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81.
Guodong Feng Yanfu Huan Yanbo Cao Shuhua Wang Xinghua Wang Jie Jiang Aimin Yu Qinhan Jin Hongmei Yu 《Microchemical Journal》2004,76(1-2):17
An unique miniature simultaneous microwave plasma torch (MPT) atomic emission spectrometer employing linear UV intensified charge-coupled device (ICCD) array detector has been developed and studied preliminarily. The detection limits and precisions of the spectrometer for Ag, Al, Ba, Ca, Cr, Cu, Fe, Mg, Mn, Sr and V by using different CCD exposure times have been determined. An analysis of a practical sample has been carried out. The preliminary results demonstrate that such simultaneous spectrometer has advantages of saving sample and time, especially suitable for use as detector for chromatography and in combination with flow injection systems. Taking analytical figures of merit and portability into accounts, the miniature simultaneous MPT system will have extended application areas and greater competition potential as compared with commercialized scanning MPT spectrometers. 相似文献
82.
The electric conduction in the fibrous medium constructed by a homogeneous array of parallel, identical, charged, circular cylinders having an arbitrary zeta potential filled with the solution of a symmetrically charged electrolyte is analytically examined. The thickness of the electric double layers surrounding the dielectric cylinders is assumed to be small relative to the radius of each cylinder and to the gap width between two neighboring cylinders, but the polarization of the mobile ions in the diffuse layers is allowed. The effect of interactions among individual cylinders is taken into explicit account by employing a unit cell model. The appropriate equations of conservation of electrochemical potential energies of ionic species are solved for each cell, in which a cylinder is envisaged to be surrounded by a coaxial cylindrical shell of the fluid solution. Analytical expressions for the effective electric conductivity are obtained in closed forms as functions of the porosity of the fiber matrix and other characteristics of the porous system. Comparisons of the results of the cell model with different conditions at the outer boundary of the cell are made. Under an otherwise identical condition, the electric conductivity in a porous medium composed of an array of parallel cylinders in the transverse direction is smaller than that of a suspension of spheres. The effect of interactions among the cylinders or spheres on the effective conductivity can be quite significant under appropriate conditions. 相似文献
83.
Using potentially bidentate ligands (-SC2H4NH2), we produced [2Fe-2S]+ species of different coordination geometries by fission of [4Fe-4S]2+ complexes. Even though the ligands are monodentate in the cubane complexes, both mono- and bidentate complexes were observed in the [2Fe] fission products through self-assembly because of the high reactivity of the tricoordinate iron sites. The electronic structure of the [2Fe] species was probed using photoelectron spectroscopy and density functional calculations. It was found that tetracoordination significantly decreases the electron binding energies of the [2Fe] complexes, thus increasing the reducing capability of the [2Fe-2S]+ clusters. 相似文献
84.
The electrophoretic motion of two charged colloidal spheres with very thin electrical double layers in a constant applied electric field along their line of centers is considered. The particles may differ in radius and in zeta potential at the surface. The electrostatic and hydrodynamic governing equations are solved in the quasi-steady situation using bipolar coordinates and the electrophoretic velocities of particles are calculated for various cases. The interaction effect between particles can be very significant when the distance between particle surfaces gets close to zero. The particle with smaller zeta potential is speeded up by the motion of the other, which is retarded at the same time by the motion of the former one, if the two spheres have unequal zeta potentials of the same electrical sign. For two particles of different signs in zeta potential, motions of both are hindered by each other. The influence of the interaction between particles in general is stronger on the smaller one than on the larger one. For the special case of two electrophoretic spheres with identical zeta potentials, there is no particle interaction for all particle sizes and separations. 相似文献
85.
The electrochemistry of indium species was investigated at glassy carbon, tungsten and nickel electrodes in a basic 1‐ethyl‐3‐methylimidazolium chloride/tetrafluoroborate ionic liquid. Amperometric titration experiments suggest that In(III) chloride is complexed as [InCl5]2? in this ionic liquid. The electrochemical reduction of [InCl5]2? to indium metal is preceded by overpotential driven nucleations. The effective anodic dissolution of indium to indium(III) requires, however, the presence of sufficient chloride ions at the electrode surface. The electrodeposition of indium at glassy carbon and tungsten electrodes proceeds via three‐dimensional instantaneous nucleation with diffusion‐controlled growth of the nuclei. At the nickel electrode, the deposition proceeds via three‐dimensional progressive nucleation with diffusion‐controlled growth of the nuclei. Raising the deposition temperature decreases the average radius of the individual nuclei, r. Scanning electron microscopic and x‐ray diffraction data indicated that bulk crystalline indium electrodeposits could be prepared on nickel substrates within a temperature range between 30 and 120 °C. 相似文献
86.
