distant) templates led to worse models. Data document a key role of the template in homology modeling. The models differ substantially. The quality checks built into the programs do not correlate with the RMSDs to the crystallographic structure and cannot be used to select the best model. Re-docking of the antagonists present in crystallographic structure and relative binding energy estimation by calculating MM/GBSA in Prime and the binding energy function in YASARA suggested it could be possible to evaluate the quality of the orthosteric binding site based on the prediction of relative binding energies. Although estimation of relative binding energies distinguishes between relatively good and bad models it does not indicate the best one. On the other hand, visual inspection of the models for known features and knowledge-based analysis of the intramolecular interactions allows an experimenter to select overall best models manually. 相似文献
70.
Jitka Daďová Susanne Kümmel Christian Feldmeier Jana Cibulková Dr. Richard Pažout Dr. Jaroslav Maixner Prof. Dr. Ruth M. Gschwind Prof. Dr. Burkhard König Dr. Radek Cibulka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(3):1066-1075
A series of 10‐arylflavins (10‐phenyl‐, 10‐(2′,6′‐dimethylphenyl)‐, 10‐(2′,6′‐diethylphenyl)‐, 10‐(2′,6′‐diisopropylphenyl)‐, 10‐(2′‐tert‐butylphenyl)‐, and 10‐(2′,6′‐dimethylphenyl)‐3‐methylisoalloxazine ( 2 a – f )) was prepared as potentially nonaggregating flavin photocatalysts. The investigation of their structures in the crystalline phase combined with 1H‐DOSY NMR spectroscopic experiments in CD3CN, CD3CN/D2O (1:1), and D2O confirm the decreased ability of 10‐arylflavins 2 to form aggregates relative to tetra‐O‐acetyl riboflavin ( 1 ). 10‐Arylflavins 2 a – d do not interact by π–π interactions, which are restricted by the 10‐phenyl ring oriented perpendicularly to the isoalloxazine skeleton. On the other hand, N3? H???O hydrogen bonds were detected in their crystal structures. In the structure of 10‐aryl‐3‐methylflavin ( 2 f ) with a substituted N3 position, weak C? H???O bonds and weak π–π interactions were found. 10‐Arylflavins 2 were tested as photoredox catalysts for the aerial oxidation of 4‐methoxybenzyl alcohol to the corresponding aldehyde (model reaction), thus showing higher efficiency relative to 1 . The quantum yields of 4‐methoxybenzyl alcohol oxidation reactions mediated by arylflavins 2 were higher by almost one order of magnitude relative to values in the presence of 1 . 相似文献