有机硅试剂参与过渡金属催化的C-H官能团化反应形成C-C键的研究进展

作为一类重要的有机金属试剂,有机硅试剂在有机合成化学的C—C键形成中得到了广泛应用.综述了近年来有机硅试剂参与的过渡金属催化下C—H官能团化反应形成C—C键的研究进展,重点介绍了Pd催化下C—H官能团化的Hiyama偶联反应.     

均四嗪衍生物结构、生成焓及爆轰性能的理论研究

运用DFT-w B97/6-31+G**方法对23种1,2,4,5-四嗪衍生物的几何结构、自然键轨道(NBO)和生成焓(EOF)进行研究,并在此基础上运用Kamlet-Jacobs方程估算衍生物的爆轰性能,得到其爆速在6.69~9.37 km/s之间;基于统计热力学,求得部分标题化合物在200~800 K温度范围内的热力学性质,随温度T升高,热容Cp、熵Sm及焓Hm逐渐增大。根据最小键级理论,C-R(取代基)键和N-R键可能是1,2,4,5-四嗪衍生物高温裂解的热引发键。综合分析,基团-NO2、-N3和-N=N-有助于提高四嗪衍生物的生成焓和爆轰性能,3,6-二硝基-1,2,4,5-四嗪和3,6-二偶氮基-二硝基-1,2,4,5-四嗪从能量、爆轰性能上可以作为高能量密度材料候选物。     

Nickel N‐Heterocyclic Carbene Catalyzed CC Bond Formation: A New Route to Aryl Ketones

A novel nickel N‐heterocyclic carbene catalyzed cross‐coupling reaction of aryl aldehydes with boronic esters for the synthesis of aryl ketones was developed. This reaction provides a mild, practical method toward aryl ketones, which are versatile intermediates and building blocks in organic synthesis.     

Stabilization of Titanium Dioxide Nanoparticles at the Surface of Carbon Nanomaterials Promoted by Microwave Heating

TiO₂ is frequently combined with carbon materials, such as reduced graphene oxide (RGO), to produce composites with improved properties, for example for photocatalytic applications. It is shown that heating conditions significantly affect the interface and photocatalytic properties of TiO₂@C, and that microwave irradiation can be advantageous for the synthesis of carbon‐based materials. Composites of TiO₂ with RGO or amorphous carbon were prepared from reaction of titanium isopropoxide with benzyl alcohol. During the synthesis of the TiO₂ nanoparticles, the carbon is involved in reactions that lead to the covalent attachment of the oxide, the extent of which depends on the carbon characteristics, heating rate, and mechanism. TiO₂ is more efficiently stabilized at the surface of RGO than amorphous carbon. Rapid heating of the reaction mixture results in a stronger coupling between the nanoparticles and carbon, more uniform coatings, and smaller particles with narrower size distributions. The more efficient attachment of the oxide leads to better photocatalytic performance.     

Cationic Cobalt(III)‐Catalyzed Aryl and Alkenyl CH Amidation: A Mild Protocol for the Modification of Purine Derivatives

A cationic cobalt(III)‐catalyzed direct C?H amidation of unactivated (hetero)arenes and alkenes by using 1,4,2‐dioxazol‐5‐ones as the amidating reagent has been developed. This transformation proceeds efficiently under external oxidant‐free conditions with a broad substrate scope. Moreover, 6‐arylpurine compounds, which often exhibit high potency in antimycobacterial, cytostatic, and anti‐HCV activities, can be smoothly amidated, thus offering a mild protocol for their late stage functionalization.     

