Catalytic asymmetric construction of spirocyclopentaneoxindoles by a combined Ru-catalyzed cross-metathesis/double Michael addition sequence

Biologically important and synthetically challenging spirocyclopentaneoxindoles with four contiguous stereocenters including one spiroquaternary stereocenter have been constructed in good yields (72-87%) with excellent diastereoselectivity (16:1→30:1 dr) and enantioselectivity (93→99% ee) by a combined Ru-catalyzed cross-metathesis/organocatalyzed asymmetric double-Michael addition sequence.     

Qualitative and quantitative analyses of Epimedium wushanense by high-performance liquid chromatography coupled with diode array detection and electrospray ionization tandem mass spectrometry

A new HPLC-DAD-ESI-MS(n) method was developed for rapid separation, characterization and quantitation of flavonoids in Epimedium wushanense, a popular Chinese herbal medicine. For qualitative identification, a total of 37 compounds were characterized from the underground and aerial parts of E. wushanense. Among them, 28 compounds were prenylated flavonoids, and 23 were confirmed by comparing with reference standards. For quantitative analysis, 12 major flavonoids including kaempferol glycosides, desmethylicaritin glycosides, and icaritin glycosides were simultaneously determined by HPLC/UV. Samples were separated on a Waters Symmetry C(18) column at 35 °C eluted with a gradient three-component mobile phase of acetonitrile, methanol, and water containing 0.03% v/v formic acid. All the flavonoids showed good linearity (r(2) ≥0.9997). The recoveries varied from 92.6 to 106.1% at three concentration levels. This method was applied to the determination of 20 samples of different geographical sources, harvesting time, and plant parts. Contents of the predominant flavonoid, epimedin C, ranged from 1.4 to 5.1% in aerial parts and 1.0 to 2.8% in underground parts. The methods established in this paper were simple and reliable and could be used for the quality control of E. wushanense.     

Micelles from amphiphilic block copolyphosphates for drug delivery

Amphiphilic block copolyphosphates (PEP-b-PIPPs) are synthesized by two-step ROP of cyclic phosphate monomers with different pedant groups. They can spontaneously self-assemble into approximately spherical micelles ranging in size between 89 and 198 nm in water. A typical hydrophobic anti-cancer drug DOX is encapsulated into the micelles. The release rate of DOX slows down with increasing hydrophobic block length of PIPP. DOX-loaded micelles are investigated for the proliferation inhibition of Hela cells and the DOX dose required for 50% cellular growth inhibition is found to be 0.8 μg mL(-1). It is demonstrated that PEP-b-PIPP micelles can be used as a safe and promising drug delivery system.     

Solving diffusion equation using wavelet method

A wavelet-based numerical method based on wavelets of Hermite cubic splines is presented for computing singularly perturbed convection-dominated diffusion equation. The advantages of the method are explained. To improve the accuracy of singular areas, wavelets are configured hierarchically for solving algebraic equations. Numerical examples show that the proposed method has good efficiency and precision.     

Efficient integration for a class of highly oscillatory integrals

This paper presents some quadrature methods for a class of highly oscillatory integrals whose integrands may have singularities at the two endpoints of the interval. One is a Filon-type method based on the asymptotic expansion. The other is a Clenshaw-Curtis-Filon-type method which is based on a special Hermite interpolation polynomial and can be evaluated efficiently in O(N log N) operations, where N + 1 is the number of Clenshaw-Curtis points in the interval of integration. In addition, we derive the corresponding error bound in inverse powers of the frequency ω for the Clenshaw-Curtis-Filon-type method for the class of highly oscillatory integrals. The efficiency and the validity of these methods are testified by both the numerical experiments and the theoretical results.     

Computation of generalized differentials in nonlinear complementarity problems

Let f and g be continuously differentiable functions on R ⁿ . The nonlinear complementarity problem NCP(f,g), 0≤f(x)⊥g(x)≥0, arises in many applications including discrete Hamilton-Jacobi-Bellman equations and nonsmooth Dirichlet problems. A popular method to find a solution of the NCP(f,g) is the generalized Newton method which solves an equivalent system of nonsmooth equations F(x)=0 derived by an NCP function. In this paper, we present a sufficient and necessary condition for F to be Fréchet differentiable, when F is defined by the “min” NCP function, the Fischer-Burmeister NCP function or the penalized Fischer-Burmeister NCP function. Moreover, we give an explicit formula of an element in the Clarke generalized Jacobian of F defined by the “min” NCP function, and the B-differential of F defined by other two NCP functions. The explicit formulas for generalized differentials of F lead to sharper global error bounds for the NCP(f,g).     

基于Vague集的水电工程方案模糊综合评价

水利工程建设方案决策是多目标综合评价问题,系统指标信息具有复杂、多变,模糊、不确定等特点,采用Vague集相似度量评价模型构建水利工程建设方案综合决策模型,建立基于Vlague集的指标隶属度计算方法,构造基于Vague集相似度的多目标方案评价.针对建设方案决策评价指标的不确定性,通过肯定、踌躇、否定的Vague集相似度量概念延伸了传统模糊集的评价、分析方式.将方法应用于水利工程建设方案决策实例,取得较为满意的结果,表明了方法的合理可行性,为水利工程的建设方案评价提供了科学决策的新途径.     

改进模糊一致矩阵及其在工程评标中的应用

基于模糊一致矩阵的决策方法的不足之处,对模糊优先关系矩阵的构造、模糊一致矩阵的转化、排序方法等方面进行了改进.将改进后的决策方法用于建筑工程的综合评价,将决策者的思维量化,由定性向定量进行转化,构造出建筑工程的综合评价方案优选的改进模糊一致矩阵数学模型,为建筑工程评标数学模型的建立提供了影响因素量化排序的分析方法.实证分析结果表明,改进后的决策方法能更好地反映参评对象的实际情况.     

Oxidation of Au by surface OH: nucleation and electronic structure of gold on hydroxylated MgO(001)

The nucleation and electronic structure of vapor-deposited Au on hydroxylated MgO(001) surfaces has been investigated under ultrahigh vacuum conditions. Hydroxylated MgO(001) surfaces with two different hydroxyl coverages, 0.4 and 1 monolayer, respectively, were prepared by exposure to water (D(2)O) at room temperature. Scanning tunneling microscopy experiments show significantly higher gold particle densities and smaller particle sizes on the hydroxylated MgO surface as compared to gold deposited on clean MgO(001). Infrared spectroscopy and X-ray photoelectron spectroscopy experiments were performed to reveal details about the initial nucleation of gold. Gold atoms are found to chemically interact with a specific type of hydroxyl groups on the MgO surface, leading to the formation of oxidized gold particles. The enhanced adhesion of Au particles, which is due to the formation of strong Au-O interfacial bonds, is responsible for the observed higher stability of small Au clusters toward thermal sintering on hydroxylated MgO surfaces. The results are compared to similar studies on Au/TiO(2)(110) model systems and powder samples prepared by the deposition-precipitation route.