Efficient Synthesis of β‐Hydroxy‐α‐Amino Acid Derivatives via Direct Catalytic Asymmetric Aldol Reaction of α‐Isothiocyanato Imide with Aldehydes

An easily available and efficient chiral N,N′‐dioxide–nickel(II) complex catalyst has been developed for the direct catalytic asymmetric aldol reaction of α‐isothiocyanato imide with aldehydes which produces the products in morderate to high yields (up to 98 %) with excellent diastereo‐ (up to >99:1 d.r.) and enantioselectivities (up to >99 % ee). A variety of aromatic, heteroaromatic, α,β‐unsaturated, and aliphatic aldehydes were found to be suitable substrates in the presence of 2.5 mol % L ‐proline‐derived N,N′‐dioxide L5 –nickel(II) complex. This process was air‐tolerant and easily manipulated with available reagents. Based on experimental investigations, a possible transition state has been proposed to explain the origin of reactivity and asymmetric inductivity.     

15N chemical shifts of a series of isatin oxime ethers and their corresponding nitrone isomers

In this article, we describe the characteristic ¹⁵N chemical shifts of isatin oxime ethers and their isomer nitrone. These oxime ethers and nitrones are the alkylation reaction products of isatin oximes. In our study, the ¹⁵N chemical shifts observed in these oxime ethers were in the 402–408 (or 22–28) ppm range, although those for their corresponding nitrone series were in the 280–320 (or ?100 to ?60) ppm range. This remarkable difference in ¹⁵N NMR chemical shift values could potentially be used to determine the O‐ versus N‐alkylation of oximes, even when only one isomer is available. In this paper, the differences in ¹⁵N NMR chemical shifts serve as the basis for a discussion about how to distinguish both regioisomers derived from the oximes alkylation. Copyright © 2010 John Wiley & Sons, Ltd.     

PREPARATIVE ISOLATION AND PURIFICATION OF FIVE FLAVONOIDS FROM POGOSTEMON CABLIN BENTH BY HIGH-SPEED COUNTERCURRENT CHROMATOGRAPHY AND PREPARATIVE HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY

High-speed countercurrent chromatography (HSCCC) and preparative high-performance liquid chromatography (prep-HPLC) were successively used for the separation of pogostone and four flavonoids from Pogostemon cablin (Blanco) Benth. An efficient HSCCC separation was achieved on a two-phase solvent system composed of n-hexane-ethyl acetate-methanol-water (11:5:11:5, v/v/v/v). Three well-separated peaks were obtained in the HSCCC chromatogram. The first and the second fractions each contained two flavonoids which were further separated by preparative HPLC. Consequently, the separation yielded 11.5 mg of 4', 5-Dihydroxy-3', 7-dimethoxyflavanone at a purity of 99%, 20.3 mg of 5- Hydroxy-7, 3', 4'-trimethoxyflavanone at a purity of 98%, 18 mg of 5, 4'-Dihydroxy-3, 7, 3'-trimethoxyflavone at a purity of 96%, and 8 mg of 5-Hydroxy-3, 7, 4'-tetramethoxyflvone at a purity of 98%. The third HSCCC fraction yielded 18.5 mg of pogostone at a purity of 95%. The chemical structures of these compounds were identified by ESI-MS(n), (1)H-NMR, and (13)C-NMR.     

(RXNR)_4(X=B，Al，Ga)簇合物的结构与化学键性质

用自洽场理论（HF）和密度泛函理论（DFT）的B3LYP方法,在6-311G~*水平上 ,首次从理论上研究了(RXNR)_4 (R = B,Al,Ga;R = H,CH_3,NH_2,OH)簇合 物及其先驱化合物（RXNR）_2的几何构型、电子结构和化学键性质,并与其异构体 及其等电子化合物进行了比较。结果表明,(RBNR)_4为环状骨架结构,(RAlNR)_4 和(RGaNR)_4为建立骨架结构。     

