Efficient Synthesis of Triarylamines Catalyzed by Copper(I) Diazabutadiene Complexes

Cuprous chloride was coordinated by diazabutadiene (DAB‐R) ligands to form Cu(I)‐(DAB‐R) complexes, most of which have a 1:1 ratio of Cu to DAB‐R as reported. In the case of a special DAB‐ⁱPP, N,N′‐bis(2,6‐diisopropylphenyl)‐1,4‐diaza‐1,3‐butadiene, an unexpected composition of complex was found with the formula Cu(I)Cl(DAB)₂. When employed as catalyst for triarylamine synthesis from the coupling of aryl halides with primary and secondary arylamines, the new Cu(I)‐(DAB‐ⁱPP) complex displayed high efficiency.     

An on-line solid phase extraction-liquid chromatography tandem mass spectrometry method for the determination of perfluoroalkyl substances in the Antarctic ice core samples

An on-line solid phase extraction-high performance liquid chromatography-tandemmass spectrometry method for the analysis of perfluoroalkyl substances (PFASs) in water samples was developed. The optimal analytical conditions were obtained through the optimization of the extraction efficiency of online solid phase extraction column, sample loading rate and loading volume, and the concentration of ammonium acetate in mobile phase. Under the optimal condition, the analytical method displayed good linearity (r² > 0.99) for 12 PFASs (C5-C14 perfluoroalkyl carboxylic acids and C6/C8 perfluoroalkyl sulfonic acids) over a concentration range of 0.5-100 ng/L. The limits of quantitation for samples were between 0.025 ng/L and 0.5 ng/L and the relative standard deviations (RSD) of five consecutive analyses were less than 10% for 1 ng/L standard solution. Satisfactory results were obtained using this analytical method for the analysis of perfluoroalkyl substances in Antarctic ice core samples. The recoveries of all perfluoroalkyl substances were in a range of 73%-117% when the sampleswere spiked with standards at the concentrations of 2.5 ng/L and 25 ng/L.     

Redox kinetics of NiO/YSZ for chemical-looping combustion and the effect of support on reducibility

This paper explores the reaction kinetics of NiO supported on YSZ (Yttria Stabilized Zirconia) as an oxygen carrier for chemical looping combustion. Nickel particles with size less than 1 μm mixed with YSZ nano-powders are used to prepare the solid mixture, with 45% mol of NiO. Redox reactivity and oxygen carrying capacity are measured in a laboratory scale fixed bed reactor in the temperature range 500–1000 °C with different concentrations of the reactive gasses. Samples are subjected to repeated redox cycles using synthetic air (O₂+Ar) for oxidation, and H₂/H₂O/Ar mixtures for reduction. NiO/YSZ demonstrates superb cyclic regenerability starting with the 2nd cycle, with full utilization of its oxygen carrying capacity. Compared to pure nickel, pronounced improvement is achieved in the kinetics and oxygen utilization. Full reduction is achieved, and the presence of H₂O does not affect the reduction rate. Reactivity is also determined as a function of conversion. Global models of redox conversion are developed, in which surface chemistry and solid diffusion are considered. Oxidation exhibits the characteristics of a shrinking-core model with internal reactions at the Ni/NiO interface being the rate limiting step, and it is weakly temperature dependent. Reduction with H₂ generally exhibits surface chemistry limitation (adsorption-desorption), with surface product formation being the rate limiting step. YSZ significantly enhances ionic transport during oxidation and reduction. Reaction rate dependencies on conversion during the two steps suggest an optimal range for the oxygen carrying capacity of the material.     

