Cationic para‐phenyl‐substituted α‐diimine nickel catalyzed ethylene and 4‐methyl‐1‐pentene (co)polymerizations via living/controlled chain‐walking

Upon activation with diethylaluminium chloride (Et₂AlCl), a series of phenyl‐substituted α‐diimine nickel precatalysts conducted 4‐methyl‐1‐pentene (4MP) and ethylene (E) (co)polymerizations via controlled chain‐walking to generate branched amorphous polymers with high molecular weight and narrow molecular weight distribution (M_w/M_n < 1.6). The obtained poly(4MP)s were amorphous elastomers with glass transition temperature (T_g) of ?10 ~ ?24 °C, which are higher than that of E‐4MP copolymer ( ? 63.0 °C). At room temperature (25 °C), 4MP polymerization proceeds in a living manner. The microstructures of the produced poly(4MP)s indicated the 2,1‐ and 1,2‐insertion followed by chain‐walking, the latter being predominant. The NMR analyses of the polymers showed that the obtained poly(4MP) possessed methyl, isobutyl, 2,4‐dimethylpentyl and 2‐methylhexyl groups, while the isobutyl and 2,4‐dimethylalkyl branches derived from 4MP were observed in the E‐4MP copolymer. The branch structures and the insertion‐type of monomer were depended on the polymerization temperature, and the content of methyl branch increased with an increase in the polymerization temperature.     

Stereoselective Remote Functionalization via Palladium-Catalyzed Redox-Relay Heck Methodologies

Exploration of novel, three-dimensional chemical space is of growing interest in the drug discovery community and with this comes the challenge for synthetic chemists to devise new stereoselective methods to introduce chirality in a rapid and efficient manner. This Minireview provides a timely summary of the development of palladium-catalyzed asymmetric redox-relay Heck-type processes. These reactions represent an important class of transformation for the selective introduction of remote stereocenters, and have risen to prominence over the past decade. Within this Minireview, the vast scope of these transformations will be showcased, alongside applications to pharmaceutically relevant chiral building blocks and drug substances. To complement this overview, a mechanistic summary and discussion of the current limitations of the transformation are presented, followed by an outlook on future areas of investigation.     

固体异质结界面结构预测方法及AutoInterface程序实现

预测材料异质结的界面原子结构对于理解界面对性能的影响至关重要. 目前, 从理论上预测材料界面结构仍具有极大挑战, 主要是缺乏普适有效的理论计算方法. 本文介绍了本课题组在异质结界面结构预测方面取得的最新进展. 结合马氏体相变唯象理论、 图论和随机表面行走算法, 提出了界面结构的一种有效预测方法, 可以实现自动化的计算预测. 通过GaP/TiO₂半导体异质结等展示了该方法的有效性和在催化等领域的应用前景.     

变长度弹性伸缩腿双足机器人动力学与控制

研究了半被动双足机器人的平面稳定行走的控制问题．基于弹簧质点模型，采用拉格朗日方法分别得到双足机器人单支撑阶段与双支撑阶段的动力学方程，对机器人系统的动力学方程求得周期解．应用非线性系统状态反馈线性化理论，在双足机器人的单支撑阶段和双支撑阶段中，通过控制双足机器人的腿长度，实现稳定的周期行走．在理论分析的基础上，对控制算法进行了仿真与研究．结果表明：在周期行走过程中，文中采用的变长度控制算法可以使双足机器人克服外界的干扰，并具有较强的抗干扰性．     

Precision Chain‐Walking Polymerization of trans‐4‐Octene Catalyzed by α‐Diimine Nickel(II) Catalysts Bearing ortho‐sec‐Phenethyl Groups

