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41.
We investigated the performance of the approximative density functional method DFTB versus BLYP and G2 with respect to zero-point corrected reaction energies, vibrational frequencies, and geometry parameters for a set of 28 reactions and 22 representative molecules containing C, H, N, and O (DFTB--density-functional based tight-binding approximation). The DFTB reaction energies show a mean absolute deviation versus the G2 reference of 4.3 kcalmol only. The corresponding value for the vibrational frequencies amounts to 75 cm(-1) versus BLYP/cc-pVTZ. With very few exceptions bond lengths and angles are in excellent agreement with the results of higher-level methods. 相似文献
42.
P.W. Jolly C. Krüger R. Salz J.C. Sekutowski 《Journal of organometallic chemistry》1979,165(3):C39-C42
The stoichiometric reaction between allene, zerovalent nickel and a chelating diphosphane leads to the formation of a bis-methylenenickelacyclopentane derivative whose structure has been established by X-ray crystallography. 相似文献
43.
In this study, chemometric techniques such as cluster analysis (CA), discriminant analysis (DA), principal component analysis (PCA) and partial least squares (PLS) were used to analyse the wastewater dataset to identify the factors which affect the composition of sewage of domestic origin, spatial and temporal variations, similarity/dissimilarity among the wastewater characteristics of cis- and trans-drains and discriminating variables. Samples collected from 24 wastewater drains in Lucknow city and from three sites on Gomti river in the month of January/February, May, August and November during the period of 5 years (1994-1999) were characterized for 32 parameters. The multivariate techniques successfully described the similarities/dissimilarities among the sewage drains on the basis of their wastewater characteristics and sources signifying the effect of routine domestic/commercial activities in respective drainage areas. Spatial and seasonal variations in wastewater composition were also determined successfully. CA generated six groups of drains on the basis of similar wastewater characteristic. PCA provided information on seasonal influence and compositional differences in sewage generated by domestic and industrial waste dominated drains and showed that drains influenced by mixed industrial effluents have high organic pollution load. DA rendered six variables (TDS, alkalinity, F, TKN, Cd and Cr) discriminating between cis- and trans-drains. PLS-DA showed dominance of Cd, Cr, NO3, PO4 and F in cis-drains wastewater. The results suggest that biological-process based STPs could treat wastewater both from the cis- as well as trans-drains, however, prior removal of toxic metals will be required from the cis-drains sewage. Further, seasonal variations in wastewater composition and pollution load could be the guiding factor for determining the STPs design parameters. The information generated would be useful in selection of process type and in designing of the proposed sewage treatment plants (STPs) for safe disposal of wastewater. 相似文献
44.
Renata Ga<parová Daniel Zbojek Margita Lácová Katarína Král'ová Anton Gatial Branislav Horváth Alžbeta Krutošíková 《Central European Journal of Chemistry》2005,3(4):622-646
The reactions of substituted furo[3,2-b]pyrrole-5-carboxhydrazides 1 with 5-arylfuran-2-carboxaldehydes 2, 4,5-disubstituted furan-2-carboxaldehydes 3 and thiophene-2-carboxaldehyde 4 has been studied. The advantage of microwave irradiation on some of these reactions was reflected in the reduced reaction
time and increased yields. Reactions of 1 with 4-substituted 1,3-oxazol-5(4H)-ones 11 led to diacylhydrazines 13 or to imidazole derivatives 14 depending on the temperature. 1,2,4-Triazole-3-thione 17 was synthesized by two-step reaction of 1 with phenylisothiocyanate and subsequent base-catalyzed cyclization of thiosemicarbazide 16. The effects of hydrazones 5–10 on inhibition of photosynthetic electron transport in spinach chloroplasts and chlorophyll content in the antialgal suspensions
of Chlorella vulgaris were investigated. 相似文献
45.
1H NMR spectra of dimethyl selenide with 13C and 77Se satellites and of dimethyl telluride with 13C, 123Te and 125Te satellites have been investigated. The structural information has been derived and is found to be in good agreement with microwave results for dimethyl selenide. For dimethyl telluride our results disagree with earlier data obtained by extrapolation from similar molecules. 相似文献
46.
František Kvasnička Rudolf Ševčík Michal Voldřich Jana Krátká 《Central European Journal of Chemistry》2004,2(3):417-424
A simple and rapid capillary zone electrophoresis (CZE) method for the determination of aristolochic acid (AA) in dietary
supplements and selected herbs is described. A clear separation of AA from other sample constituents was achieved within 5
minutes without any sample clean up. A mixture of 20 mM-morpholinethanesulphonic acid+10 mM-BisTrisPropane+0.2% hydroxyethylcelullose
in 10% methanol serves as a background electrolyte. The linearity, accuracy, intra-assay and detection limit of the developed
method are 200–6000 ng/mL, 95–103%, 3.5%, and 50 ng/ml, respectively. Ease of use, sufficient sensitivity and low running
cost are the most important attributes of the CZE method. The proposed CZE method was compared with HPLC. 相似文献
47.
