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71.
A series of bimetallic N-heterocyclic carbene (NHC) ruthenium(II) complexes were synthesized, which comprise two [RuCl(2)(cymene)(NHC)] units that are interlinked via the NHC nitrogens by alkyl chains of different length. Electrochemical characterization revealed two mutually dependent oxidation processes for the complex with a methylene linker, indicating moderate intramolecular electronic coupling of the two metal centers (class II system). The degree of coupling decreases rapidly upon increasing the number of CH(2) units in the linker and provides essentially decoupled class I species when propylene or butylene linkers are used. Electrochemical analyses combined with structural investigations suggest a through-bond electronic coupling. Replacement of the alkyl linker with a p-phenylene group afforded cyclometalated complexes, which were considerably less stable. The electronic coupling in the methylene-linked complex and the relatively robust NHC-ruthenium bond may provide access to species that are switchable on the molecular scale. 相似文献
72.
Rangel TB Assreuy AM Pires Ade F Carvalho AU Benevides RG Simões Rda C Silva HC Bezerra MJ Nascimento AS Nascimento KS Nagano CS Sampaio AH Delatorre P Rocha BA Fernandes PM Cavada BS 《Molecules (Basel, Switzerland)》2011,16(6):5087-5103
DwL, a lectin extracted from the seeds of Dioclea wilsonii, is a metalloprotein with strong agglutinating activity against rabbit and ABO erythrocytes, inhibited by glucose and mannose. DwL was purified by affinity chromatography on a Sephadex G-50 column and ion exchange chromatography on a HiTrap SP XL column. SDS-PAGE revealed three electrophoretic bands corresponding to the α (25,634 ± 2 Da), β (12,873 ± 2 Da) and γ (12,779 ± 2 Da) chains. Protein sequencing was done by Tandem Mass Spectrometry. The primary sequence featured 237 amino acids and was highly homologous to other reported Diocleinae lectins. A complete X-ray dataset was collected at 2.0 ? for X-Man-complexed DWL crystals produced by the vapor diffusion method. The crystals were orthorhombic and belonged to the space group I222, with the unit-cell parameters a = 59.6, b = 67.9 and c = 109.0 ?. DWL differed in potency from other ConA-like lectins and was found to induce neutrophil migration in rats, making it particularly useful in structural/functional studies of this class of proteins. 相似文献
73.
We fabricated a TiO(2)-ZrO(2) affinity chromatography micro-column on 2 mm PMMA plates, and demonstrated the enrichment and separation of (a) a standard mono- and tetra-phosphopeptide, and (b) phosphopeptides contained in a tryptic digest of β-Casein. The chromatography column consisted of 32 parallel microchannels with common input and output ports and was fabricated by lithography directly on the polymeric substrate followed by plasma etching (i.e. standard MEMS processing) and sealed with lamination. The liquid deposited TiO(2)-ZrO(2) stationary phase was characterized by X-ray diffraction and was found to be mostly TiO(2) and ZrO(2) in crystalline phases. Off-chip UV detection and MALDI MS identification of the separated effluents were used. The chip had a capacity of >1.4 μg (0.7 nmol) of a prototype mono-phosphopeptide and a recovery of 94 ± 3%, and can be used with small samples (less than 0.1 μL depending on the syringe pump used). The chip design allows an expansion of its capacity by means of increasing the number of parallel microchannels at a constant sample volume. Our approach provided an alternative to off-line extraction tips (with typical capacities of 1-2 μg and sample volumes of 1-10 μL), and to on-chip efforts based on packed bed and frit formats. 相似文献
74.
V��ctor Hugo Rol��n-Garrido Julia Antonia Resch Friedrich Wolff Joachim Kaschta Helmut M��nstedt Manfred H. Wagner 《Rheologica Acta》2011,50(7-8):645-653
The linear and nonlinear steady-state viscosities and elastic compliances were measured in shear and elongational flows for two low-density polyethylenes, a linear polypropylene, and two metallocene catalyzed polyethylenes (one linear and one long-chain branched) by Wolff et al. (Rheol Acta 49:95?C103, 2010) and Resch (dissertation, 2010). Comprehensive data of this type are rarely found in the literature, and comprehensive modeling of both viscous and elastic effects is even rarer. In this contribution, the reliability of a modeling approach proposed by Laun (J Rheol 30(3):459?C501, 1986) and based on the damping function concept is tested. The strain hardening seen for the long-chain branched polymers and its absence in the case of the linear polymer, the stronger decrease of the tensile compliance in comparison to the shear compliance with increasing stress, as well as the extended linear-viscoelastic regime of the shear viscosity in contrast to the shear compliance are correctly modeled. While the modeling of the nonlinear response in shear can be achieved with only one material parameter for most of the polymers considered here, the nonlinear modeling in elongation is achieved with two parameters. The same parameter values are shown to describe viscous as well as elastic properties of the melts, and thus the relations of Laun can be used to test the consistency of viscosity and compliance measurements. 相似文献
75.
76.
Spectral corrections, which are based on local isotropy, are presented for all the spatial derivatives of velocity and temperature fluctuations which feature in the average dissipations of turbulent energy and temperature. The corrections, which compensate for the spectral attenuation due to the separation between sensors, depend only weakly on the choice of the three-dimensional energy (or temperature) spectrum and therefore on the turbulence Reynolds number. Corrections are also obtained for the variances of velocity and temperature derivatives. The diagonal velocity derivatives require smaller corrections than either the off-diagonal velocity derivatives or the temperature derivatives. Corrections of comparable magnitude are required for the average dissipations of turbulent energy and temperature. 相似文献
77.
78.
Use is made of computer simulated turbulent signals to calculate the rms of the velocity cone angle. The calculation compares
favourably with X-probe data close to the axis of a circular jet. In this flow, the vector cone angle can exceed 90°, even
on the axis. As a consequence, the rms values of the cone angle and of the lateral velocity fluctuation can be seriously underestimated
with a 90° X-probe. Support for this is provided by measurements with a 120° X-probe. 相似文献
79.
Spectra and spectral coherences of mainly the lateral velocity fluctuations, measured in the wake of a circular cylinder, strongly suggest that the origin of the far-wake organised motion can be traced back to the cylinder. A possible mechanism for the development of the organised motion is suggested. 相似文献
80.