α‐Diimine nickel complexes bearing bulky ortho‐sec‐phenethyl groups (bis{[N,N′‐(4‐methyl‐2,6‐di‐sec‐phenethylphenyl)imino]‐1,2‐dimethylethane}dibromonickel ( 1 ), bis{[N,N′‐(4,6‐dimethyl‐2‐sec‐phenethylphenyl)imino]‐1,2‐dimethylethane}dibromonickel ( 2 ), bis{[N,N′‐(4‐methyl‐2‐sec‐phenethylphenyl)imino]‐1,2‐dimethylethane}dibromonickel ( 3 )) and {bis[N,N′‐(2,4,6‐trimethylphenyl)imino]‐1,2‐dimethylethane}dibromidonickel ( 4 ) are used as a precatalyst for the polymerization of trans‐4‐octene upon activation with modified methylaluminoxane. These catalysts conduct chain‐walking polymerization of trans‐4‐octene to give polymers possessing propyl and butyl branches with high molecular weight and narrow molecular weight distribution. The branching structure depends on the nickel complex as well as the polymerization temperature, and the ratio of propyl branch was increased with increasing the bulkiness of the ligand and decreasing the polymerization temperature. Consequently, the most bulky 1 among the complexes used is found to polymerize trans‐4‐octene with high 1,5‐regioselectivity at −20 °C to give poly(1‐propylpentan‐1,5‐diyl).

     

Bifurcation and chaos of a simple walking model driven by a rhythmic signal

The walk of animals is achieved by the interaction between the dynamics of their mechanical system and the central pattern generator (CPG). In this paper, we analyze dynamic properties of a simple walking model of a biped robot driven by a rhythmic signal from an oscillator. In particular, we examine the long-term global behavior and the bifurcation of the motion that leads to chaotic motion, depending on the model parameter values. The simple model consists of a hip and two legs connected at the hip through a rotational joint. The joint is driven by a rhythmic signal from an oscillator, which is an open loop. In order to analyze the bifurcation, we first obtained approximate solutions of the walking motion and then constructed discrete dynamics using the Poincaré map. As a result, we found that consecutive period-doubling bifurcations occur as the model parameter values change, and that the walking motion leads to chaotic motion over the critical value of the model parameters. Moreover, we approximately obtained the period-doubling solutions and the critical value by employing a Newton-Raphson method. Our analytical results were verified by the numerical simulations.     

Discriminating on dynamical stability of biped walking

In paper, a biped with 7 rigids and 12 degrees of freedom is taken as a research mould. The discriminating conditions on dynamical walking stability are derived and discussed in detail. The discriminating condition could be used to check biped motive planning and to modify it.     

基于步态切换的欠驱动双足机器人控制方法

由于高维、非线性、欠驱动等特点, 3-D双足机器人的稳定性控制依然是一个研究难点. 一些传统的控制方法, 如基于事件的反馈控制方法和PD控制方法, 抗扰动能力较弱, 鲁棒性较差. 通过观察, 人类受到外部扰动影响时, 会通过调整步态重新获得稳定性,相较之下仅依靠一个步态获得的稳定性是有限的. 受此启发, 本文针对上述问题提出一种基于步态切换的欠驱动3-D双足机器人控制方法. 首先, 以能耗最少为优化目标, 通过非线性优化方法预先设计多组不同步长、步速的步态作为参考步态, 以构建一个步态库; 然后, 通过综合考虑步态切换过程中的稳定性与能效, 建立了多目标步态切换函数; 最后, 将该步态切换函数作为优化目标, 并求解该最小化问题获得下一步的参考步态, 从而实现步态切换, 达到使用步态库?多轨迹方法来提高鲁棒性的目的. 在仿真实验中运用该步态切换控制方法, 欠驱动3-D双足机器人可实现相对高度在[-20, 20] mm内随机变化的不平整地面上行走, 而仅采用单步态控制策略则无法克服这样的外部扰动, 从而说明了基于步态切换的欠驱动双足机器人控制方法的有效性.      

双足模型步行中的倍周期步态和混沌步态现象

被动行走模型只依赖重力可以在斜坡上形成自然的周期步态.当模型参数改变时,步态随之改变.应用胞映射方法与Newton-Raphson迭代结合来获取被动行走模型周期步态的不动点,消除了迭代方法在初值选取上的随机性,并获得了模型的吸引盆.通过对不同参数的模型的仿真,讨论了参数变化对步态的影响.结果表明,转动惯量增大会导致倍周期步态到混沌步态的产生,足半径减小和质心位置降低也会导致分岔的出现. 关键词： 胞映射 双足步行 倍周期 混沌