Diphosphine Ligand-Enabled Nickel-Catalyzed Chelate-Assisted Inner-Selective Migratory Hydroarylation of Alkenes

The precise control of the regioselectivity in the transition metal-catalyzed migratory hydrofunctionalization of alkenes remains a big challenge. With a transient ketimine directing group, the nickel-catalyzed migratory β-selective hydroarylation and hydroalkenylation of alkenyl ketones has been realized with aryl boronic acids using alkyl halide as the mild hydride source for the first time. The key to this success is the use of a diphosphine ligand, which is capable of the generation of a Ni(II)-H species in the presence of alkyl bromide, and enabling the efficient migratory insertion of alkene into Ni(II)-H species and the sequent rapid chain walking process. The present approach diminishes organosilanes reductant, tolerates a wide array of complex functionalities with excellent regioselective control. Moreover, this catalytic system could also be applied to the migratory hydroarylation of alkenyl azahetereoarenes, thus providing a general approach for the preparation of 1,2-aryl heteroaryl motifs with wide potential applications in pharmaceutical discovery.     

Rare Earth Evoked Subsurface Oxygen Species in Platinum Alloy Catalysts Enable Durable Fuel Cells

Alleviating the degradation issue of Pt based alloy catalysts, thereby simultaneously achieving high mass activity and high durability in proton exchange membrane fuel cells (PEMFCs), is highly challenging. Herein, we provide a new paradigm to address this issue via delaying the place exchange between adsorbed oxygen species and surface Pt atoms, thereby inhibiting Pt dissolution, through introducing rare earth bonded subsurface oxygen atoms. We have succeeded in introducing Gd−O dipoles into Pt₃Ni via a high temperature entropy-driven process, with direct spectral evidence attained from both soft and hard X-ray absorption spectroscopies. The higher rated power of 0.93 W cm⁻² and superior current density of 562.2 mA cm⁻² at 0.8 V than DOE target for heavy-duty vehicles in H₂-air mode suggest the great potential of Gd−O−Pt₃Ni towards practical application in heavy-duty transportation. Moreover, the mass activity retention (1.04 A mg_Pt⁻¹) after 40 k cycles accelerated durability tests is even 2.4 times of the initial mass activity goal for DOE 2025 (0.44 A mg_Pt⁻¹), due to the weakened Pt−O_ads bond interaction and the delayed place exchange process, via repulsive forces between surface O atoms and those in the sublayer. This work addresses the critical roadblocks to the widespread adoption of PEMFCs.     

New bosonic excitation operators in many-electron wave functions

New excitation operators which have perfect bosonic symmetry are constructed for many-electron wave functions by regarding the system of many electrons as that of many species of bosons. Any electronic configurations can be generated by the new bosonic “void” operators. A coherent state is constructed with the bosonic operators and is adopted as a trial function for the time-dependent variational principle. The equation of motion which has exactly the same form as Hamilton's equation in classical mechanics is obtained with the complex variational parameters, the number of which is equal to the number of electrons. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 67: 71–75, 1998     

STOCHASTIC VIBRATION CONTROL BASED ON PIEZOELECTRIC STACK INERTIAL ACTUATOR1)

本文主要研究了基于压电叠堆惯性作动器的随机振动控制方法并分析了控制力时滞对控制效果的影响规律。首先,对压电叠堆惯性作动器的动力学特性进行分析,建立了考虑惯性作动器动力学的主结构的随机动力学模型;接着,提出主结构随机振动 "线性"二次高斯控制(linear quadratic Gaussian,LQG)方法,并探讨了作动器惯性质量和刚度等对控制效果的影响规律;最后,研究了控制力时滞对控制效果的影响,并提出了利用时滞优化控制效果的方法。研究结果表明,压电叠堆惯性作动器对结构的随机振动具有较好的控制效果,当控制时滞时间$\tau = 0.025$s时控制效果可以得到进一步优化。     

