Remote Fluorination and Fluoroalkyl(thiol)ation Reactions

Remote functionalization reactions have the power to transform a C−H (or C−C) bond at a distant position from a functional group. This Review summarizes recent advances and key breakthroughs in remote fluorination, trifluoromethylation, difluoromethylation, trifluoromethylthiolation, and fluoroalkenylation reactions. Several powerful strategies have emerged to control the reactivity and distal selectivity such as the undirected radical approach, the 1,5-hydrogen atom transfer, the metal migration, the use of distant directing groups, and the ring-opening reactions. These unconventional and predictable C−H (and C−C) functionalization transformations should allow for the preparation of a wide range of otherwise-difficult-to-access alkyl, aromatic, heteroaromatic, and structurally complex fluorides.     

Asymmetric Three‐Component Heck Arylation/Amination of Nonconjugated Cyclodienes

Substituted cyclohexylamines are becoming increasingly important in drug discovery. Asymmetric Heck insertion/amination of nonconjugated cyclodienes proceeds to give 5‐aryl cyclohexenylamines with good enantioselectivity and exclusive trans configurations. Primary and secondary anilines, indoline, and benzylamines are suitable amines. The weakly donating diphosphite Kelliphite forms a deep unsymmetrical pocket, which is essential for stereoselective anti attack of amines.     

Wound Healing Attributes of Polyelectrolyte Multilayers Prepared with Multi‐l‐arginyl‐poly‐l‐aspartate Pairing with Hyaluronic Acid and γ‐Polyglutamic Acid

Biodegradable multi‐l ‐arginyl‐poly‐l ‐aspartate (MAPA), more commonly cyanophycin, prepared with recombinant Escherichia coli contains a polyaspartate backbone with lysine and arginine as side chains. Two assemblies of polyelectrolyte multilayers (PEMs) are fabricated at three different concentration ratios of insoluble MAPA (iMAPA) with hyaluronic acid (iMAPA/HA) and with γ‐polyglutamic acid (iMAPA/γ‐PGA), respectively, utilizing a layer‐by‐layer approach. Both films with iMAPA and its counterpart, HA or γ‐PGA, as the terminal layer are prepared to assess the effect on film roughness, cell growth, and cell migration. iMAPA incorporation is higher for a higher concentration of the anionic polymer due to better charge interaction. The iMAPA/HA films when compared to iMAPA/γ‐PGA multilayers show least roughness. The growth rates of L929 fibroblast cells on the PEMs are similar to those on glass substrate, with no supplementary effect of the terminal layer. However, the migration rates of L929 cells increase for all PEMs. γ‐PGA incorporated films impart 50% enhancement to the cell migration after 12 h of culture as compared to the untreated glass, and the smooth films containing HA display a maximum 82% improvement. The results present the use of iMAPA to construct a new layer‐by‐layer system of polyelectrolyte biopolymers with a potential application in wound dressing.     

Tris(2‐aminoethyl)amine‐based ferrocene‐terminated dendrimers as burning rate catalysts for ammonium perchlorate‐based propellant decomposition

Ferrocene‐based derivatives show potential application as burning rate catalysts (BRCs) for solid composite propellants. However, migration problems of simple ferrocene‐based derivatives limit their application as BRCs in solid composite propellants. To overcome the migration problems of ferrocene‐based BRCs and to enhance the burning rate of ammonium perchlorate (AP)‐based propellants, zero‐ to second‐generation tris(2‐aminoethyl)amine‐based ferrocene‐terminated dendrimers (G0, G1 and G2) were synthesized. The structures of G0, G1 and G2 were confirmed using ¹H NMR, Fourier transform infrared and UV–visible spectroscopies. The electrochemical behavior of G0, G1 and G2 was investigated using cyclic voltammetry. It was found that G0, G1 and G2 showed redox behavior due to the presence of ferrocene and this redox behavior was diffusion controlled over the investigated scan range. The burning rate catalytic effect of G0, G1 and G2 on thermal decomposition of AP was investigated using thermogravimetry and differential thermogravimetry. G0, G1 and G2 showed good catalytic effect on the thermal decomposition of AP. Anti‐migration studies showed that migration of G0, G1 and G2 was much slower than that of 2,2‐bis(ethylferrocenyl)propane (catocene) and ferrocene.     

离子迁移忆阻混沌电路及其在语音保密通信中的应用

忆阻器是一种具有记忆功能和纳米级尺寸的非线性元件, 作为混沌系统的非线性部分, 能够使系统的物理尺寸大大减小, 同时可以得到各种丰富的非线性曲线, 提高混沌系统的复杂度和信号的随机性. 因此, 本文采用离子迁移忆阻器的磁控模型设计了一个新的混沌系统. 通过理论推导、数值仿真、Lyapunov指数谱、分岔图和Poincaré截面图研究了系统的基本动力学特性, 并分析了改变不同参数时系统动力学行为的变化. 同时, 建立了模拟该系统的SPICE电路, SPICE仿真结果与数值分析相符, 从而验证该混沌系统的混沌产生能力. 最后, 利用线性反馈同步控制方法实现了新构造的离子迁移忆阻混沌系统的同步, 并且采用该同步方法有效实现了语音信号的保密通信. 数值仿真证实了新混沌系统的存在性以及同步控制应用的可行性.     

