Synthesis and magnetic properties of organic multilayer films based on the layer‐by‐layer assembly

Two polymers containing pyridine rings were prepared by free‐radical polymerization and confirmed by Fourier transform infrared and ¹H NMR spectra. The preparation of four multilayer films that were obtained by self‐assembly of the polymer and the transition metal neutralized polyelectrolyte on PE substrate was described. UV–vis spectra and atomic force microscopy images were applied to characterize these films and indicate the uniform assembling process. The driving force for building up the multilayer films was identified by infrared spectroscopy to be the coordination interaction. The magnetic behavior was examined as a function of magnetic field strength at 30 kOe and as a function of temperature (5–300 K). All films display strong soft ferromagnetic properties and higher than those of the bulk materials. The magnetic results show that the layer‐by‐layer self‐assembling approach is beneficial to the ordered alignment of adjacent paramagnetic spins and induces better magnetic phenomena. Copyright © 2015 John Wiley & Sons, Ltd.     

One‐Pot Cannizzaro Cascade Synthesis of ortho‐Fused Cycloocta‐2,5‐dien‐1‐ones from 2‐Bromo(hetero)aryl Aldehydes

An intramolecular Cannizzaro‐type hydride transfer to an in situ prepared allene enables the synthesis of ortho‐fused 4‐substituted cycloocta‐2,5‐dien‐1‐ones with unprecedented technical ease for an eight‐ring carboannulation. Various derivatives could be obtained from commercially available (hetero)aryl aldehydes, trimethylsilylacetylene, and simple propargyl chlorides in good yields.     

Trimethylaluminum: Bonding by Charge and Current Topology

The charge density distribution of the trimethylaluminum dimer was determined by high‐angle X‐ray diffraction of a single crystal and quantum‐chemical methods and analyzed using the quantum theory of atoms in molecules. The data can be interpreted as Al₂Me₆ being predominantly ionically bonded, with clear indications of topological asymmetry for the bridging Al? C bonds owing to delocalized multicenter bonding. This interpretation is supported by the calculated magnetic response currents. The data shed new light on the bonding situation in this basic organometallic molecule, which was previously described by contradicting interpretations of bonding.     

Isotactic rac‐Lactide Polymerization with Copper Complexes: The Influence of Complex Nuclearity

Diiminopyrrolide copper alkoxide complexes, LCuOR (OR¹=N,N‐dimethylamino ethoxide, OR²=2‐pyridyl methoxide), are active for the polymerization of rac‐lactide at ambient temperature in benzene to yield polymers with M_w/M_n=1.0–1.2. X‐ray diffraction studies showed bridged dinuclear complexes in the solid state for both complexes. While LCuOR¹ provided only atactic polylactide, LCuOR² produced partially isotactic polylactide (P_m=0.7). The difference in stereocontrol is attributed to a dinuclear active species for LCuOR² in contrast to a mononuclear species for LCuOR¹.     

Synthesis of Carbazole Alkaloids by Ring‐Closing Metathesis and Ring Rearrangement–Aromatization

Aprocess for the assembly of carbazole alkaloids has been developed on the basis of ring‐closing metathesis (RCM) and ringrearrangement–aromatization (RRA) as the key steps. This method is based on allyl Grignard addition to isatin derivatives to provide smooth access to 2,2‐diallyl 3‐oxindole derivatives through a 1,2‐allyl shift. The diallyl derivatives were used as RCM precursors to afford a novel class of spirocyclopentene‐3‐oxindole derivatives, which underwent a novel RRA reaction to afford carbazole derivatives. The synthetic sequence to carbazoles was shortened by combining the RCM and RRA steps in an orthogonal tandem catalytic process. The utility of this methodology was further demonstrated by the straightforward synthesis of carbazole alkaloids, including amukonal derivative, girinimbilol, heptaphylline, and bis(2‐hydroxy‐3‐methylcarbazole).     

机抖激光陀螺随机噪声注入方法研究

机抖激光陀螺通过在抖动驱动信号中注入一定强度的随机噪声来消除动态闭锁误差.为了适应机抖激光陀螺小型化和其控制电路数字化的发展,设计了在以抖动驱动信号采用方波形式的基础上,其随机噪声的注入采取了应用寄存器产生的伪随机噪声-m序列按照对方波占空比进行调制的方式,并建立了抖动机构的数学模型,应用所建立的模型通过Matlab中的Simulink进行了仿真.依照随机噪声注入效率的计算方法,文中采用的方式其噪声注入效率要高于以往采用的应用高斯白噪声对交变正弦波驱动信号进行幅值调制的方式,对此进行了实验验证,证明这种随机噪声注入方式效果良好.     

试验确定自增强圆筒的表面裂纹K1因子和疲劳扩展规律

本文提供了一种可以进行自增强处理的圆筒试样,通过实验用柔度法确定了该试样的表面裂纹的应力强度因子,介绍了含表面裂纹试样的柔度测试技术,导出了柔度与表面裂纹尖端前缘各点的应力强度因子的关系式,该式可作为各种含表面裂纹试样柔度法测表面裂纹 K_1因子的参考,本文还测定了不同自增强程度下,自增强圆筒的表面裂纹疲劳扩展规律。