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1.
The methanolysis of the insecticide paraoxon (2) was investigated in methanol solution containing varying [La(OTf)(3)] (OTf = (-)OS(O)(2)CF(3)) as a function of at 25 degrees C. Plots of the pseudo-first-order rate constants (k(obs)) for methanolysis as a function of [La(OTf)(3)](total) were obtained under buffered conditions from 5.15 to 10.97, and the slopes of the linear parts of these were used to determine the second-order rate constants (k(2)(obs)) for the La(3+)-catalyzed methanolysis of 2. Detailed analysis of the potentiometric titration data of La(OTf)(3) in methanol through fits to a multicomponent equilibrium mixture of dimers of general stoichiometry La(3+)(2)((-)OCH3)n, where n assumes values of 1-5, gives the equilibrium distribution of each as a function of. These data, when fit to a second expression describing k(2)(obs) in terms of a linear combination of individual rate constants k(2)(2:1), k(2)(2:2).k(2)(2:)n for the dimers, allow one to describe the overall catalytic profile in terms of the individual contributions. The most catalytically important species are the three dimers La(3+)(2)((-)OCH3)1, La(3+)(2)((-)OCH3)2, and La(3+)(2)((-)OCH3)3. The catalysis of the methanolysis of 2 is spectacular: a 2 x 10(-3) M solution of [La(3+)](total), at neutral, affords a 10(9)-fold acceleration relative to the base reaction (t(1/2) approximately 20 s at 8.2) with excellent turnover. A mechanism of the catalyzed reaction involving the La(3+)(2)((-)OCH3)2 species is proposed. 相似文献
2.
We discuss the notion of spin squeezing considering two mutually exclusive classes of spin-s states, namely, oriented and non-oriented states. Our analysis shows that the oriented states are not squeezed while non-oriented
states exhibit squeezing. We also present a new scheme for construction of spin-s states using 2s spinors oriented along different axes. Taking the case of s=1, we show that the ‘non-oriented’ nature and hence squeezing arise from the intrinsic quantum correlations that exist among
the spinors in the coupled state. 相似文献
3.
M. V. Yakunin G. A. Al’shanskii Yu. G. Arapov V. N. Neverov G. I. Harus N. G. Shelushinina O. A. Kuznetsov A. de Visser L. Ponomarenko 《Physics of the Solid State》2005,47(1):49-53
The structure of the quantum-well valence band in a Ge(111) two-dimensional layer is calculated by the self-consistent method. It is shown that the effective mass characterizing the motion of holes along the germanium layer is almost one order of magnitude smaller than the mass for the motion of heavy holes along the [111] direction in a bulk material (this mass is responsible for the formation of quantum-well levels). This creates a unique situation in which a large number of subbands appear to be populated at moderate values of the layer thickness d w and the hole concentration p s . The depopulation of two or more upper subbands in a 38-nm-thick germanium layer at a hole concentration p s = 5 × 1015 m?2 is revealed from the results of measuring the magnetoresistance in a strong magnetic field aligned parallel to the germanium layers. The destruction of the quantum Hall state at a filling factor ν = 1 indicates that the two lower subbands merge together in a self-formed potential profile of the double quantum well. It is demonstrated that, in a quasi-two-dimensional hole gas, the latter effect should be sensitive to the layer strain. 相似文献
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3-Cyclopropyl-3-oxopropionitrile anion obtained by cathodic reduction of 5-cyclopropylisoxazole in an aprotic medium was used
as an example to demonstrate that cyano ketone anions show a dual reactivity. The reaction of acetyl chloride with the electrogenerated
tetrabutylammonium salt of 3-cyclopropyl-3-oxopropionitrile gave O-acylation products, whereas the reaction with its sodium salt gives C-acylation products. The reactions of these salts with hydroxylamine hydrochloride follow a different route: in the case of
the tetrabutylammonium salt, resinification takes place, while in the case of the sodium salt, 5-amino-3-cyclopropylisoxazole
is formed. The condensation of this product with 4,4,4-trifluoro-1-(2-thienyl)butane-1,3-dione in glacial AcOH affords 3-cyclopropyl-6-(2-thienyl)-4-(trifluoromethyl)isoxazolo[5,4-b]pyridine in 85% yield.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2110–2114, November, 2007. 相似文献
7.
AA Yan LI Kai CAO ZhongHua & HU WenRui Key Laboratory of Microgravity 《中国科学:物理学 力学 天文学(英文版)》2011,(2)
The dependency of the critical Marangoni number on the geometrical aspect ratio of the floating half zone is essential to predict the onset of oscillatory thermocapillary convection.The experimental studies in the microgravity conditions on floating half zones of several centimeters in diameter have predicted that the critical Marangoni number increases with the increasing aspect ratio,and the terrestrial experimental studies have predicted the contradictory conclusion for floating half zones of several mil... 相似文献
8.
Non-Gravitational Effects with Density-Matching in Evaluating the Influence of Sedimentation on Colloidal Coagulation 下载免费PDF全文
The method of density matching between the solid and liquid phases is often adopted to effectively eliminate the effect of sedimentation of suspensions in studies on dynamic behaviour of a colloidal system. However, the associated changes in the solvent composition may bring side effects to the properties investigated and therefore might lead to a faulty conclusion if the relevant correction is not made. To illustrate the importance of this side effect, we present an example of the sedimentation influence on the coagulation rate of suspensions of 2μm (diameter) polystyrene. The liquid mixtures, in the proper proportions of water (H2O), deuterium oxide (D2O) and methanol (MeOH) as the liquid phase, density-matched and unmatched experiments are performed. Besides the influence of viscosity, the presence of methanol in solvent media, used to enhance the sedimentation effect, causes significant changes (reduction) in rapid coagulation rates compared to that in pure water. Without the relevant corrections for those non-gravitational factors it seems that gravitational sedimentation would retard the coagulation. The magnitude of the contribution from the non-gravitational factor is quantitatively determined, making the relevant correction possible. After necessary the influence of the sedimentation on coagulation rates at corrections for all factors, our experiments show that the initial stage of the coagulation is not observable. 相似文献
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