从“最强酸碱”话题入手介绍超强酸、超强碱

酸碱质子理论是普通化学中的重要模块。学习酸碱质子理论一般从弱酸水溶液入手,若将应用范围扩展为所有含质子的化合物,该理论将被赋予更多的内涵。在含质子的已知化合物中,K_a的范围十分宽广,跨越了100个数量级以上。哪种酸碱“最强”一直是学生间喜闻乐见的话题,以此话题出发,介绍了常见的超强酸、超强碱与相关概念及应用。这些概念的介绍不仅拓展了学生的视野,更能够加深学生对酸碱质子理论的理解,对未来分析化学、无机化学、有机化学的教育产生积极意义。     

高选择性高效液相色谱-电化学检测法测定丹参中5种酚类物质

发展了一种高灵敏度的高效液相色谱-电化学检测（HPLC-ECD）方法,用于丹参中5种酚类物质的定量分析。为了获得较高的检测灵敏度,对流动相的pH、缓冲溶液类型和浓度、有机相种类和梯度以及流速做了系统研究。在较低的pH（2.8）、较低的缓冲盐浓度（20 mmol/L NaH₂PO₄）和较缓的乙腈梯度下,以0.2 mL/min流速可为5种酚类的分离检测提供较好的分离度和较高的检测灵敏度。在获得优化的分离参数后,将其用于14批丹参药材中5种酚类物质的定量分析。结果表明,该方法可获得较好的回收率（>95%）、较宽的线性范围（高达4个数量级）、较好的重复性（RSD<4.01%）和较高的灵敏度（咖啡酸的LOQ低至1.5μg/L）。与紫外检测方法相比,ECD检测方法具有更高的选择性,可减少非抗氧化活性的物质的干扰。     

探求高效裂解生产乙烯的新途径

乙烯是裂解反应过程中的中间产物，其收率随反应时间变化．在最佳反应时间，收率最高．裂解反应温度愈高，峰值收率愈高，最佳反应时间则愈短．当前通用的竖管裂解炉难以满足大幅度提高乙烯收率并降低生产成本的要求．评述了几种激波加热方法的优缺点．简要描述了我们目前正在研究中的反向射流混合加热方法．     

ON UNILATERALLY CONSTRAINED MOTIONS OF RIGID BODIES SYSTEMS

ＯＮＵＮＩＬＡＴＥＲＡＬＬＹＣＯＮＳＴＲＡＩＮＥＤＭＯＴＩＯＮＳＯＦＲＩＧＩＤＢＯＤＩＥＳＳＹＳＴＥＭＳＬｉＨｏｎｇｂｏ（李洪波）（ＭＭＲＣ，ＩｎｓｔｉｔｕｔｅｏｆＳｙｓｔｅｍｓＳｃｉｅｎｃｅ，ＡｃａｄｅｍｉａＳｉｎｉｃａ，Ｂｅｉｊｉｎｇ１０００８０...     

Unsteady model of drop Marangoni migration in microgravity

The experiments of drop Marangoni migration have been performed by the drop shift facility of short period of 4.5 s, and the drop accelerates gradually to an asymptotic velocity during the free fall. The unsteady and axisymmetric model is developed to study the drop migration for the case of moderate Reynolds numberRe=O(1), and the results are compared with the experimental ones in the present paper. Both numerical and experimental results show that the migration velocity for moderate Reynolds number is several times smaller than that given by the linear YGB theory. The project supported by the National Natural Science Foundation (19789201) and the Ministry of Science and Technology of China (95-Yu-34)     

Compact finite difference-Fourier spectral method for three-dimensional incompressible Navier-Stokes equations

A new compact finite difference-Fourier spectral hybrid method for solving the three dimensional incompressible Navier-Stokes equations is developed in the present paper. The fifth-order upwind compact finite difference schemes for the nonlinear convection terms in the physical space, and the sixth-order center compact schemes for the derivatives in spectral space are described, respectively. The fourth-order compact schemes in a single nine-point cell for solving the Helmholtz equations satisfied by the velocities and pressure in spectral space is derived and its preconditioned conjugate gradient iteration method is studied. The treatment of pressure boundary conditions and the three dimensional non-reflecting outflow boundary conditions are presented. Application to the vortex dislocation evolution in a three dimensional wake is also reported. The project supported by the National Natural Science Foundation of China     

精密角接触球轴承的固体润滑失效分析

角接触球轴承是航天器的许多重要功能的实施部件，因而对其润滑性能的要求极为严格，迫切需要弄清其润滑失效机理。因此，对ＭｏＳ２溅射膜润滑的Ｃ６２０５球轴承进行了寿命试验，进而对经过丙酮超声清洗的各元件工作面的形貌和组成作了系统分析。