[formula: see text] A new synthetic strategy has been developed for a general approach toward the synthesis of a variety of 1-N-iminosugar-type glycosidase inhibitors utilizing precursors developed by the PET-mediated cyclization of alpha-trimethylsilylmethylamine radical cation to a tethered pi-functionality. 相似文献
48.
Chemometric analysis of groundwater quality data of alluvial aquifer of Gangetic plain, North India 总被引:10,自引:0,他引:10
Kunwar P. Singh Amrita Malik Vinod K. Singh Dinesh Mohan Sarita Sinha 《Analytica chimica acta》2005,550(1-2):82-91
Water quality data set from the alluvial region in the Gangetic plain in northern India, which is known for high fluoride levels in soil and groundwater, has been analysed by chemometric techniques, such as principal component analysis (PCA), discriminant analysis (DA) and partial least squares (PLS) in order to investigate the compositional differences between surface and groundwater samples, spatial variations in groundwater composition and influence of natural and anthropogenic factors. Trilinear plots of major ions showed that the groundwater in this region is mainly of Na/K-bicarbonate type. PCA performed on complete data matrix yielded six significant PCs explaining 65% of the data variance. Although, PCA rendered considerable data reduction, it could not clearly group and distinguish the sample types (dug well, hand-pump and surface water). However, a visible differentiation between the water samples pertaining to two watersheds (Khar and Loni) was obtained. DA identified six discriminating variables between surface and groundwater and also between different types of samples (dug well, hand pump and surface water). Distinct grouping of the surface and groundwater samples was achieved using the PLS technique. It further showed that the groundwater samples are dominated by variables having origin both in natural and anthropogenic sources in the region, whereas, variables of industrial origin dominate the surface water samples. It also suggested that the groundwater sources are contaminated with various industrial contaminants in the region. 相似文献
49.
Klaus van Benthem Stephan Krämer Wilfried Sigle Manfred Rühle 《Mikrochimica acta》2002,138(3-4):181-193
An understanding of the correlation between microstructures and properties of materials require the characterization of the
material on many different length scales. Often the properties depend primarily on the atomistics of defects, such as dislocations
and interfaces. The different techniques of transmission electron microscopy allow the characterization of the structure and
of the chemical composition of materials with high spatial resolution to the atomic level: high resolution transmission electron
microscopy allows the determination of the position of the columns of atoms (ions) with high accuracy. The accuracy which
can be achieved in these measurements depends not only on the instrumentation but also on the quality of the transmitted specimen
and on the scattering power of the atoms (ions) present in the analyzed column.
The chemical composition can be revealed from investigations by analytical microscopy which includes energy dispersive X-ray
spectroscopy, mainly quantitatively applied for heavy elements, and electron energy-loss spectroscopy. Furthermore, the energy-loss
near-edge structure of EELS data results in information on the local band structure of unoccupied states of the excited atoms
and, therefore, on bonding. A quantitative evaluation of convergent beam electron diffraction results in information on the
electron charge density distribution of the bulk (defect-free) material.
The different techniques are described and applied to different problems in materials science. It will be shown that nearly
atomic resolution can be achieved in high resolution electron microscopy and in analytical electron microscopy. Recent developments
in electron microscopy instrumentation will result in atomic resolution in the foreseeable future. 相似文献
50.
Sonnenschein H Kreher T Gründemann E Krüger RP Kunath A Zabel V 《The Journal of organic chemistry》1996,61(2):710-714
The first compounds of a new series of redox-active cyclophanes were prepared by dehydrocyclization of bridged indolizines of type 1. The bridged dipyridino-compounds 2a and 2b obtained by reaction of 2 mol of lithiated alpha-picolines with dihalides were used as starting materials. Subsequent treatment of 2a,b with 2 mol of alpha-bromo ketones gave quaternary pyridinium halides. Ring closure in an alkaline medium (Chichibabin reaction) yielded the starting material for the synthesis of the macrocycles. Oxidative C-C coupling gave the diastereomeric cyclophanes of type 3. In all cases one pair of the enantiomers was obtained in excess. CV-investigations have shown that the main products are reversible redox systems. To clarify their conformations, compounds 3c, 3d/1, and3d/2 were subjected to X-ray analysis. 相似文献