Two Chiral Building Blocks for the Stereocontrolled Synthesis of Anti-and Syn-1,3-Diols

During the last decade, chiral building blocks for 1, 3-diols of various configurations have been synthesized and applied widely in the total synthesis of natural polyene macrolide antibiotics1 and 1(, 25-dihydroxyvitamin D3 analogues2,3. The synthesis of the building block has attracted much interest in recent years. Herein, we report the synthesis of two chiral building blocks 1 and 2 in 8 steps and 7 steps respectively, starting from the readily available and inexpensive D (+)-xylose 3 as o…     

Alternating,gradient, block,and block–gradient copolymers of ethylene and norbornene by Pd–Diimine‐Catalyzed “living” copolymerization

We demonstrate, in this article, the facile synthesis of a broad class of low‐polydispersity ethylene–norbornene (E–NB) copolymers having various controllable comonomer composition distributions, including gradient, alternating, diblock, triblock, and block–gradient, through “living”/quasiliving E–NB copolymerization facilitated with a single Pd – diimine catalyst ( 1 ). This synthesis benefits from two remarkable features of catalyst 1 , its high capability in NB incorporation and high versatility in rendering E–NB “living” copolymerization at various NB feed concentrations ([NB]₀) while under an ethylene pressure of 1 atm and at 15 °C. At higher [NB]₀ values between 0.42 and 0.64 M, E–NB copolymerization with 1 renders nearly perfect alternating copolymers. At lower [NB]₀ values (0.11–0.22 M), gradient copolymers yield due to gradual reduction in NB concentration, with the starting chain end containing primarily alternating segments and the finishing end being hyperbranched polyethylene segments. Through two‐stage or three‐stage “living” copolymerization with sequential NB feeding, diblock or triblock copolymers containing gradient block(s) have been designed. This work thus greatly expands the family of E–NB copolymers. All the copolymers have controllable molecular weight and relatively low polydispersity (with polydispersity index below 1.20). Most notably, some of the gradient and block–gradient copolymers have been found to exhibit the characteristic broad glass transitions as a result of their possession of broad composition distribution. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Diblock copolymer–azobenzene complexes through hydrogen bonding: Self‐assembly and stable photoinduced optical anisotropy

We have demonstrated the preparation of a series of photoaddressable supramolecular block copolymers by mixing a carboxy‐terminated azobenzene derivative, 6‐[4‐(4′‐cyanophenylazo)phenyloxy]hexanoic acid (AZO), and two polystyrene‐b‐poly(4‐vinylpiridine) (PS‐b‐P4VP) block copolymers. AZO can be selectively attached to the P4VP block of PS‐b‐P4VP through hydrogen bonding interactions. The assembly of AZO with vinylpyridine group‐containing polymers was initially investigated on a model system composed of P4VP homopolymer and AZO. Homogeneous liquid crystalline materials were obtained for ratios of AZO to vinylpyridine repeating unit, x, lower or equal to 0.50. Mixtures with higher x resulted in heterogeneous materials showing clear macrophase separation. Accordingly, a series of hydrogen‐bonded complexes of PS‐b‐P4VP and AZO, PS‐b‐P4VP(AZO)_x, with x = 0.25 and x = 0.50 were prepared. Lamellar and spherical morphologies were observed for the complexes based on PS24‐b‐P4VP9.5 (M_n,PS = 24,000, M_n,P4VP = 9500) and PS24‐b‐P4VP1.9 (M_n,PS = 24,000, M_n,P4VP = 1900), respectively. Photoinduced orientation of the azobenzene units was obtained in films of P4VP(AZO)_x and PS‐b‐P4VP(AZO)_x with x = 0.25 and 0.50 by using 488 nm linearly polarized light and characterized through birefringence and dichroism measurements. This investigation shows a versatile and less laborious approach to azobenzene‐containing polymer materials with low chromophore content, of interest in optical application. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Asymptotic exponential cones of Metzler matrices and their use in the solution of an algebraic problem

The aim of this paper is that of investigating the asymptotic exponential cone of a single Metzler matrix, introduced in [23], and of defining and analysing the new concept of asymptotic exponential cone of a family of Metzler matrices (along a certain direction). These results will provide necessary and/or sufficient conditions for the solvability of an interesting algebraic problem that arises in the context of continuous-time positive switched systems and, specifically, in the investigation of the reachability property [21,22,25].     

Dodging matrix effects in liquid chromatography tandem mass spectrometric assays—compilation of key learnings and perspectives

Triple quad liquid chromatography mass spectrometric assays (LC/MS/MS) have revolutionized the analysis of drug(s)/metabolite(s) with exceptional speed, sensitivity and selectivity features. From inception to date, several new and innovative features have been regularly proposed by researchers to further enhance the value in the applicability of this analytical tool. However, owing to such compressed run times and scanty sample preparation procedures, LC/MS/MS assays that are not fully optimized generally have issues of matrix effects, where ionization potential is either suppressed or enhanced due to the presence of other materials (endogenous/exogenous) in the matrix. By definition, even co‐medications, isomeric or isobaric impurities, and drug excipients used in dosing solutions could also potentially contribute to matrix effects. This article captures some of the interesting work carried out by researchers to understand and handle matrix effects. Additionally, it provides perspectives to effectively deal with matrix effects. Copyright © 2008 John Wiley & Sons, Ltd.     

一类积分微分方程概周期解的存在性和唯一性

考虑具无穷时滞的非线性积分微分方程概周期的存在性和唯一性问题,利用矩阵测度和不动点方法获得了一类方程的概周期的存在性和唯一性的充分条件,推广了相应文献的结果.     

Joint Distribution of Rises and Falls

The marginal distributions of the number of rises and the number of falls have been used successfully in various areas of statistics, especially in non-parametric statistical inference. Carlitz (1972, Duke Math. J. 39, 268–269) showed that the generating function of the joint distribution for the numbers of rises and falls satisfies certain complex combinatorial equations, and pointed out that he had been unable to derive the explicit formula for the joint distribution from these equations. After more than two decades, this latter problem remains unsolved. In this article, the joint distribution is obtained via the probabilistic method of finite Markov chain imbedding for random permutations. A numerical example is provided to illustrate the theoretical results and the corresponding computational procedures.     

Adaptive selection of parameters for precise computation of matrix exponential based on padé approximation

讨论了基于Pad\'{e}逼近的矩阵指数精细积分方法中加权系数N 和展开项数q的自适应选择问题. 参数(N,q)的选择直接影响到矩阵指数计算的精度和效 率. 采用矩阵函数逼近理论，研究了参数N和q的增加对精度的影响程度，据此，提出了 参数(N,q)优化组合的递推自适应选择方法. 该方法可以根据矩阵本身的性态选择合适的参 数(N,q),而参数选择的计算量与矩阵指数的计算量相比几乎可以忽略，这对于增强矩阵指 数精细积分方法的适应性和提高计算效率是很有益处的. 算例验证了该方法的正确性和有效性.     

Robust H∞ filtering for discrete-time impulsive systems with uncertainty

This paper investigates robust filter design for linear discrete-time impulsive systems with uncertainty under H∞ performance. First, an impulsive linear filter and a robust H∞ filtering problem are introduced for a discrete-time impulsive systems. Then,a sufficient condition of asymptotical stability and H∞ performance for the filtering error systems are provided by the discrete-time Lyapunov function method. The filter gains can be obtained by solving a set of linear matrix inequalities (LMIs). Finally, a numerical example is presented to show effectiveness of the obtained result.