考虑周长约束的圆柱薄壳初始几何缺陷随机场建模方法

利用随机场对圆柱薄壳结构的初始几何缺陷进行建模,并据此建立了一种用于含初始几何缺陷轴压圆柱薄壳屈曲分析的随机分析方法。首先,指出已有将圆柱薄壳初始几何缺陷表征为二维高斯随机场的方法会导致与实际不相符的初始几何缺陷,如圆柱周长显著增大或缩小的几何缺陷。其次,提出一种考虑周长不变约束的随机场建模方法,以剔除与实际不相符的随机几何缺陷。最后,基于所建立的初始几何缺陷随机场模型,利用非干涉多项式混沌展开法进行圆柱薄壳的随机屈曲分析,给出临界屈曲载荷的概率分布。数值试验结果表明,基于随机场理论的初始几何缺陷建模方法可有效刻画几何缺陷对结构承载能力的影响,而提出的约束随机场建模方法又能有效减小结果的分散性。     

Some pansystems studies on panchaos and strange panattractor

Paper [1] discussed the relations among panchaos and strange panattractor and pansystems operators. Paper [2] gave the applications of the fixed-point pansystems theorems to these typical nonlinear problems. In this paper, we firstly present several concepts: increasing relation, maximal panchaos, etc., and discuss the relations among them. We also discuss the problems when two increasing relations have the same panchaos and when panchaos of g is panchaos of g^t as well.     

利用特征光谱荧光标记与高斯拟合分析水体中有机物的特性

讨论了一种自然水体中有机物的快速分析方法,以激光诱导荧光(LIF)方法测量了水体的总荧光光谱(TLS);利用特征光谱荧光标记(SFS)技术对水体中溶解有机物(DOM)及叶绿素a(Chl a)的荧光光谱进行了正确的指认和提取。以最小二乘法-Gaussian拟合对水体的TLS进行了拟合,可有效地分离出拉曼散射及荧光光谱,拟合的相关系数优于0.996 4。结果表明,通过在TLS中利用SFS技术正确的指认特定污染物,并以Gaussian拟合进行有效地提取,可以进行水体污染物的快速、实时和在线监测。     

克尔效应对高斯光束聚焦特性的影响

利用菲涅尔—基尔霍夫衍射积分公式,研究薄片近似情况下的Kerr效应带来的波前畸变对高斯光束聚焦特性的影响.在相位延迟为－2~2 rad的范围内进行的模拟计算表明：正Kerr效应能提高高斯光束的聚焦强度、增大相对焦移量、提高聚焦光束的焦平面桶中功率和降低几何焦平面的峰值光强;而负Kerr效应,则会降低聚焦强度、增大相对焦移量、降低聚焦光束的焦平面桶中功率和几何焦平面的峰值光强.可以通过增大光束菲涅尔数来抑制Kerr效应对聚焦特性的影响.     

高斯光束照射下的等倾双光束干涉

根据等倾干涉原理,对高斯光束经薄膜反射后的光强、可见度、条纹分布进行了理论分析,讨论了入射角对光强、可见度分布的影响,相位角对条纹可见度的影响.数值模拟计算表明：沿着垂直于光传播方向的平面,反射光束叠加区域为一圆斑,随着入射角的增大,可见度逐渐减小,光强分布偏离了高斯分布,光斑变大,峰值减小.干涉条纹在空间的分布类似于平面波的薄膜等倾干涉,主要由入射角及薄膜厚度决定.     

空气隙偏光镜对单模高斯光束光强分布影响的分析

根据光在格兰泰勒棱镜和格兰傅科棱镜空气隙胶合层中的干涉效应,分析了空气隙偏光棱镜对单模高斯光束光强分布的影响;结果表明:对于某一波长的入射光,当空气隙的厚度一定时,透射光强随光在空气隙介面上入射角的变化作周期性振荡;当入射角一定时,透射光强随空气隙厚度的变化作周期性变化;且透射高斯光束的形状也随光的入射角以及空气隙厚度的改变发生变化;且无论是透射光强的周期性振荡,还是透射高斯光束的形状的变化,格兰泰勒棱镜的影响均小于格兰傅科棱镜;这说明前者的综合性能优于后者。