Observation of the multiple halogenation of peptides in the electrospray ionization source

The chlorination of peptides and proteins is an important posttranslational modification, which is a physiological signature of an enzyme myeloperoxidase and can serve as a potential biomarker of some diseases (Parkinson's disease, Alzheimer's disease, etc.). The quantification of the chlorinated peptides has been very challenging in part due to their low levels and artifacts associated with sample preparation. One of the most convenient and promising methods to detect and investigate the chlorinated peptides in the biological samples is the electrospray ionization (ESI) mass spectrometry coupled to the fragmentation techniques (collision‐induced dissociation and electron capture dissociation/electron transfer dissociation). We have shown that if the chlorine anions are present in the solution, then the peptide can undergo the chlorination during the ESI ionization. The effect was found to depend on the values of electric potentials of metal parts of the ESI interface. It was found that the grounding of ESI syringe results in the formation of an additional electric loop leading to the electrolytic production of Cl₂ and as a consequence the hypochlorous acid inside the ESI needle. Hypochlorous acid reacts with amino groups of peptides and proteins producing chloramine or causing the protein cleavage. In the paper, it is shown on the example of the solution of the several peptides in the presence of HCl that by manipulating the ESI syringe potential, it is possible to create complexes with up to five Cl atoms for sample peptides when the ESI is operated in the positive mode. Copyright © 2015 John Wiley & Sons, Ltd.     

线型聚能装药的理论研究

本文提出了一端起爆的线型聚能装药射流形成的不定常理论模型。根据这一模型,当金属罩在爆轰波作用下的运动速度为已知时,则不论此速度是否是时间或初始位置的函数,都能得到射流形成时的速度,质量和位置等参数。 按照本文模型,Defourneaux.M.的定常射流形成定常模型是一个简单的特例。我们利用本文的模型对等厚度装药的情况进行了计算,并与实验结果比较,两者符合良好。同时计算结果表明,考虑射流形成的不定常因素,可以较好地解释射流头部的质量堆积和射流内部的反向速度梯度等实验现象。本文的模型可以为线型聚能切割索的设计提供较为准确的理论指导。     

Direct numerical simulations of two-layer viscosity-stratified flow

Two-dimensional simulations of flow instability at the interface of a two-layer, density-matched, viscosity-stratified Poiseuille flow are performed using a front-tracking/finite difference method. We present results for the small-amplitude (linear) growth rate of the instability at small to medium Reynolds number for varying thickness ratio n, viscosity ratio m, and wavenumber. We also present results for large-amplitude non-linear evolution of the interface for varying viscosity ratio and interfacial tension. For the linear case, the interfacial mode is neutrally stable for as predicted by analysis. The growth rate is proportional to Reynolds number for small Re, and increases with viscosity ratio. The growth rate also increases when the thickness of the more viscous layer is reduced. Strong non-linear behavior is observed for relatively large initial perturbation amplitude. The higher viscosity fluid is drawn out as a finger that penetrates into the lower viscosity layer. The simulated interface shape compares well with previously reported experiments. Increasing interfacial tension retards the growth rate of the interface as expected, whereas increasing the viscosity ratio enhances it. Drop formation at the small Reynolds number considered in this study is precluded by the two-dimensional nature of the calculations.     

BEWARE OF THE BEACH HIDDEN KILLER--RIP CURRENT

离岸流是垂直于海岸线、向外海方向快速移动的强劲海流。对于海边的人员来说非常危险,没有经验的游泳者一旦被离岸流带离浅滩,很难与之对抗游回岸边,往往因力竭而溺水。每年海滨区域都有大量的溺亡事件与此相关,但有关离岸流的知识在公众的视野里仍比较缺乏。本文从流体力学的角度对离岸流的危害、形成、特征以及分类进行了简要介绍,并在如何防范离岸流、保障自身安全等方面给出了一些建议。     

Turbulent flow past a transverse cavity with inclined side walls. 1. Flow structure

The process of vortex formation in a cavity with inclined walls, which has a moderate aspect ratio, is experimentally studied, and the distribution of pressure coefficients is measured. The angle of inclination of the side walls ϕ is varied from 30 to 90°. It is found that the flow in the cavity becomes unstable in the range of inclination angles ϕ = 60–70°. Flow reconstruction occurs, which substantially alters the surface-temperature and static-pressure distributions. Large changes in these characteristics and their nonuniform distributions for these angles are observed across the cavity on its frontal wall and on the bottom. For small angles (ϕ = 30 and 45°), the pressure on the rear wall drastically increases, which leads to a small increase in pressure averaged over the entire cavity surface. __________ Translated from PrikladnayaMekhanika i Tekhnicheskaya Fizika, Vol. 47, No. 5, pp. 68–76, September–October, 2006.