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101.
《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(1):130-137
We have shown previously that iodosylbenzene–iron(III ) porphyrin intermediates ( 2 ) are generated in the reactions of oxoiron(IV ) porphyrin π‐cation radicals ( 1 ) and iodobenzene (PhI), that 1 and 2 are at equilibrium in the presence of PhI, and that the epoxidation of olefins by 2 affords high yields of epoxide products. In the present work, we report detailed mechanistic studies on the nature of the equilibrium between 1 and 2 in the presence of iodoarenes (ArI), the determination of reactive species responsible for olefin epoxidation when two intermediates (i.e., 1 and 2 ) are present in a reaction solution, and the fast oxygen exchange between 1 and H218O in the presence of ArI. In the first part, we have provided strong evidence that 1 and 2 are indeed at equilibrium and that the equilibrium is controlled by factors such as the electronic nature of iron porphyrins, the electron richness of ArI, and the concentration of ArI. Secondly, we have demonstrated that 1 is the sole active oxidant in olefin epoxidation when 1 and 2 are present concurrently in a reaction solution. Finally, we have shown that the presence of ArI in a reaction solution containing 1 and H218O facilitates the oxygen exchange between the oxo group of 1 and H218O and that the oxygen exchange is markedly influenced by factors such as ArI incubation time, the amounts of ArI and H218O used, and the electronic nature of ArI. The latter results are rationalized by the formation of an undetectable amount of 2 from the reaction of 1 and ArI through equilibrium that leads to a fast oxygen exchange between 2 and H218O. 相似文献
102.
In this paper, the authors deal with bifunctions defined on complete metric spaces and with values in locally convex spaces ordered by closed convex cones. The aim is to provide a vector version of Ekeland’s theorem related to equilibrium problems. To prove this principle, a weak notion of continuity of a vector-valued function is considered, and some of its properties are presented. Via the vector Ekeland’s principle, existence results for vector equilibria are proved in both compact and noncompact domains. 相似文献
103.
104.
q变形对相干态的相位概率分布特性 总被引:2,自引:0,他引:2
通过推广Pegg和Barnett的相位算符和相位态到q变形的双模情况, 应用数值计算
研究了q变形对相干态的相位概率分布特性. 结果表明, q变形对相干态的相位概率分布受到相位参数、q参数和参数│ξ│的调节, 从而反映出不同的量子相干特性. 相似文献
105.
基于傅立叶变换轮廓术的物面相位提取 总被引:1,自引:0,他引:1
采用傅立叶变换轮廓术,针对基频提取的关键技术采用逐行傅立叶变换,准确提取基频信息的方法恢复相位信息.在此基础上,以未畸变条纹为基准,得出被测物体的真实位相值.该方法只需一幅条纹图,节约了测量时间.实验证明可实现无接触面型的自动传感. 相似文献
106.
Uptake of trace elements into fish otoliths is governed by several factors such as life histories and environment in addition to stock and species differences. In an attempt to elucidate the elemental signatures of rare earth elements (REEs) in otoliths, a solid phase extraction (SPE) protocol was used in combination with electrothermal vaporization (ETV) as a sample introduction procedure for the determinations by inductively coupled plasma quadrupole mass spectrometry (ICP-MS). Effects of various parameters, such as carrier gas flow rate, atomization temperature and chemical modification, were examined for optimization of the conditions by ETV-ICP-MS. Atomization was achieved at 2800 °C. Lower temperatures (i.e. 2600 °C) resulted in severe memory problems due to incomplete atomization. Palladium was used as a chemical modifier. It was found that an increase in Pd concentration up to 0.5 μg in the injection volume (70 μl) led up to four-fold enhancement in the integrated signals. This phenomenon is attributed to the carrier effect of Pd rather than the stabilization since no significant losses were observed for high temperature drying around 700 °C even in the absence of Pd. Preconcentration was performed on-line at pH 5 by using a mini-column of Toyopearl AF-Chelate 650M chelating resin, which also eliminated the calcium matrix of otolith solutions. After preconcentration of 6.4 ml of solution, the concentrate was collected in 0.65 ml of 0.5% (v/v) HNO3 in autosampler cups, and then analyzed by ETV-ICP-MS. The method was validated with the analysis of a fish otolith certified reference material (CRM) of emperor snapper, and then applied to samples. Results obtained from otoliths of fish captured in the same habitat indicated that otolith rare earth element concentrations are more dependent on environmental conditions of the habitat than on species differences. 相似文献
107.
108.
Using an infinite-horizon two-player differential game, we derive and compare Bertrand and Cournot equilibria for a differentiated duopoly engaging in the process of R&D competition. The main findings of this study are as follows. First, Bertrand competition is more efficient if either R&D productivity is low or products are very different. Second, Cournot competition is more efficient provided that R&D productivity is high, products are close substitutes, and spillovers are not close to zero. This last result is different from what has been obtained in the literature. Hence, this shows that considering a dynamic model and more general investment costs does have an impact on the efficiency results. 相似文献
109.
Werner Kaller 《Journal of Quantitative Spectroscopy & Radiative Transfer》2004,87(2):107-117
The angular dependence of light scattered by aerosol particles in the atmosphere—the aerosol phase function—is one of the key properties of every radiative transfer and climate model. Side-scattering in the atmosphere is currently believed to be underestimated by most of the radiative transfer models in certain cases. The aerosol phase function can be measured with polar nephelometers.An innovative polar nephelometer able to measure the phase function of ambient aerosol directly is presented in this publication. The performance of the device was simulated completely using ray-tracing techniques. The results of these simulations are used to interpret the measurement data precisely. The measurements with the new polar nephelometer are fully automated. The quality of the measurement results was verified using different approaches. The values of the statistical and systematic error in measuring atmospheric aerosol are about 4% each. Scattering angles from 10° to 160° were measured and it is shown that with the same design this range can be extended to 3-177° in steps of 0.16° with an aperture of less than 1.8°.Measurements of the aerosol phase function are presented and compared with data taken with an integrating nephelometer and measurements of the particulate matter concentration. All data correlate very well. The described polar nephelometer can measure the phase function and the scattering coefficient of atmospheric aerosol with high accuracy and can be used for continuous monitoring measurements as well as in field campaigns. 相似文献
110.
J. L. Hernández–Pastora O. V. Manko V. S. Manko J. Martín E. Ruiz 《General Relativity and Gravitation》2004,36(4):781-797
The extended quadruple–Kerr metric is used to consider equilibrium states of four collinear Kerr particles. We explain our previous failure to solve numerically the full set of the balance equations, and we derive a self–consistent system of the axis conditions leading to the equilibrium of all four constituents which can be black holes or hyperextreme objects. The equilibrium configurations obtained in this paper exhibit similar features with those occurring in the systems of two Kerr particles, for instance, the balance of four Kerr black holes with positive masses does not seem possible. Equilibrium states of two identical compound Kerr objects are also discussed. 相似文献