Synthesis of Poly(Arylene Alkenylene)s by Pd‐Catalyzed Three‐Component Coupling Polycondensation of Diiodoarenes,Non‐Conjugated Dienes,and Nucleophiles that Involves Chain Walking Isomerization

The Pd‐catalyzed three‐component coupling polycondensation of diiodoarenes, nonconjugated dienes, and carbonucleophiles afforded poly(arylene alkenylene)s with moderate molecular weight in good yield. The reaction involves Mizoroki‐Heck coupling, olefin migration via chain walking, and addition of the carbonucleophile to the resulting π‐allylpalladium species. The polymerization with a slight excess of nucleophile with respect to diiodoarene also proceeded to give the polymer without significant decrease in molecular weight in spite of the nonstoichiometric mixture of the monomers. The Pd‐catalyzed three‐component coupling polycondensation of diiodoarenes, nonconjugated dienes, and diimide also proceeded. The base used in the reaction is critical for yield and molecular weight of the product. The reaction using NaHCO₃ afforded the product with low solubility, which can be explained by the high molecular weight of the polymer and/or the strong interaction of the electron donating dimethoxyphenylene groups and electron accepting diimide groups in the polymer. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2535–2542     

儿童倒走足底压力的分布特征研究

为探讨倒走锻炼相对于正常向前行走在足底压力分布方面的特征,对12名 健康男性小学生正、倒走足底压力分布进行采集. 然后对足底10个区的最大压力和冲量进行 分析. 结果表明,儿童正、倒走足底压力分布差异明显. 与正走相比,倒走时足弓、 第4,5趾骨区的压力均变为较高压力区域,而大拇指、第1,2趾骨区变为较低压力区域. 该结果提 示,倒走足底压力分布特征可能是倒走所具有的锻炼、康复特殊效果主要原因之一.     

New chiral α‐diimine nickel(II) complexes bearing ortho‐sec‐phenethyl groups for ethylene polymerization

A series of new α‐diimine nickel(II) catalysts bearing bulky chiral sec‐phenethyl groups have been synthesized and characterized. The molecular structure of representative chiral ligand, bis[N,N′‐(4‐methyl‐2,6‐di‐sec‐phenethylphenyl)imino]‐1,2‐dimethylethane rac‐1c and chiral complexes, {bis[N,N′‐(4‐methyl‐2‐sec‐phenethylphenyl)imino]‐2,3‐butadiene}dibromidonickel rac‐2a and bis{bis[N,N′‐(4‐methyl‐2‐sec‐phenethylphenyl)imino]‐2,3‐butadiene}dibromidonickel rac‐2b, were confirmed by X‐ray crystallographic analysis. Complex rac‐2c bearing two chiral sec‐phenethyl groups in the ortho‐aryl position and a methyl group in the para‐aryl position, activated by diethylaluminum chloride (DEAC), showed highly catalytic activity for the polymerization of ethylene [4.12 × 10⁶ g PE (mol Ni.h.bar)^?1], and produced highly branched polyethylenes under low ethylene pressure (branching degree: 104, 118 and 126 branches/1000 C at 20, 40 and 60°C, respectively). Chiral 20‐electron bis‐α‐diimine Ni(II) complex rac‐2b also exhibited high activity toward ethylene polymerization [1.71 × 10⁶ g PE (mol Ni · h · bar)^?1]. The type and amount of branches of the polyethylenes obtained were determined by ¹H and ¹³C NMR. Copyright © 2013 John Wiley & Sons, Ltd.     

摩擦与滚阻对被动行走器步态影响的研究

本文研究了圆弧足被动行走器支撑足与地面间的摩擦系数和滚阻系数对被动行走器步态的影响. 首先分别利用扩展的 赫兹接触力模型和LuGre摩擦模型描述了支撑足与地面接触点处的法向支撑力和切向摩擦力,并考虑了行走过程中支撑足 所受的滚动摩阻;其次利用第二类Lagrange方程推导出了该系统的动力学方程,并通过与已有成果的对比确定 了合适的LuGre摩擦模型参数;最后仿真分析了摩擦系数和滚阻系数对被动行走器步态的影响. 研究发现:摩擦系数的改变 虽然对被动行走器行走的平均速度、步幅,以及支撑足接触点处的最大法向接触力的影响较小,但摩擦系数的减小 会改变其行走步态类型,如发生倍周期分岔甚至混沌现象;然而,滚阻系数的改变会对行走器行走的 平均速度、步幅,以及支撑足接触点处的最大法向接触力的影响较大,尚未发现滚阻系数的改变会引起其行走步态的变化.      

