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151.
152.
The template reaction of salicylaldehyde and its substituted derivatives and 2-hydroxy-5-bromobenzylamine or 2-hydroxy-5-chlorobenzylamine with copper(II) acetate in dimethyl sulphoxide (dmso) afforded eight dinuclear Cu(II) complexes, [Cu2(L)2(dmso)2] (H2 L = N-salicylidene-2-hydroxy-5-bromobenzylamine, N-salicylidene-2-hydroxy-5-chlorobenzylamine and their 5-bromo, 5-nitro and 5-methyl-substituted salicylidene derivatives). These Cu(II) complexes were characterised by IR and UV-VIS-NIR spectroscopy, electric conductivity, cyclic voltammetry, and temperature dependence of magnetic susceptibilities (4.5–300 K). In the THF solution, the complexes are nonelectrolytes and exhibit a characteristic CT band due to phenoxido-bridging at 360–384 nm. In the cyclic voltammograms, an irreversible reduction process was observed at ?1.18–1.54 V vs Fc/Fc+. Single-crystal X-ray crystallography revealed that two Cu(II) ions were bridged by the two phenoxido-oxygen atoms of the two Schiff-base ligands with axial coordination of dmso molecules forming a square pyramid with a Cu-Cu distance of 3.0628(8)–3.0931(6) °A. In accordance with the crystal structures, the magnetic interaction between the two Cu(II) ions is relatively anti-ferromagnetic with ?2J value of 386–575 cm?1. The axial coordination effect of the dmso molecule was discussed in relation to the correlation between the Cu-O-Cu angle and the ?2J value.  相似文献   
153.
149Sm nuclear resonant inelastic scattering was carried out in a charge density wave compound SmNiC2. We have investigated temperature dependences of the Sm partial phonon density of states and recoil-free fraction at the Sm site and the average sound velocity estimated from the Sm partial density of states. The Sm partial density of states exhibits temperature dependence, suggesting that the phonon modes between 20 and 25 meV may correlate with the charge density wave. Temperature dependence of the recoil-free fraction is difficult to prove the correlation with either the charge density wave or ferromagnetic ordering. The average sound velocity obtained by the Sm partial phonon density of states exhibits temperature dependence, agreeing qualitatively with very recent elastic constant measurements.  相似文献   
154.
We optimised the simultaneous analysis of four analytes, namely three anti-influenza drugs (oseltamivir (OS), zanamivir (ZAN) and amantadine (AMN)) and one metabolite of OS (oseltamivir carboxylate (OC)), in sewage treatment plant (STP) influent and effluent by verifying the types and conditions of solid phase extraction (SPE) appropriate for LC-MS/MS analysis. In summary, these target analytes were extracted from aqueous samples (30–50 mL) by using strong cation-exchange SPE cartridges (500 mg adsorbent) under acidic conditions (pH 3–4). After washing of the cartridges with acidified water (pH 3.0, 3 mL) and methanol (3 mL), the analytes were eluted with a mixed solvent (2 mL) of 10% (v/v) triethylamine in a 1:1 (v/v) mixture of acetone and water. Application of this technique to the target compounds should yield a comprehensive understanding of the occurrence and fate of anti-influenza drugs in the water environment.  相似文献   
155.
S‐((Phenylsulfonyl)difluoromethyl)thiophenium salts were designed and prepared by a triflic acid catalyzed intramolecular cyclization of ortho‐ethynyl aryldifluoromethyl sulfanes. The thiophenium salts were found to be efficient as electrophilic difluoromehtylating reagents for introduction of a CF2H group to sp3‐hybridized carbon nucleophiles such as of β‐ketoesters and dicyanoalkylidenes. The (phenylsulfonyl)difluoromethyl group can be readily transformed into CF2H under mild reaction conditions. Enantioselective electrophilic difluoromethylation was also achieved in the presence of bis(cinchona) alkaloids.  相似文献   
156.
Structural information of a transmembrane (TM) helix dimer is useful in understanding molecular mechanisms of important biological phenomena such as signal transduction across the cell membrane. Here, we describe an umbrella sampling (US) scheme for predicting the structure of a TM helix dimer in implicit membrane using the interhelical crossing angle and the TM–TM relative rotation angles as the reaction coordinates. This scheme conducts an efficient conformational search on TM–TM contact interfaces, and its robustness is tested by predicting the structures of glycophorin A (GpA) and receptor tyrosine kinase EphA1 (EphA1) TM dimers. The nuclear magnetic resonance (NMR) structures of both proteins correspond to the global free‐energy minimum states in their free‐energy landscapes. In addition, using the landscape of GpA as a reference, we also examine the protocols of temperature replica‐exchange molecular dynamics (REMD) simulations for structure prediction of TM helix dimers in implicit membrane. A wide temperature range in REMD simulations, for example, 250–1000 K, is required to efficiently obtain a free‐energy landscape consistent with the US simulations. The interhelical crossing angle and the TM–TM relative rotation angles can be used as reaction coordinates in multidimensional US and be good measures for conformational sampling of REMD simulations. © 2013 Wiley Periodicals, Inc.  相似文献   
157.
The resolution of a numerical scheme in both physical and Fourier spaces is one of the most important requirements to calculate turbulent flows. A conservative form of the interpolated differential operator (IDO-CF) scheme is a multi-moment Eulerian scheme in which point values and integrated average values are separately defined in one cell. Since the IDO-CF scheme using high-order interpolation functions is constructed with compact stencils, the boundary conditions are able to be treated as easy as the 2nd-order finite difference method (FDM). It is unique that the first-order spatial derivative of the point value is derived from the interpolation function with 4th-order accuracy and the volume averaged value is based on the exact finite volume formulation, so that the IDO-CF scheme has higher spectral resolution than conventional FDMs with 4th-order accuracy. The computational cost to calculate the first-order spatial derivative with non-uniform grid spacing is one-third of the 4th-order FDM. For a large-eddy simulation (LES), we use the coherent structure model (CSM) in which the model coefficient is locally obtained from a turbulent structure extracted from a second invariant of the velocity gradient tensor, and the model coefficient correctly satisfies asymptotic behaviors to walls.  相似文献   
158.
We have successfully fabricated insoluble copper(I) complex [Cu(μ-I)dppet]2 nanocrystals by developing the heterogeneous reaction process between rod-like nanocrystals of dppet ligand prepared in advance and added acetonitrile solution of copper(I) halide. During this reaction process, the shape of dppet ligand nanocrystals was dramatically changed from rod-like to spherical. Probably, the complexation reaction and subsequent nanocrystallization would proceed on or near swollen surface of dppet nanocrystals in acetonitrile droplet as restricted reaction field.  相似文献   
159.
Dihydroxybenziphthalocyanine 1 , with bulky aryloxy groups, has been synthesized and characterized by X‐ray crystallography, NMR and UV/Vis‐NIR spectroscopy, and theoretical calculations. Macrocycle 1 is the first example of an aromatic benziphthalocyanine with an 18π‐electron structure, and was found to exist as an equilibrium mixture of weakly aromatic and strongly aromatic tautomers. The aromaticity and near‐IR absorption can be controlled by chemical modification at the reactive resorcinol moiety and by variation of the solvent.  相似文献   
160.
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