Mechanistic Study of Unprecedented Highly Regioselective Hydrocyanation of Terminal Alkynes: Insight into the Origins of the Regioselectivity and Ligand Effects

Density functional theory (DFT) calculations were performed to gain insight into the mechanism of the nickel-catalyzed hydrocyanation of terminal alkynes with Zn(CN)₂ and water to exclusively generate the branched nitrile with excellent Markovnikov selectivity. After precatalyst activation to give the LNi(0) active species, the transformation proceeds via the following steps: (1) oxidative addition of H₂O to the LNi(0) provides the intermediate LNi(II)H(OH); (2) ligand exchange of LNi(II)H(OH) with Zn(CN)₂ gives the intermediate LNi(II)H(CN); (3) alkyne insertion to the LNi(II)H(CN) forms the alkenyl nickel complex, followed by the reductive elimination step reaching the final product. This mechanism is kinetically and thermodynamically more favorable than that of the experimental proposed ones. On the basis of the experimental observations, more water molecules cannot further improve the reaction as it has also been rationalized. Furthermore, the origin of the high regioselectivity of the product, the variable effectiveness of the metal mediator as function of ligands, as well as the high yield of the alkyl-substituted alkynes substrates, is analyzed in detail. © 2019 Wiley Periodicals, Inc.     

A Single‐Atom Manipulation Approach for Synthesis of Atomically Mixed Nanoalloys as Efficient Catalysts

Synthesis of well‐defined atomically mixed alloy nanoparticles on desired substrates is an ultimate goal for their practical application. Herein we report a general approach for preparing atomically mixed AuPt, AuPd, PtPd, AuPtPd NAs(nanoalloys) through single‐atom level manipulation. By utilizing the ubiquitous tendency of aggregation of single atoms into nanoparticles at elevated temperatures, we have synthesized nanoalloys on a solid solvent with CeO₂ as a carrier and transition‐metal single atoms as an intermediate state. The supported nanoalloys/CeO₂ with ultra‐low noble metal content (containing 0.2 wt % Au and 0.2 wt % Pt) exhibit enhanced catalytic performance towards complete CO oxidation at room temperature and remarkable thermostability. This work provides a general strategy for facile and rapid synthesis of well‐defined atomically mixed nanoalloys that can be applied for a range of emerging techniques.     

基于夹层氮化硅波导的可见-中红外超连续谱特性研究

提出一种低厚度氮化硅-蓝宝石-氮化硅夹层波导结构。利用其色散波辐射现象和中红外相位匹配条件,结合波导脉冲传输模型,讨论了夹层波导不同物理尺寸对相位匹配点和光谱展宽的影响,数值模拟获得了0.5~4 μm的超连续谱展宽,并且在-40 dB水平下具有更远中红外色散波产生。通过该模型,详细解释了非线性波导脉冲传输的潜在机制。理论模型分析表明,通过优化氮化硅及蓝宝石夹层的物理尺寸,进而改变相位匹配条件,可以在较宽的波长范围内控制色散波的位置。     

Fracture Prediction for an Advanced High-Strength Steel Sheet Using the Fully Coupled Elastoplastic Damage Model with Stress-State Dependence

In this study,the numerical simulations of sheet metal forming processes are performed based on a fully coupled elastoplastic damage model.The effects of stress...     

Effects of nuclear charge fluctuations on dilepton photoproduction

Fluctuations of dilepton production from two photon interactions γγ→l~+l~- are studied in semicentral and peripheral nuclear collisions.Based on the Weizsacker-Williams approach,electromagnetic(EM) fields generated by moving nuclear charges are approximated as quasi-real photons.As fluctuating EM fields in each collision event are hard to be measured directly in experiments due to its short lifetime,we study the dilepton photoproduction with fluctuating EM fields,which are crucial for the EM fields induced chiral and charged particle evolutions,and calculate the relative standard deviation of the dilepton mass spectrum with the event-by-event fluctuating nuclear charge distributions.This fluctuation effect becomes smaller in more peripheral collisions where the shift of proton positions is implicit for EM fields outside the nucleus.The uncertainty of effective impact parameter △b on the standard deviation is also studied,and its effect is around one-third of the effect of nuclear charge fluctuations when △b is taken as～1 fm.     

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Based on the structure design and characteristics of the sealing welding of tritium-breeding blanket cap runner, the ultrasonic microscopic detection technology is studied. The testing parameters and the applicability of the method are determined. The JSR DPR500 ultrasonic microscopic detection system is selected to study the testing parameters. The characteristics of the probe parameters and the focus of the sound beam in the ultrasonic microscopy detection are analyzed. Different parameters and water layer thicknesses are used to improve the detection sensitivity. The problem that the small defects in the sealing welding of cap runner are difficult to detect is solved.     

高碘酸氧化法快速测定进口粗甘油中甘油含量

建立了高碘酸氧化法快速测定进口粗甘油中甘油含量的分析方法。对高碘酸钠加入量、溶液pH值和放置时间等主要影响因素进行了考察。经试验确定了最佳实验条件:质量浓度为60 g/L的高碘酸钠溶液加入量35mL,pH值在0.4～1.6之间,放置时间40 min。在选定实验条件下,该方法测定结果的相对标准偏差为1.26%(n=7),加标回收率为97.2%～104.1%。     

泡生法蓝宝石单晶炉热屏对热场的影响分析

对泡生法生长蓝宝石单晶进行了数值模拟,计算分析了晶体温度场分布规律.通过改变顶部保温屏的层数、侧壁保温屏的层数、反射屏的开口半径大小,分析热场的影响,得到了各参数与温度分布及温度梯度的变化关系.模拟发现,适当减少顶部保温屏层数,增大反射屏开口,可以增加晶体径向温度梯度;适当增加顶部保温屏层数,增大反射屏开口,可减小晶体轴向温度梯度.而侧壁屏层数几乎无影响.最后将分析结果与实验相结合,进行实验验证,成功获得了质量较好的蓝宝石单晶.