Association and Dissociation of Grignard Reagents RMgCl and Their Turbo Variant RMgCl⋅LiCl

Grignard reagents RMgCl and their so‐called turbo variant, the highly reactive RMgCl?LiCl, are of exceptional synthetic utility. Nevertheless, it is still not fully understood which species these compounds form in solution and, in particular, in which way LiCl exerts its reactivity‐enhancing effect. A combination of electrospray‐ionization mass spectrometry, electrical conductivity measurements, NMR spectroscopy (including diffusion‐ordered spectroscopy), and quantum chemical calculations is used to analyze solutions of RMgCl (R=Me, Et, Bu, Hex, Oct, Dec, iPr, tBu, Ph) in tetrahydrofuran and other ethereal solvents in the absence and presence of stoichiometric amounts of LiCl. In tetrahydrofuran, RMgCl forms mononuclear species, which are converted into trinuclear anions as a result of the concentration increase experienced during the electrospray process. These trinuclear anions are theoretically predicted to adopt open cubic geometries, which remarkably resemble structural motifs previously found in the solid state. The molecular constituents of RMgCl and RMgCl?LiCl are interrelated via Schlenk equilibria and fast intermolecular exchange processes. A small portion of the Grignard reagent also forms anionic ate complexes in solution. The abundance of these more electron‐rich and hence supposedly more nucleophilic ate complexes strongly increases upon the addition of LiCl, thus rationalizing its beneficial effect on the reactivity of Grignard reagents.     

Thermal Behavior of Polypropylene-g-glycidyl Methacrylate Prepared by Melt Grafting

The thermal behaviors of glycidyl methacrylate (GMA)-grafted polypropylene (PP) (PP-g-GMA) with two different grafting degrees, namely, GPP1 and GPP2, were investigated by differential scanning calorimetry (DSC), polarized optical microscopy (POM), wide-angle X-ray diffraction (WAXD), dynamic mechanical analysis (DMA), and thermogravimetrical analysis (TGA). DSC results suggested that the GMA grafted PP exhibited higher crystallization temperature T_c, higher melting temperature T_m, and higher crystallinity compared with the neat PP. The isothermal crystallization kinetics was analyzed with the Avrami equation and the total crystallization activation energy was calculated. It was concluded that the crystallization processes of PP and the grafted PP were controlled by nucleation and the values of the crystallization activation energy of PP and the grafted PP were almost identical. POM results suggested that the GMA grafted PP exhibited smaller spherulites size compared with the neat PP. WAXD patterns indicated that the neat PP encouraged the formation of γ phase, compared with the grafted PP, during the crystallization process. DMA results showed that melt grafting did not induce a clear effect on the γ-transition and β-transition of the amorphous phase but resulted in a decrease in mobility of the PP chains in the crystals. TGA curves suggested that the melt grafting slightly improved the thermal stability of PP.     

D-admissible hybrid control of a class of singular systems

This paper mainly studies the problem of designing a hybrid state feedback D-admissible controller for a class of linear and nonlinear singular systems. Based on the relationship between singular discrete systems and singular delta operator systems, several necessary and sufficient conditions for a linear singular delta operator system to be D-admissible (i.e. regular, causal and all finite poles lie in a prescribed circular region) with different representations are derived. Then, the existence conditions and explicit expressions of a desirable D-admissible controller are given by means of matrix inequalities and strict linear matrix inequalities, respectively. We further extend the obtained results to singular delta operator systems with Lipschitz nonlinear perturbations, and the design methods of hybrid controller are presented for the nonlinear case as well. Finally, numerical examples as well as simulations are provided to illustrate the effectiveness of the theoretical outcomes obtained in the paper.     

基于ip-iq法的并联有源滤波器在微网中的应用

首先分析了基于三相瞬时无功理论的ip-iq谐波电流检测法的基本原理,将基于ip-iq法的并联有源滤波器应用于微网系统,分析有源滤波器的控制方式,并在SIMULINK中建立接有非线性负载的微电网模型,对其基波电流、谐波电流、电网电流和负载电流进行检测分析,计算电流畸变率,以证明基于ip-iq谐波电流检测法的并联有源滤波器在微网中应用的可行性。     

基于Minim OSD的水质采样船状态反馈的研究与实现

APM是国外的一个飞控系统,由于是完全开源的,因此受到广大航模爱好者的喜爱。 Minim OSD是APM系统专用的作为人机交互的视频显示模块,其在整个飞控系统中显得尤为重要。本文介绍了Minim OSD的工作原理并根据它的工作原理介绍了一种方法,将其成功移植到水质采样船中,来实现采样船各状态的反馈。     

一种筛选电网脆弱节点的新方法

为了快速有效的确定电网的脆弱节点,提出了一种利用多种指标综合筛选电力系统脆弱节点的方法。首先通过绘制出系统各负荷节的 PV,QV 曲线,求取各负荷节点的电压变化指标和无功功率裕度指标;随后将这两种指标进行综合,用于判断电力系统脆弱节点。通过设置不同的权重系数可以实现不同情况下的脆弱节点判断。并将此方法应用于实际电网,将得出的脆弱节点分析结果与通过传统的模态分析法得出的结果进行比较,证明了此方法在筛选系统脆弱节点方面的正确性与有效性。     

反应性液晶修饰的光敏聚芳醚光取向稳定性研究

采用反应性液晶通过光聚合反应与聚芳醚光取向膜复合方法,制备了平面转换(In-plane switching,IPS)液晶显示器件,并在高温状态下对其光电显示和取向稳定性能进行了研究。结果显示,与单一聚芳醚光取向膜相比,利用复合光取向膜制备的IPS器件在高温状态下的光电显示和液晶取向稳定性能都得到了明显提高,在65℃明亮显示20h无液晶取向变化,在120℃维持2h无明显光量渗透。在线偏振紫外光下,光敏聚芳醚薄膜发生各向异性光交联反应,其交联程度最高可达67.4%。SEM分析结果发现,反应性液晶单体在UV光照射下,在聚芳醚光取向膜表面上发生了各向异性光聚合反应,沿先前光取向方向形成长度为0.4μm左右的棒状聚合物,有效限制了光取向膜中未交联的柔性基团的活动能力,进而有效增强了复合取向膜对液晶的取向稳定性。     

电信运营商基于大数据的业务模式分析

随着4G网络的大规模商用,移动互联网、物联网蓬勃发展,人们的行为、位置、甚至身体生理数据等每一点变化都成为了可被记录和分析的数据,这使电信运营商面临着不小的机遇和挑战。在综述大数据时代电信运营商所面临的主要机遇的基础上,分析了电信运营商在大数据应用方面的相对优势,介绍了数据挖掘及平台架构,探讨了电信运营商基于大数据的业务模式,以推进相关技术和应用,提升客户感知,支撑流量经营。     

一种提高部分反馈预编码MIMO系统安全性能方案

MIMO(Mutiple-In Mutiple-Out,多输入多输出)技术是无线移动通信领域智能天线技术的重大突破。无线通信的广播特性容易引起信息泄露,开展研究提高无线通信网络安全性能的课题十分必要。目前,MIMO系统中的预编码技术已成为无线通信领域的研究热点。本文将介绍一种加密技术控制下通过旋转码本提高预编码系统安全性能的方案。通过仿真,验证了该方案可以使无线通信可靠性接近1,并且该方案的设计思想可以推广到其他预编码系统中。