Rhodium(III)‐Catalyzed N‐Nitroso‐Directed CH Addition to Ethyl 2‐Oxoacetate for Cycloaddition/Fragmentation Synthesis of Indazoles

Rh^III‐catalyzed N‐nitroso‐directed C?H addition to ethyl 2‐oxoacetate allows subsequent construction of indazoles, a privileged heterocycle scaffold in synthetic chemistry, through the exploitation of reactivity between the directing group and installed group. The formal [2+2] cycloaddition/fragmentation reaction pathway identified herein, a unique reactivity pattern hitherto elusive for the N‐nitroso group, emphasizes the importance of forward reactivity analysis in the development of useful C?H functionalization‐based synthetic tools. The synthetic utility of the protocol is demonstrated with the synthesis of a tricyclic‐fused ring system. The diversity of covalent linkages available for the nitroso group should enable the extension of the genre of reactivity reported herein to the synthesis of other types of heterocycles.     

TiO2-SiO2复合氧化物结构和红外光谱的量子化学研究

 构建了TiO2-SiO2复合氧化物晶胞结构,采用HyperChem量子化学程序中的从头计算方法以3-21G*基组对其进行了全优化计算,并进行了振动分析,预测了TiO2-SiO2复合氧化物各化学键的红外特征吸收频率. 采用IR谱对TiO2-SiO2复合氧化物进行了表征,通过理论计算与实验数据相结合的方法确定了TiO2-SiO2复合氧化物的分子结构,对其平衡几何构型、IR谱、电子结构和Lewis酸性进行了讨论.     

Radon transforms on Siegel-type nilpotent Lie groups

Let \mathfrak{N}:={{\displaystyle H}}_n\times {ℂ}^n be the Siegel-type nilpotent group, which can be identified as the Shilov boundary of Siegel domain of type II, where {{\displaystyle H}}_n denotes the set of all n\times n Hermitian matrices. In this article, we use singular convolution operators to define Radon transform on \mathfrak{N} and obtain the inversion formulas of Radon transforms. Moveover, we show that Radon transform on \mathfrak{N} is a unitary operator from Sobolev space W^n;2 into L²(\mathfrak{N}):     

CuCl对Et3NHCl/AlCl3离子液体催化性能的影响

 用CuCl对Et3NHCl/AlCl3离子液体进行改性,并考察了其对异丁烷-丁烯烷基化反应的催化性能. 结果表明,烷基化油的收率达到178%,C8组分的含量达到85%,辛烷值(RON)达到94.8. 通过结构组成及电荷分布分析可知,在CuCl改性的Et3NHCl/AlCl3离子液体中形成了新的配位结构AlCl4CuCl-,它作为更好的碳正离子受体,在反应过程中可降低碳正离子的浓度,进而降低烯烃的聚合程度,抑制较长碳链烷烃的生成,改善烷基化油的组成.     

Effect of tungsten oxide loading on metathesis activity of ethene and 2-butene over WO<Subscript>3</Subscript>/SiO<Subscript>2</Subscript> catalysts

The metathesis of ethene and 2-butene to propene was studied over WO₃/SiO₂ catalysts with various WO₃ loadings (2, 4, 8, 12, 16, and 24 wt%). The 2-butene conversion and propene selectivity increased greatly with WO₃ loading increasing from 2 to 8 wt%, reached maximum at 8–12 wt% WO₃ loading, and then decreased when the WO₃ loading was higher than 12 wt%. From the above results and taking the economics into account, the optimal amount of WO₃ loading was ~8 wt%. The catalysts were characterized by physico-chemical and spectroscopic techniques to elucidate the effect of different tungsten oxide loadings on the metathesis reactivity of ethene and 2-butene. The characterization data indicated that three types of tungsten species (i.e., surface tetrahedral tungsten species, surface octahedral polytungstate species, and WO₃ crystallites) were present in the catalysts. It was found that WO₃ was not the active centers, and surface tetrahedral tungsten species might be more active than octahedral polytungstate species in metathesis reaction. The reduced form of tungsten species [W⁺⁴, W⁺⁵, and W^+(6−y) (0 < y < 1)] may be the suitable state of W species acting as metathesis active centers.     

