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121.
CNDO/force calculations have been employed to calculate the O-H stretching force constants for various structures of associated
water species such as water-dimethylether, water-acetonitrile, water-lithium fluoride, linear and cyclic water polymers. The
variation in the O-H stretching force constant in Am… O-H… Dn species where Am
and Dn represent, respectively,m number of electron-acceptor andn number of electron-donor molecules, is explained on the basis of the cooperativity effect. With increasing electron-acceptor
power of A and electron-donor power of D, the hydrogen-bonded O-H stretching force constant is significantly reduced. The
results obtained in these studies are in general agreement with experimental observations reported earlier. 相似文献
122.
N. S. Kopelev V. Chechersky A. Nath B. -H. O M. I. Larkin J. T. Markert J. -L. Peng R. L. Greene 《Journal of Radioanalytical and Nuclear Chemistry》1995,190(2):391-400
The as-prepared electron-doped system Nd2–xCexCuO4 (where x0.16) is not superconducting. It becomes superconducting only after removal of a minuscule amount of extraneous oxygen (0.02 of O per unit formula). Mössbauer effect studies were carried out for oxygenated and deoxygenated Nd2–xCexCu(57Co)O4 with x=0.14, 0.16, and 0.18. The spectra show evidence of oxygen anions attaching to the probe57Co in apical positions, to form 5- and 6-coordinated species. A conventional procedure for deoxygenation brings about little change in the Mössbauer spectra both above and below the optimal superconducting concentration; however, for x=0.16, a dramatic change is observed—a major fraction of the magnetically split five-coordinated species manifests itself as a paramagnetically relaxed doublet upon deoxygenation, which costitutes a microscopic measure of the superconducting volume fraction. This apparently anomalous behavior at x0.16, where the extraneous oxygen is more readily desorbed, may be related to an electronic and/or local structural change in the CuO2 plane. 相似文献
123.
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
124.
Conductance data for sodium nitrite, chloride, and acetate in water andN,N-dimethylformamide (DMF)-water mixtures (74.82D42.48) for the concentration range 0.001–0.04N, as well as the densities, viscosities, and dielectric constants of the solvent mixtures at 35°C, are reported. The data have been analyzed by the Fuoss (1975) equation. The existence of a maximum in the viscosity at a 13 mole ratio of DMF and water is indicated. The Walden products for all the three salts pass through a maximum while the equivalent conductances show a minimum with increasing DMF content. The maxima in the Walden product are attributed to the dehydration of ions by the cosolvent (DMF).Part I:Indian J. Chem.
14A, 1015 (1976).Deceased. 相似文献
125.
Gurucharan Mukherjee Sailendra Nath Poddar Kingshuk Choudhury Kamalendu Dey 《Transition Metal Chemistry》1988,13(1):58-63
Summary Iron(III) complexes of a quadridentate N2S2 donor ligand, 1,2-di(o-aminophenylthio)ethane (DAPTE) and its Schiff Base with salicylaldehyde, a hexadentate N2S2O2 donor ligand,viz. 1,2-di(o-salicylaldiminophenylthio)ethane (H2DSALPTE) have been synthesised and characterised.The Schiff base ligand (1 mol) gave a dark green tri-iron(III) [Fe3(DSALPTE)(HDSALPTE)Cl3]Cl2 complex when reacted with anhydrous iron(III) chloride (1 mol). The Mössbauer data of this complex suggest the presence of three iron sites, one of which is octahedral and the other two tetrahedral. On the other hand, Fe(ClO4)3 reacted smoothly with H2DSALPTE in ethanol to give a mononuclear pseudo-octahedral complex in which the ligand functions in a dibasic hexadentate fashion. Mössbauer data suggest the presence of a low-spin-high-spin equilibrium in the solid state. The manganese(III) and cobalt(III) complexes of the Schiff base, H2DSALPTE, are also studied for the sake of comparison with the corresponding iron(III) complex. The N2S2 ligand, however, formed a low-spin pseudo-octahedral iron(III) complex. The complexes have been characterised by elemental analysis, molar conductance values, cryomagnetic data and i.r., electronic and Mössbauer spectral data. 相似文献
126.
