碳负离子重排的DFT计算研究

采用密度泛函方法计算了碳负离子1,2-迁移和1,4-迁移两个反应的过渡态的分子轨道,发现在过渡态中迁移原子携带正电荷,剩余部分则形成双碳负离子。在1,2-迁移过渡态中,剩余的双碳负离子的HOMO位相与迁移原子的LUMO位相不匹配。但在1,4-迁移过渡态中,剩余的双碳负离子的HOMO位相与迁移原子的LUMO位相匹配。所以碳负离子的1,2-迁移是轨道对称性禁阻的反应,而1,4-迁移则是轨道对称性允许的反应。本文的计算可以为我国高等有机化学教学提供良好参考。     

Stabilization of nonlinear systems in compound critical cases

In this paper, we study the stabilization of nonlinear systems in critical cases by using the center manifold reduction technique. Three degenerate cases are considered, wherein the linearized model of the system has two zero eigenvalues, one zero eigenvalue and a pair of nonzero pure imaginary eigenvalues, or two distinct pairs of nonzero pure imaginary eigenvalues; while the remaining eigenvalues are stable. Using a local nonlinear mapping (normal form reduction) and Liapunov stability criteria, one can obtain the stability conditions for the degenerate reduced models in terms of the original system dynamics. The stabilizing control laws, in linear and/or nonlinear feedback forms, are then designed for both linearly controllable and linearly uncontrollable cases. The normal form transformations obtained in this paper have been verified by using code MACSYMA.     

Nonlinear heave-roll coupling and ship rolling

A nonlinear model for simulating the heave-roll motions of ships in following waves is presented. The parametric excitation is modeled by a Hill's type equation, instead of the conventional Mathieu's equation. The model includes not only the linear but also the quadratic coupling term. Instability conditions for parametrically excited rolling motions are derived using the harmonic balance method. The results are verified by numerical analyses. The effects of including the quadratic coupling term on the instability conditions and nonlinear responses are studied. The complex dynamic behaviour of the coupled system in the various instability regions is also investigated. Bifurcations of the flip, fold and pitchfork types are observed in the Poincaré mapping of the numerically simulated responses. Chaotic motions leading to boundary crises and inevitable capsize are also reported.     

Optically high transparency and light color of organosoluble polyamides containing trifluoromethyl and kink diphenylmethylene linkage

New polyamides were prepared directly from a diamine, bis[4‐(2‐trifluoromethyl 4‐aminophenoxy)phenyl] diphenylmethane, containing an electron‐withdrawing trifluoromethyl group and a kink diphenylmethylene linkage with various aromatic dicarboxylic acids having inherent viscosities ranging from 0.66 to 0.83 dL g^?1. All the polyamides showed outstanding solubility and could be easily dissolved in amide‐type polar aprotic solvents (e.g., N‐methyl‐2‐pyrrolidinone, N,N‐dimethylacetamide, and N,N‐dimethylformamide) and even dissolved in less polar solvents (e.g., pyridine, cyclohexanone, and tetrahydrofuran). The dielectric constants of the polyamide films were 3.37–3.87 (100 KHz) and decreased with an increase in the frequency, which ranged from 1 Hz to 100 KHz. A low coefficient of thermal expansion for the polyamides was observed in the range of 54–78 ppm/°C (by thermomechanical analysis). These polyamides showed excellent thermal stability, and the 10% weight loss temperatures were in the range of 484–507 °C in an atmosphere of nitrogen. The polymers had an initial modulus of 1.8–2.2 GPa. The polyamides with kink and electron‐withdrawing trifluoromethyl units afforded light‐color polymer films with high transmittance in the visible region (400–700 nm), and their cutoff wavelength was lower than 362 nm. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4559–4569, 2005     

A 2D honeycomb-shaped network based on a starburst cluster: [Ag4(micro3-Cl)(PPh2(CH2)2PPh2)1.5{S2P(OR)2}3](R = Et, Pri)

The first 2D metal-organic framework utilizing PPh2(CH2)2PPh2 (dppe) units as the linkers and tetranuclear silver clusters, [Ag4(micro3)-Cl){S2P(OR)2}3], as the network nodes in the formation of the honeycomb-shaped layer structure is reported.     

氦同位素原子与钠分子碰撞转动激发积分散射截面的理论计算

多体刚性椭球模型是一种比较精确的描述氦原子与钠分子碰撞的理论模型.本文用多体刚性椭球模型计算了不同能量下He的同位素原子3He,4He,7He,10He与Na2分子碰撞的转动激发积分散射截面,表明增加椭球等势面个数可以得到更准确的转动激发积分散射截面;总结出3He,4He,7He,10He-Na2碰撞体系转动激发积分散射截面随相对入射能量和体系约化质量变化的规律;讨论了相对入射能量为100meV时,相互作用势的不同区域对4He-Na2碰撞体系转动激发积分散射截面的影响情况.     

胃康灵胶囊中15种元素含量分析

微波消解法制备供试品,电感耦合等离子体-质谱(ICP-MS)法测定中成药胃康灵胶囊中15种元素的含量,探讨其宏量、微量元素与疗效的关系。胃康灵胶囊中常量元素含量丰富,微量元素含量差别较大,Fe含量最多,Se含量最少,有害元素含量不高。胃康灵胶囊中元素与胃炎及胃溃疡的治疗密切相关。     

Linear-cavity fiber laser using subring-cavity incorporated saturable absorber for single-frequency operation

By using a subring cavity incorporated with a saturable absorber, a stable single-frequency selection is realized in a linear-cavity fiber laser, which is constructed using a broadband fiber mirror and a partial reflectance fiber Bragg grating as the cavity ends. At 1550.33 nm, the laser has an optical signal-to-noise-ratio of >53.28 dB and with linewidth less than 1 MHz. The pumping efficiency is 25% improved by recycling the residual pump power to gain medium. The power stability and wavelength stability have also been studied.     

Real-time monitoring implementation in a remote-pumped WDM PON

We report on an improved configuration to monitor a passive optical network with high quality in service. This proposed system comprises fiber-Bragg gratings, a 1 × 4 optical switch, and an optical time-domain reflectometry to diagnose the broken point in real time. It could simultaneously detect multioptical network units in a WDM PON. The remote-pump integrated residual pumping reused function is implemented. Broken points in different optical paths can be detected simultaneously even when the distances to the central office are identical. The bit-error rate testing is verified with a small power penalty, making it an ideal solution for the real-time monitoring in a WDM PON.