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1.
A nucleophilic substitution reaction between 4-tert-butylbenzyl bromide and a series of iodide salts has been performed in oil-in-water microemulsions based on either a fatty alcohol ethoxylate or a sugar surfactant. The reaction kinetics was compared with the kinetics of the same reaction performed in a microhomogeneous reaction medium, d-MeOH. Previous results showing a particularly high reactivity in the microemulsion based on the fatty alcohol ethoxylate was confirmed. It was shown that in both microemulsions the reaction rate was almost independent of the choice of counterion to iodide. This indicates that complexation of the cation with the surfactant headgroup, which, in particular, could have taken place with surfactants containing oligooxyethylene chains (a “crown ether effect”), seems not to be of importance.

127I NMR studies, as well as quadrupole splitting experiments performed by 2H NMR, indicate that there is a certain accumulation of iodide at the oil–water interface of the microemulsions. It is difficult to draw any quantitative conclusions in this respect, however.

The results obtained in this study, combined with results from previous investigations of the same reaction, indicate that the unexpectedly high reactivity obtained in the microemulsion based on a surfactant containing an oligooxyethylene headgroup is most probably due to the nucleophile being poorly solvated when present in the headgroup layer of such a microemulsion. Poorly solvated anions are known to be highly reactive nucleophiles.  相似文献   

2.
静电加速管中强流空间电荷效应的研究   总被引:1,自引:0,他引:1       下载免费PDF全文
 对一种工业用大功率电子加速器(450kW)的加速管中的空间电荷效应作了5点假设,建立了物理模型。对模型的束内外径向电位分布、空间电荷对轴上电位的影响,以及空间电荷力对束流传输的影响等进行了理论分析,得到了束内径向电位分布。结果表明:束流内部径向电位沿径向均呈抛物线变化,并在轴上达到最小值;而空间电荷产生的束内电场与半径呈线性变化;空间电荷不仅会引起轴上电位的跌落,而且对束流有发散作用,特别是在电子速度较低时更为明显。在考虑了空间电荷效应后,强流静电加速管的电场设计关键在加速管的前端,与弱流加速管相比,强流加速管的电场变化要大得多。  相似文献   
3.
Using the path integral method we derive quantum wave function and quantum fluctuations of charge andcurrent in the mesoscopic RLC circuit. We find that the quantum fluctuation of charge decreases with time, oppositely,the quantum fluctuation of current increases with time monotonously. Therefore there is a squeezing effect in the circuit.If some more charge devices are used in the mesoscopic-damped circuit, the quantum noise can be reduced. We also findthat uncertainty relation of charge and current periodically varies with the period π/2 in the under-damped case.  相似文献   
4.
New photocrosslinkable maleimide copolymers have been synthesized by the attachment of a tricyanopyrrolidene‐based chromophore. The 2‐(3‐cyano‐4‐(2‐{4‐[hexyl‐(6‐hydroxy‐hexyl)‐amino]‐phenyl}‐vinyl)‐5‐oxo‐1‐{4‐[4‐(3‐oxo‐3‐phenyl‐propenyl)‐ phenoxy]‐butyl}‐1,5‐dihydro‐pyrrol‐2‐ylidene)‐malononitrile chromophore exhibits nonlinear optical activity and contains a chalcone moiety that is sensitive to UV light (λ = 330–360 nm) for crosslink formation. The maleimide monomers have also been functionalized with chalcone moieties. The resultant copolymers exhibit great processability, and one of them shows a maximum electrooptic coefficient of 90 pm/V at 1300 nm. We could control the thermal stability of the electrooptic coefficient with the newly synthesized photoreactive copolymers successfully. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 531–542, 2007  相似文献   
5.
We report on a new type of Fano effect, named as Andreev-Fano effect, in a hybrid normal-metal/supeeconductor (N/S) interferometer embedded with a quantum dot. Compared with the conventional Fano effect, AndreevFano effect has some new features related to the characteristics of Andreev reflection. In the Iinear response regime, the line shape is the square of the conventional Fano shape, while in the nonlinear transport, a sharp resonant structure is superposed on an expanded interference pattern, which is qualitatively different from the conventional Fano effect. The phase dependence of the hybrid N/S interferometer is also distinguished from those of all-N or all-S interferometers.  相似文献   
6.
提出了在无外力作功的情况下,具有Bauschinger效应的弹塑性材料处于屈服状态产生自发的塑性流动时应满足的条件.这个条件不仅与材料的力学性能有关,而且还处决于材料的具体的载荷边界条件和变形.举例说明了承受拉一扭组合的薄壁圆筒中,采用组合强化模型时,产生塑性流动的具体条件.  相似文献   
7.
8.
沈云  王海 《量子光学学报》2004,10(3):125-130
应用密度矩阵方程计算了四能级原子系统中三阶非线性极化率随信号光和探针光频率失谐的变化关系。结果表明,由于量子干涉对信号光强度的敏感性,使四能级原子介质的交叉Kerr非线性作用大大增强,与三能级系统相比,四能级原子介质的Kerr非线性系数可增强两个数量级。  相似文献   
9.
The reinforcement and nonlinear viscoelastic behavior have been investigated for silica (SiO2) filled solution‐polymerized styrene butadiene rubber (SSBR). Experimental results reveal that the nonlinear viscoelastic behavior of the filled rubber is similar to that of unfilled SSBR, which is inconsistent with the general concept that this characteristic comes from the breakdown and reformation of the filler network. It is interesting that the curves of either dynamic storage modulus (G′) or loss tangent (tan δ) versus strain amplitude (γ) for the filled rubber can be superposed, respectively, on those for the unfilled one, suggesting that the primary mechanism for the Payne effect is mainly involved in the nature of the entanglement network in rubbery matrix. It is believed there exists a cooperation between the breakdown and reformation of the filler network and the molecular disentanglement, resulting in enhancing the Payne effect and improving the mechanical hysteresis at high strain amplitudes. Moreover, the vertical and the horizontal shift factors for constructing the master curves could be well understood on the basis of the reinforcement factor f(φ) and the strain amplification factor A(φ), respectively. The surface modification of SiO2 causes a decrease in f(φ), which is ascribed to weakeness of the filler–filler interaction and improvement of the filler dispersion. However, the surface nature of SiO2 hardly affects A(φ). © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2594‐2602, 2007  相似文献   
10.
利用精炼的C语言进行程序设计,定量模拟狭义相结论的运动时钟变慢,并对处于两种不同时空观的时钟运行进行对比,使得时间膨胀效应变得直观。  相似文献   
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