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101.
Slow crystallisation at lowered temperature yielded crystals of the “third‐generation” tris(pyrazolyl)borate transfer agent p‐BrC6H4TpCs (Tp′Cs) 1 (triclinic; P$\bar{1}$ ; a = 8.540(4), b = 15.045(6), c = 15.879(7) Å; α = 65.853(8), β = 88.457(8), γ = 75.056(8)°; V = 1791.4(13) Å3; Z = 4). The central caesium ion in 1 interacts with three individual p‐BrC6H4Tp ligands in two different chelating fashions.In particular, κ1N‐coordination and η5‐π‐coordination of pyrazole moieties as well as η6‐π‐coordination of the p‐BrC6H4 substituent are observed. Further, comparable coordination of neighbouring caesium ions leads to the formation of polymeric structures connected by two bridging modes.  相似文献   
102.
The paramagnetic dinuclear complexes 1,8-bis(cobaltocenyl)naphthalene (2) and 1,8-bis[(pentamethyl-η(5)-cyclopentadienyl)(η(5)-cyclopentadiendiyl)cobalt(II)]naphthalene (4) were synthesized. The molecular structures were characterized by X-ray structure analysis and consisted of two cobaltocenes linked through a distorted naphthalene clamp. Electronic interactions between the two cobalt atoms were observed by cyclic voltammetric studies. Superconducting quantum interference device (SQUID) measurements of the pure compounds and diluted in their diamagnetic iron derivatives, as well as variable-temperature NMR spectroscopy experiments in solution are presented. Magnetic measurements revealed an antiferromagnetic coupling of the electrons in complexes 2 and 4. From NMR spectroscopy experiments, Curie behavior in the temperature range from -60 to +60 °C can be deduced. The electronic structure and magnetic behavior is supported by results of broken-symmetry DFT and multireference calculations along with UV/Vis spectroscopic data, which revealed an intramolecular through space π-π interaction between the cobaltocene units.  相似文献   
103.
An oxidative chemical vapor deposition (OCVD) process was used to coat flexible textile fiber (viscose) with highly conductive polymer, poly (3,4‐ethylenedioxythiophene) (PEDOT) in presence of ferric (III) chloride (FeCl3) oxidant. OCVD is a solvent free process used to get uniform, thin, and highly conductive polymer layer on different substrates. In this paper, PEDOT coated viscose fibers, prepared under specific conditions, exhibited high conductivity 14.2 S/cm. The effects of polymerization conditions, such as polymerization time, oxidant concentration, dipping time of viscose fiber in oxidant solution, and drying time of oxidant treated viscose fiber, were carefully investigated. Scanning electron microscopy (SEM) and FT‐IR analysis revealed that polymerization of PEDOT on surface of viscose fiber has been taken place and structural analysis showed strong interactions between PEDOT and viscose fiber. Thermogravimetric analysis (TGA) was employed to investigate the amount of PEDOT in PEDOT coated viscose fiber and interaction of PEDOT with viscose fiber. The effect of PEDOT coating on the mechanical properties of the viscose fiber was evaluated by tensile strength testing of the coated fibers. The obtained PEDOT coated viscose fiber having high conductivity, could be used in smart clothing for medical and military applications, heat generation, and solar cell demonstrators. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   
104.