大体积采样结合高分辨气相色谱-电子捕获负化学源-低分辨质谱法测定空气中的短链氯化石蜡

建立了大体积采样结合高分辨气相色谱-电子捕获负化学源-低分辨质谱(HRGC-ECNI-LRMS)测定空气中短链氯化石蜡(SCCPs)的定量分析方法。联合使用酸化硅胶复合层析柱和碱性氧化铝层析柱净化处理空气样品中的SCCPs,并对净化条件进行优化。使用该方法计算得到氯含量为58.1%~63.3%的SCCPs系列标准储备溶液的总响应因子与氯含量线性相关,相关系数(R²)大于0.99。该方法的仪器检出限(S/N≥3)为4.2 pg,定量限(S/N≥10)为12 pg。SCCPs的方法检出限(MDL)为0.34 ng/m³(n=7),实际样品加标回收率均达80%以上。该方法灵敏度高、选择性好,能满足空气样品中SCCPs的监测和分析需求。     

Air flow exploration of abrasive feed tube

An abrasive water-jet cutting process is one in which water pressure is raised to a very high pressure and forced through a very small orifice to form a very thin high speed jet beam. This thin jet beam is then directed through a chamber and then fed into a secondary nozzle, or mixing tube. During this process, a vacuum is generated in the cham- ber, and garnet abrasives and air are pulled into the chamber, through an abrasive feed tube, and mixes with this high speed stream of water. Because of the restrictions introduced by the abrasive feed tube geometry, a vacuum gradient is generated along the tube. Although this phenomenon has been recog- nized and utilized as a way to monitor nozzle condition and abrasive flowing conditions, yet, until now, conditions inside the abrasive feed line have not been completely understood. A possible reason is that conditions inside the abrasive feed line are complicated. Not only compressible flow but also multi- phase, multi-component flow has been involved in inside of abrasive feed tube. This paper explored various aspects of the vacuum creation process in both the mixing chamber and the abrasive feed tube. Based on an experimental exploration, an analytical framework is presented to allow theoretical calculations of vacuum conditions in the abrasive feed tube.     

淹没磨料射流的空泡运动分析

通过对淹没条件下磨料射流的空泡运动分析研究,建立了淹没磨料射流的空泡运动方程,揭示了淹没磨料射流中空泡的溃灭特性,数值模拟了淹没磨料射流的磨料体积浓度以及空泡所处流场压力对空泡运动及溃灭的影响规律.分析表明:淹没磨料射流中磨料的存在增大流体的粘性系数,增大空泡溃灭历时,减弱射流的空蚀破坏能力;流场压力的改变对空泡溃灭过程影响显著,压力越高,空泡溃灭历时越短.     

Stability and Hopf bifurcation of a delayed Cohen–Grossberg neural network with diffusion

In this paper, a delayed Cohen–Grossberg neural network with diffusion under homogeneous Neumann boundary conditions is investigated. By analyzing the corresponding characteristic equation, the local stability of the trivial uniform steady state and the existence of Hopf bifurcation at the trivial steady state are established, respectively. By using the normal form theory and the center manifold reduction of partial function differential equations, formulae are derived to determine the direction of bifurcations and the stability of bifurcating periodic solutions. Numerical simulations are carried out to illustrate the main results. Copyright © 2016 John Wiley & Sons, Ltd.     

指数凸函数的积分不等式及其在Gamma函数中的应用

仿对数凸函数的概念,给出指数凸函数的定义,并证明有关指数凸函数的几个积分不等式,作为应用,得到一个新的Kershaw型双向不等式.     

修正的IPA算法的建立及在不等式约束凸优化问题中的应用

本文首先对IPA算法进行了修正，并证明了修正IPA算法的收敛性，然后将修正后的IPA应用到不等式约束凸优化问题中得到新的内点算法，并与传统的障碍函数法作了比较，从理论上体现了新算法的优势，并给出了其工程解求解法以及收敛性的证明．