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991.
A. S. Culf M. Čuperlović‐Culf R. J. Ouellette 《Magnetic resonance in chemistry : MRC》2009,47(2):158-164
Highly coloured Janovsky complexes have been known for over 120 years, being used in many colourimetric analytical procedures. In this present study, two novel and stable nitrocyclohexadienyl spirobicyclic, zwitterionic Janovsky anionic hydantoin σ‐complexes, rac‐1,3‐diisopropyl‐6‐nitro‐2,4‐dioxo‐1,3‐diazaspiro[4.5]deca‐6,9‐dien‐8‐ylideneazinate, ammonium internal salt (1) and 1,3‐diisopropyl‐2,4‐dioxo‐1,3‐diazaspiro[4.5]deca‐6,9‐dien‐8‐ylideneazinate, ammonium internal salt (2) have been prepared and characterised by NMR, electrospray ionization mass spectrometry (ESI‐MS) and UV/visible methods. For the p‐mononitro‐substituted complex (2), we discovered chemical exchange behaviour using 1D saturation transfer and 2D exchange spectroscopy (EXSY) 1H NMR techniques. The coalescence temperature was determined to be 62 °C in d3‐acetonitrile. Analysis of these data provided a Gibbs free energy of activation, ΔG ?, of + 67 kJ mole?1, a rate constant, k, coalescence of 220 Hz and an equilibrium constant, Keqm, of 0.98 as estimates of the exchange process in this solvent. Of the two mechanisms proposed for this fluxional behaviour, ring opening to a substituted benzene or proton exchange, a further theoretical modelling study of 1D 1H NMR spectra was able to confirm that simple proton exchange between the two nitrogen sites of the hydantoin ring provided an accurate simulation of the observed experimental evidence. Interestingly, the o,p‐dinitro‐substituted complex (1) did not show any chemical exchange behaviour up to 150 °C in d3‐acetonitrile (to 75 °C) and d6‐dimethyl sulfoxide (DMSO). Molecular modelling at the MM2 level suggests that steric collisions of an N‐acyl isopropyl substituent of the hydantoin ring with the ortho‐nitro group of the spirofused cyclohexadienyl ring prevents the proposed proton exchange mechanism occurring in this case. Copyright © 2008 Crown in the right of Canada. Published by John Wiley & Sons, Ltd 相似文献
992.
Numerical simulation results derived from a Schrödinger–Poisson tool applied to scaled double-gate (DG) MOSFETs, supplemented by analytical characterizations of the pertinent physics, are presented to give insight concerning the near-ideal features of DG devices and to explain how the low-voltage drive current of the asymmetrical DG MOSFET, having only one predominant channel, can be comparable to, and even higher than, that of the symmetrical-gate counterpart designed to have the same off-state current. 相似文献
993.
由一道证明题引申出一个命题,对该命题给出了证明;通过几个实例说明应用该命题可以简便地求解某些接地导体的感应电荷. 相似文献
994.
The effective charge state is an important particle parameter which is required for the calculation of many effects concerning the interaction between radiation and matter such as an estimate of the radial dose of swift heavy projectiles, stopping power and so on. A new method for the determination of effective charge states of heavy ions is based on the measurement of the number of high-energy delta-electrons which are ejected from a target by the penetrating ion. These electrons are detectable with a CCD-detector and their number can be correlated to the effective charge state of the projectile for known particle velocities. This method is even applicable to operation with single swift heavy ions within statistical bounds. 相似文献
995.
我们研制了CEBQ程序和ENVLOP程序,模拟稳态相对论电子束在二极管区的产生和加速,以及电子束在阳极通道内的传输过程。CEBQ程序模拟二极管区电子轨道,当阳极电压为1.5MV时,阴极总发射电流为17.9kA,进入阳极通道内的传输电流为4.3kA,阳极入口处D=4cm的束发射度为24.9cm.mrad。ENVLOP程序使用线性近似下的包络方程,描述电子束包络在螺旋管引导磁场作用下的变化,讨论了外加引导磁场对包络的影响。计算结果表明,在合适引导磁场作用下,束包络起伏较小,进入阳极通道的束流(4.3kA)能全部通过。 相似文献
996.