Au/MOF催化剂的制备、表征及其催化三组分偶联反应

采用后合成共价修饰法和一锅法分别制备了催化剂IRMOF-3-SI-Au(PS)和IRMOF-3-SI-Au(OP),运用X射线衍射、红外光谱、热重-差热分析、透射电镜以及程序升温还原对催化剂进行了表征,探索了这两种催化剂在醛、炔和胺三组分偶联反应中的催化性能,并推测了可能的反应机理.结果表明,两种催化剂对醛、炔和胺三组分偶联反应均具有较高的催化活性,产物炔丙基胺类选择性为100%,且可循环使用;结晶度较低的IRMOF-3-SI-Au(PS)的活性高于结晶度较高的IRMOF-3-SI-Au(OP);催化剂对芳香醛和脂肪醛以及环状胺均具有较高的催化活性,且对带有吸电子基团的芳香醛的活性高于带有供电子基团的.     

波浪扰动下河口幂律异重流的动力场分布特性

河口底层浮泥异重流的运动特性对于河口维持以及港口航道泥沙淤积过程具有重要的作用, 是海岸学科研究的关键内容, 也是热点内容之一. 本文首先综述了河口泥沙异重流研究的重要意义, 分析并总结了各家异重流理论模型的不同点和适应条件; 其次, 根据本文研究问题的实际需要, 构建了波浪与底泥相互作用的双层流体理论分析模式, 将上层流体简化为常见的牛顿体, 而将下层流体的流变关系设置为幂律函数, 研究了波浪作用下河口底部幂律异重流的流场特性. 这些特性包括:波浪速度场、底泥运动的流速场、不同密度影响下的压力场以及异重流泥面波与表面 波的波幅比等, 分析了泥层密度、波动圆频率以及底泥幂律指数对流场及界面波的影响. 研究发现, 在波浪扰动下, 两层流体交界处速度分量连续, 压强出现突变. 在下部泥层中, 水平速度幅值曲线存在极大值. 随着波动圆频率增加以及泥层密度与流动指数的减小, 界面处上下压强差值呈现增大的趋势. 本模型与实测波幅比的数据进行对比结果证实了模型的合理性.      

三角范畴的recollement与AR-三角

设{D＇，D，D＇＇；i^＊，i＊=i!，i^!，j!，j^＊=j^!，j＊）是一个recollement，本文证明了当D有AR-三角时，D＇，D＇＇也有AR-三角，并且它们的AR-三角完全可由D中AR-三角诱导．     

Experimental and computational studies on flow behavior of gas-solid fluidized bed with disparately sized binary particles

This paper presents experimental and computational studies on the flow behavior of a gas-solid fluidized bed with disparately sized binary particle mixtures. The mixing/segregation behavior and segregation efficiency of the small and large particles are investigated experimentally.Particle composition and operating conditions that influence the fluidization behavior of mixing/segregation are examined. Based on the granular kinetics theory, a multi-fluid CFD model has been developed and verified against the experimental results. The simulation results are in reasonable agreement with experimental data. The results showed that the smaller particles are found near the bed surface while the larger particles tend to settle down to the bed bottom in turbulent fluidized bed. However, complete segregation of the binary particles does not occur in the gas velocity range of 0.695--0.904 m/s. Segregation efficiency increases with increasing gas velocity and mean residence time of the binary particles, but decreases with increasing the small particle concentration. The calculated results also show that the small particles move downward in the wall region and upward in the core. Due to the effect of large particles on the movement of small particles, the small particles present a more turbulent velocity profile in the dense phase than that in the dilute phase.