Generation of Electrical Currents and Magnetic Fields by Grain Boundary Motion

The effect of an induced magnetic moment due to grain boundary motion in a magnetic field was studied theoretically in a microscopic and a mesoscopic approximation. It was found that the induced moment generates a drag force on the boundary, which depends on the orientation of the magnetic field with regard to the crystal axis, as observed experimentally. However, the magnitude of the theoretically predicted dependency is much smaller than experimentally observed and even opposite with regard to the orientation dependence. Therefore, the electromagnetic drag can be neglected in comparison with other driving forces for grain boundary motion, but the effect may play a role for fast moving dislocations in a magnetic field.     

三层同轴液柱内的热毛细对流的近似解析解

1引言在微重力下用浮区法生长高质量、大体积单晶体是一种很有应用前景的方法，但热毛细对流所引起的诸如宏观不均匀性、生长条纹等缺陷严重限制了这一方法的应用。目前，人们试着用液封方法抑制热毛细对流。文献［1～3］分别对两层流体系统内的热毛细对流所作的研究表明：通过液封，被封层内的热毛细对流可以得到显著抑制。本文对圆柱三层流体系统内的热毛细对流进行研究，为热毛细对流规律的揭示以及进一步总结出其控制方法提供了理论数值依据。2控制方程和边界条件考虑长为L的互不溶混的三层轴对称同轴液柱，如图1所示，两端壁保持定温T…     

市场潜能、预期收入与跨省人口流动——基于空间计量模型的分析

综合新经济地理学模型与迁移效应函数,本文构建了包含市场潜能和预期收入的人口迁移理论模型,并采用空间计量模型及其稳健性检验进行了中国数据的实证分析。研究结果表明:市场潜能和预期收入及其空间溢出效应对人口迁入有显著的促进作用,但是两者对人口迁移的作用路径不同,市场潜能仅对本地区有直接正向作用,对相邻地区的空间溢出效应不明显,相邻地区则对本地区的人口迁移存在负向反馈效应;而预期收入对本身以及相邻地区的影响为正向,相邻地区的预期收入反馈效应也为正;地区的人口密度和消费水平则对人口迁移有显著的负向作用。     

Theoretical study on the mechanism of thieno[3,2‐b]benzofuran bromination: the importance of Lewis and non‐Lewis type NBOs interactions along the reaction path

A density functional theory study has been performed to estimate the electrophilic thieno[3,2‐b]benzofuran bromination reaction. Optimized structures for all stationary points were examined by employing the B3LYP and BMK at the 6‐31++G(d,p), 6‐311G(d,p), and 6‐311++G(d,p) levels of theory. The solvent polarity has a significant effect on a reduction of activation energies barriers. The reaction involves the formation of a triangle complex, migration of a proton through the bromine moiety followed by ionization of the bromine bond, and activation to the σ‐complex. Finally, the σ‐complex transforms into the reaction products. The natural bond orbital (NBO) population analysis was performed along the reaction minimal energy path defined as a function of the intrinsic reaction coordinate (IRC). The evolution of interaction energies between filled and empty NBOs along IRC has been estimated. The importance of these interactions for the disruption of Br?Br and C?H bonds and creation of C?Br and H?Br bonds have been emphasized. The changes in NBOs hybridization, covalency effects, electrostatic potential density maps, and occupancy of natural bonds have been investigated along IRC. The results obtained explain well the essence of bonding transformations and electron density changes during the reaction. Copyright © 2015 John Wiley & Sons, Ltd.     

强磁场条件下金属凝固过程中第二相的迁移行为

理论分析表明,第二相的迁移行为可以通过迁移速度进行表征.影响迁移速度的因素包括第二相和熔体的物理性质、磁场强度和梯度大小、第二相的形状和体积等因素.强磁场下洛伦兹力的效果为促进第二相在基体中的均匀分布,其效率在磁场强度大于某一定值时逐渐降低.在梯度强磁场条件下,第二相迁移行为和分布状态的主要控制参数是梯度磁场下的磁化力.在磁场梯度较小时,因洛伦兹力的制约磁化力控制第二相迁移的效果不明显,随着磁场梯度的增加,磁化力的作用效果逐渐增强.通过研究强磁场下Al-Si合金、Al-Ni合金中原位自生第二相的迁移行为实 关键词： 强磁场 迁移 第二相 凝固