A palladium-catalysed intramolecular allylic (hetero)arylation strategy for the synthesis of fused cyclopentenes incorporated with all-carbon quaternary and spiro centres is described. The method is straightforward, shows broad scope, proceeds in synthetically useful yields, and provides a rare means to construct complex cyclopentanoids. The reaction is believed to involve a kinetically unfavourable 5-endo-trig carbocyclisation of the tethered (π-allyl)palladium system. Further, this method was successfully applied as the key step in the total synthesis of diterpene natural products taiwaniaquinone H and dichroanone.A palladium-catalysed intramolecular allylic (hetero)arylation strategy for the synthesis of fused cyclopentenes incorporated with all-carbon quaternary and spiro centres is described. 相似文献
127.
Namita Singh Sana Ahmed Aliyah Fakim Somayah Qutub Othman Alahmed Omar El Tall Osama Shekhah Mohamed Eddaoudi Niveen M. Khashab 《Chemical science》2020,11(41):11280
Assembling well-defined MOF superstructures remains challenging as it requires easily removable hard templates or readily available immiscible solutions for an emulsion-based soft-template approach. In this work, a single-step emulsion-free soft templating approach is reported to spontaneously prepare hollow ZIF-8 and ZIF-67 colloidosomes with no further purification. These superstructures can load different enzymes regardless of the size and charge with a high encapsulation efficiency of 99%. We envisage that this work will expand the repertoires of MOF superstructures by the judicious selection of precursors and the reaction medium.An emulsion-free approach for the preparation of hollow ZIF-8 superstructures in a single step is established based on metal sulfate hydrates in methanol. 相似文献
128.
Balamurugan V Hundal MS Mukherjee R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(7):1683-1690
Using a group of six neutral M(II)Cl(2)-containing coordination compounds as building blocks, the first systematic investigation of C-H...Cl hydrogen-bonding interactions was performed. Single-crystal X-ray structural analyses of four new compounds (pseudo-tetrahedral Co(II) and Zn(II); distorted trigonal bipyramidal Zn(II)) authenticate the metal coordination geometry. To provide a unified view of the presence of noncovalent interactions in this class of compounds, we have re-examined the packing diagram of two previously reported compounds (a distorted square-pyramidal Cu(II) complex and a trans-octahedral Co(II) complex). The organic ligands of our choice comprise bidentate/tridentate pyrazolylmethylpyridines and an unsymmetrical tridentate pyridylalkylamine. This systematic investigation has allowed us to demonstrate the existence of versatile C-H...Cl(2)M interactions and to report the successful application of such units as inorganic supramolecular synthons. Additional noncovalent interactions such as C-H...O and O-H...Cl hydrogen bonding and pi-pi stacking interactions have also been identified. Formation of novel supramolecular architectures has been revealed: 2D lamellar (p-cyclophane) and 3D lamellar, 3D "stitched staircase" (due to additional hydrogen-bonding interactions by water tetramers, with an average O-O bond length in the tetramer unit of 2.926 A, acting as "molecular clips" between staircases), 3D linked ladder, and single-stranded 1D helix. 相似文献
129.
130.
Upendra Nath Dash Banka Behari Das Uttam Kumar Biswal Tapodhan Panda 《Thermochimica Acta》1984,80(2):331-342
The standard potentials of silver—silver bromide and silver—silver iodide electrodes in glycerol+water mixtures containing 5, 10, 20 and 30 wt% glycerol were determined from electromotive force measurements of the cell Ag(s), AgX(s), KX(c)//KCl(c), AgCl(s), Ag(s), where X is Br or I, at seven different temperatures in the range 5–35°C. The standard potentials in each solvent are represented as a function of temperature. The standard thermodynamic functions for the electrode reactions, the primary medium effects of various solvents upon X−, and the standard thermodynamic quantities for the transfer of 1 g-ion of X− from water to the respective glycerol + water media are evaluated and discussed in the light of ion—solvent interactions as well as the structural changes of the solvents. From the values of the Ag/Ag+ and Ag/AgX, X− electrodes, the thermodynamic solubility product constants of silver chloride, silver bromide and silver iodide have been determined in glycerol + water solvent mixtures at different temperatures. 相似文献