In this study, poly(N-methylolacrylamide)/polymethylacrylamide (PNMA/PMAA) hybrids were produced successfully by frontal free-radical polymerization
at ambient pressure. In a typical run, the appropriate amounts of reactants (N-methylolacrylamide, NMA; methylacrylamide, MAA) and initiator (ammonium persulfate) were dissolved in dimethyl sulfoxide
at ambient temperature. Frontal polymerization (FP) was initiated by heating the wall of the tube with a soldering iron, and
the resultant hot fronts were allowed to self-propagate throughout the reaction vessel. Once initiated, no further energy
was required for polymerization to occur. The dependences of the front velocity and front temperature on the initiator concentration,
reactant dilution, and NMA/MAA components were thoroughly investigated. The front temperatures were between 69 and 116 °C,
depending on the persulfate concentration. We have also investigated the FP of PNMA/PMAA hybrids with N-methyl-2-pyrrolidone as solvent. Results show that FP can be exploited as a means for the preparation of PNMA/PMAA hybrids
with the potential advantage of higher throughput compared to the traditional mode. 相似文献
87.
Wang H Huang J Wulff WD Rheingold AL 《Journal of the American Chemical Society》2003,125(30):8980-8981
The intramolecular benzannulations of carbene complexes with alkynes are examined where the alkyne is tethered to the alpha-carbon of the vinyl carbene complex. These reactions are sensitive to the length of the tether and to the nature of the solvent. With a tether length of 16 methylenes, the reaction occurs in the same fashion as the intermolecular reactions to give a p-cyclophane. With intermediate tether lengths (n = 10, 13), the reaction gives an additional p-cyclophane in which the two oxygen substituents are meta on the arene ring. This type of product is unprecedented from the reaction of carbene complexes and alkynes and is quite surprising because the formation of this product requires that the carbon-carbon bond between the alpha- and beta-carbons of the vinyl carbene complex is broken. A mechanism is proposed to account for this process which involves the crossed intramolecular [2 + 2] cycloaddition of the alkene and a ketene in a conjugated dienyl ketene to give a benzvalenone paddalane intermediate. 相似文献
88.
IntroductionTheincreasingcommercialvalueoftransitionmetalcomplexesofxanthateshasarousedconsiderableinterestintheirchemistry .Whiletheiranalyticalapplicationsarewellknown ,1theyarenowfindingextensiveuseinvulcan izationofrubber ,frothfloatationprocessforconcentrationofsulphideores ,asantioxidants ,lubricants ,2 ,3andhavebeenfoundtopossessfungicidalandinsecticidalactivi ties .4 Recently ,molecularrecognitionbetweenhostandguestmolecules ,inclusionphenomenaandnoncovalentmolecularinteractionarefunda… 相似文献
89.
Wenxuan Jiang Wei Wei Tinglian Yuan Shasha Liu Ben Niu Hui Wang Wei Wang 《Chemical science》2021,12(24):8556
The inevitable microstructural defects, including cracks, grain boundaries and cavities, make a portion of the material inaccessible to electrons and ions, becoming the incentives for electrochemically inactive zones in single entity. Herein, we introduced dark field microscopy to study the variation of scattering spectrum and optical mass centroid (OMC) of single Prussian blue nanoparticles during electrochemical reaction. The “dark zone” embedded in a single electroactive nanoparticle resulted in the incomplete reaction, and consequently led to the misalignment of OMC for different electrochemical intermediate states. We further revealed the dark zones such as lattice defects in the same entity, which were externally manifested as the fixed pathway for OMC for the migration of potassium ions. This method opens up enormous potentiality to optically access the heterogeneous intraparticle dark zones, with implications for evaluating the crystallinity and electrochemical recyclability of single electroactive nano-objects.The schematic of single cubic-shaped Prussian blue (PB) mesocrystals formed by the oriented aggregation of small nanocrystals. The dark-field images of single PB nanoparticle at PB and Prussian white (PW) states, respectively. 相似文献
90.
The starting electrophoretic motion of a porous, uniformly charged, spherical particle, which models a solvent-permeable and ion-penetrable polyelectrolyte coil or floc of nanoparticles, in an arbitrary electrolyte solution due to the sudden application of an electric field is studied for the first time. The unsteady Stokes/Brinkman equations with the electric force term governing the fluid velocity fields are solved by means of the Laplace transform. An analytical formula for the electrophoretic mobility of the porous sphere is obtained as a function of the dimensionless parameters , , , and , where a is the radius of the particle, κ is the Debye screening parameter, λ is the reciprocal of the square root of the fluid permeability in the particle, ρp and ρ are the mass densities of the particle and fluid, respectively, ν is the kinematic viscosity of the fluid, and t is the time. The electrophoretic mobility normalized by its steady-state value increases monotonically with increases in and , but decreases monotonically with an increase in , keeping the other parameters unchanged. In general, a porous particle with a high fluid permeability trails behind an identical porous particle with a lower permeability and a corresponding hard particle in the growth of the normalized electrophoretic mobility The normalized electrophoretic acceleration of the porous sphere decreases monotonically with an increase in the time and increases with an increase in from zero at . 相似文献