Soluble epoxide hydrolase (sEH) is a promising therapeutic target for the treatment of hypertension, pain, and inflammation-related diseases. In order to enable the development of sEH inhibitors (sEHIs), assays are needed for determination of their potency. Therefore, we developed a new method utilizing an epoxide of arachidonic acid (14(15)-EpETrE) as substrate. Incubation samples were directly injected without purification into an online solid phase extraction (SPE) liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS-MS) setup allowing a total run time of only 108 s for a full gradient separation. Analytes were extracted from the matrix within 30 s by turbulent flow chromatography. Subsequently, a full gradient separation was carried out on a 50X2.1 mm RP-18 column filled with 1.7 μm core-shell particles. The analytes were detected with high sensitivity by ESI-MS-MS in SRM mode. The substrate 14(15)-EpETrE eluted at a stable retention time of 96 ± 1 s and its sEH hydrolysis product 14,15-DiHETrE at 63 ± 1 s with narrow peak width (full width at half maximum height: 1.5 ± 0.1 s). The analytical performance of the method was excellent, with a limit of detection of 2 fmol on column, a linear range of over three orders of magnitude, and a negligible carry-over of 0.1% for 14,15-DiHETrE. The enzyme assay was carried out in a 96-well plate format, and near perfect sigmoidal dose-response curves were obtained for 12 concentrations of each inhibitor in only 22 min, enabling precise determination of IC(50) values. In contrast with other approaches, this method enables quantitative evaluation of potent sEHIs with picomolar potencies because only 33 pmol L(-1) sEH were used in the reaction vessel. This was demonstrated by ranking ten compounds by their activity; in the fluorescence method all yielded IC(50) ≤ 1 nmol L(-1). Comparison of 13 inhibitors with IC(50) values >1 nmol L(-1) showed a good correlation with the fluorescence method (linear correlation coefficient 0.9, slope 0.95, Spearman's rho 0.9). For individual compounds, however, up to eightfold differences in potencies between this and the fluorescence method were obtained. Therefore, enzyme assays using natural substrate, as described here, are indispensable for reliable determination of structure-activity relationships for sEH inhibition.  相似文献   
105.
We propose a general framework for the study of L 1 contractive semigroups of solutions to conservation laws with discontinuous flux:
$ u_t + \mathfrak{f}(x,u)_x=0, \qquad \mathfrak{f}(x,u)= \left\{{ll} f^l(u),& x < 0,\\ f^r(u), & x > 0, \right.\quad\quad\quad (\rm CL) $ u_t + \mathfrak{f}(x,u)_x=0, \qquad \mathfrak{f}(x,u)= \left\{\begin{array}{ll} f^l(u),& x < 0,\\ f^r(u), & x > 0, \end{array} \right.\quad\quad\quad (\rm CL)  相似文献   
106.
107.
We present new numerical methods for constructing approximate solutions to the Cauchy problem for Hamilton–Jacobi equations of the form ut+H(Dxu)=0. The methods are based on dimensional splitting and front tracking for solving the associated (non-strictly hyperbolic) system of conservation laws pt+DxH(p)=0, where p=Dxu. In particular, our methods depend heavily on a front tracking method for one-dimensional scalar conservation laws with discontinuous coefficients. The proposed methods are unconditionally stable in the sense that the time step is not limited by the space discretization and they can be viewed as “large-time-step” Godunov-type (or front tracking) methods. We present several numerical examples illustrating the main features of the proposed methods. We also compare our methods with several methods from the literature.  相似文献   
108.
For a smooth domain with compact boundary we investigate the problem with Neumann boundary conditions, where f has superlinear but subcritical growth. Provided that is sufficiently small we show the existence of at least positive solutions with single maximum points that lie on . We replace the standard variational setting used in the case of homogeneous f by considering the restriction of the free functional to a suitable submanifold of the Sobolev Space . Received May 25, 1997 / Accepted October 3, 1997  相似文献   
109.
We suggest a quantum stabilization method for theSU(2) σ-model, based on the constant-cutoff limit of the cutoff quantization method developed by Balakrishnaet al., which avoids the difficulties with the usual soliton boundary conditions pointed out by Iwasaki and Ohyama. We investigate the baryon numberB=1 sector of the model and show that after the collective coordinate quantization it admits a stable soliton solution which depends on a single dimensional arbitrary constant. We then study the radiative decays ofJ π=3/2+ baryons using the constant-cutoff approach to theSU(3) collective treatment of the Skyrme model for hyperons. Thus we evaluate the widths and E2/M1 ratios, showing that there is a general qualitative agreement with the results obtained using the complete Skyrme model, as well as the nonrelativistic quark model and quenched lattice model, for the total widths.  相似文献   
110.
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