Self-stability of a simple walking model driven by a rhythmic signal

In this paper, we analyzed the dynamic properties of a simple walking model of a biped robot driven by a rhythmic signal from an oscillator. The oscillator receives no sensory feedback and the rhythmic signal is an open loop. The simple model consists of a hip and two legs that are connected at the hip. The leg motion is generated by a rhythmic signal. In particular, we analytically examined the stability of a periodic walking motion. We obtained approximate periodic solutions and the Jacobian matrix of a Poincaré map by the power-series expansion using a small parameter. Although the analysis was inconclusive when we used only the first order expansion, by employing the second order expansion it clarified the stability, revealing that the periodic walking motion is asymptotically stable and the simple model possesses self-stability as an inherent dynamic characteristic in walking. We also clarified the stability region with respect to model parameters such as mass ratio and walking speed.     

A Note on a Walking Machine Model

The paper continues studies intended to find out whether it is possible to create a prototype walking machine with relatively simple components. In this connection, the control problem is solved for a two-dimensional model of biped machine. It has a torso and two telescopic legs. Each leg includes a ponderable section of constant length and an imponderable section of variable length. The machine, regarded as a system with variable constraints, implements a single-stance gait (one stance leg at a time) with a step of constant duration. The contact of the swing leg with the ground is analyzed within the framework of Carnot's theorem (perfectly inelastic impact). It is assumed that the force developed in the stance leg is due to the deformation of the leg's spring and that this deformation can be controlled. An algorithm is proposed to synthesize a control system that takes into account collisions occurring at reverse of the roles of the legs. This algorithm is based on methods of optimizing periodic systems. The algorithm is compared with approaches used by other authors     

一种新型多功能助行器

本文介绍一种新型多功能助行器的设计,以及分析新型助行器在未来的发展前景及市场前景。     

Optimal Frequency and Amplitude of Vertical Viewpoint Oscillation for Improving Vection Strength and Reducing Neural Constrains on Gait

Inducing self-motion illusions referred as vection are critical for improving the sensation of walking in virtual environments (VE). Adding viewpoint oscillations to a constant forward velocity in VE is effective for improving vection strength under static conditions. However, the effects of oscillation frequency and amplitude on vection strength under treadmill walking conditions are still unclear. Besides, due to the visuomotor entrainment mechanism, these visual oscillations would affect gait patterns and be detrimental for achieving natural walking if not properly designed. This study was aimed at determining the optimal frequency and amplitude of vertical viewpoint oscillations for improving vection strength and reducing gait constraints. Seven subjects walked on a treadmill while watching a visual scene. The visual scene presented a constant forward velocity equal to the treadmill velocity with different vertical viewpoint oscillations added. Five oscillation patterns with different combinations of frequency and amplitude were tested. Subjects gave verbal ratings of vection strength. The mediolateral (M-L) center of pressure (CoP) complexity was calculated to indicate gait constraints. After the experiment, subjects were asked to give the best and the worst oscillation pattern based on their walking experience. The oscillation frequency and amplitude had strong positive correlations with vection strength. The M-L CoP complexity was reduced under oscillations with low frequency. The medium oscillation amplitude had greater M-L CoP complexity than the small and large amplitude. Besides, subjects preferred those oscillation patterns with large gait complexity. We suggested that the oscillation amplitude with largest M-L CoP complexity should first be chosen to reduce gait constraints. Then, increasing the oscillation frequency to improve vection strength until individual preference or the boundary of motion sickness. These findings provide important guidelines to promote the sensation of natural walking in VE.     

Chip‐based nanoelectrospray ionization with Fourier transform mass spectrometric detection to screen for local anesthetics intended to mask limb sore in walking horses

We report a high‐throughput chip‐based nanoelectrospray ionization method coupled with Fourier transform mass spectrometry to screen for local anesthetics in samples collected by swabbing. These drugs have been used to mask pain on the limbs of walking horses after forbidden practices of soring or physical abuse. Optimized for lidocaine, the method afforded sub‐ppm mass accuracy for nine local anesthetics included in the study. From doped cotton swabs, two third and all of the analytes were detected after adding 10 ng and 100 ng of each drug, respectively. Benzocaine and/or lidocaine were found on positive swab samples collected during walking horse competitions. Copyright © 2015 John Wiley & Sons, Ltd.     

Directed Evolution of RebH for Site‐Selective Halogenation of Large Biologically Active Molecules

We recently characterized the substrate scope of wild‐type RebH and proceeded to evolve variants of this enzyme with improved stability for biocatalysis. The substrate scopes of both RebH and the stabilized variants, however, are limited primarily to compounds similar in size to tryptophan. A substrate walking approach was used to further evolve RebH variants with expanded substrate scope. Two particularly notable variants were identified: 3‐SS, which provides high conversion of tricyclic tryptoline derivatives; and 4‐V, which accepts a broad range of large indoles and carbazoles. This constitutes the first reported use of directed evolution to enable the functionalization of substrates not accepted by wild‐type RebH and demonstrates the utility of RebH variants for the site‐selective halogenation of biologically active compounds.