本文对如何从单一二维交换谱提取速率常数进行了理论分析,提出了一种近似处理方法,即把较短混合时间τ_m内在二维平面上磁化强度传递看成是单向进行的,进而导出了二维交换谱中所有峰强随τ_m变化的表达式。所得结果与Ernst的精确结果在一级近似下完全一致,在二级近似下略有不同,但将难以求解的问题转化成简单的代数方程、用这一方法对新近获得的SnCl_4·5H_2O在水溶液中的~(119)Sn二维交换谱进行了处理,得到与实验相吻合的结果,并求得了SnCI_6~(2-)水解体系的动态交换速率常数。 相似文献
997.
The kinetics of phosphate-catalyzed proton exchange have been measured with NMR lineshape analysis for a series of amides, ureas, and carbamates. A hypothetical energy profile for transition structures of concerted phosphate catalysis ?c and of stepwise phosphate catalysis ?1, ?2 is used for discussion of the substituent effects. The concerted mechanism of phosphate catalysis operates only for amides RCONHCH3 for which the electron-donating ability of the substituent R is comparable with, or better than, that of the methyl group. We conclude that concerted phosphate catalysis is inoperative in proteins or polypeptides. 相似文献
998.
Narayanan Prakash Georg Csanády Markus R. A. Michaelis Günter Knapp 《Mikrochimica acta》1989,99(3-6):257-265
Automated preconcentration techniques for off/on-line determination with ICP-OES have been developed for various metal ions of environmental interest. Preconcentration studies were performed on two different types of chemically bonded chelating ion-exchangers, namely EDTrA-cellulose (iminoacetate groups) and HSO3 · oxine-cellulose. Enrichment studies were carried out at various preconcentration factors and also at different loadings.Presented in part at the 1989 European Winter Conference on Plasma Spectrochemistry, Reutte, Austria 相似文献
999.
自首次于聚乙炔发现导电现象以来,具有共轭结构的有机半导体材料赖其种类丰富多样、
制备工艺简捷低耗、以及优异的机械柔性等特点,在“后硅时代”中有望以先进光电子设备展现
其广阔前景,因而多年来备受学界和产业界的瞩目。如何进一步阐明有机半导体中结构和性能之
间的关系,探索电荷载流子微观动力学行为,构筑高性能、新功能的有机光电子器件,是当下有
机电子学领域的前沿核心问题,也是保证其持续发展的基石。近年来,二维有机半导体晶体材料
在秉持高度有序的分子排列与极低的杂质缺陷浓度等优点的同时,更是以“薄膜即是界面、界面
即是薄膜”为一帜,克服传统体材料在研究与应用中的瓶颈,为揭示材料构性关系及其中基本物
理过程提供了良好的平台,也是实现多样化的新型有机光电子器件的理想材料,有望为微纳电子
领域带来新一轮变革。本文从二维有机半导体晶体的制备工艺、电荷载流子微观动力学行为,再
到新型器件的光电功能应用等方面,综述了最新研究进展,做出总结和展望,并提出目前面临的
挑战及未来研究方向,旨在为进一步深入理论研究,结合有机材料与先进技术,推动有机电子学
的发展提供有益帮助。 相似文献
1000.
Exciton emission dynamics in single InAs/GaAs quantum dots due to the existence of plasmon-field-induced metastable states in the wetting layer
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《中国物理 B》2021,30(9):97805-097805
A very long lifetime exciton emission with non-single exponential decay characteristics has been reported for single InA-s/GaAs quantum dot(QD) samples,in which there exists a long-lived metastable state in the wetting layer(WL)through radiative field coupling between the exciton emissions in the WL and the dipole field of metal islands.In this article we have proposed a new three-level model to simulate the exciton emission decay curve.In this model,assuming that the excitons in a metastable state will diffuse and be trapped by QDs,and then emit fluorescence in QDs,a stretchedlike exponential decay formula is derived as I(t)=At~(β-1)e~(-(rt)β),which can describe well the long lifetime decay curve with an analytical expression of average lifetime 相似文献