Palladium-catalyzed tandem cyclization/Suzuki coupling of 1,6-enynes: reaction scope and mechanism

A palldium(0)-catalyzed tandem cyclization/Suzuki coupling reaction of various 1,6-enyne substrates was developed. This Pd-catalyzed enyne cyclization reaction represents a new process for the synthesis of stereodefined alpha-arylmethylene-gamma-butyrolactones, lactams, multifunctional tetrahydrofurans, pyrrolidines, and cyclopentanes. The mechanism of the reaction was studied by the employment of different enyne isomers and boronic acids; a pi-allyl palladium intermediate was suggested to explain the formation of the cyclic products. The stereochemistry of this reaction can be well explained by a chairlike transition state.     

Study on laminar viscosity and zero shear viscosity of latex systems

The flowing nature and rheological properties of polymethyl methacrylate latex systems in a coaxial cylinder viscometer were studied on the basis of laminar shear flow model and rheological experimental data. The physical meaning of laminar viscosity (eta(i,j)) and zero shear viscosity (eta(0)) were described. We assumed that laminar shear flows depended on position and shear time, so microrheological parameters were the function of position and shear time. eta(i,j) was the viscosity of any shear sheet i between two neighboring laminar shear flows at time t; j was denoted as j=t/Deltat; and Deltat was the interacting time of two particles or two laminar shear flows. tau(i,j) and gamma(i,j) were shear stress and shear rate of any shear sheet i at j moment. According to Newton regulation tau(i,j)=eta(i,j)gamma(i,j), apparent viscosity eta(a) should be a statistically mean value of j shear sheets laminar viscosity at j moment, i.e., eta(a)= summation operator(i=j)eta(i,j)gamma(i,j)/ summation operator(i=j)gamma(i,j). eta(0) was defined as shear viscosity between a laminar shear flow and a still fluid surface, i.e., eta(0)=(tau(i,j)/gamma(i,j))(j-i-->0). These new ideas described above may be helpful in the study of the micromechanisms of latex particle systems and worthy of more research.     

A Theoretical Study on the Conductivity of Carbon Doped BNNT

From the changes in energy band, density of state (DOS) and electronic structure calculated by the DFT/B3LYP method, the conductivity of carbon doped boron‐nitride nanotube (BNNT), which is formed by C‐C bond substituting B‐N bond, was discussed. The results indicate that the substitution will strengthen the conductivity of the tube, and its semi‐conductivity might be adjusted by controlling the substitution.     

Catalytic oxidation of alcohols with polymer-supported ruthenium complex under mild conditions

Polymer-supported ruthenium-containing complex PS–Phen–Ru was synthesized (where PS = chloromethyl polystyrene resin, Phen = 1,10-phenanthroline) and was characterized by FT-IR, ICP, and XPS. The supported complex was used to catalyze the oxidation of primary aliphatic alcohols as well as aromatic alcohols in the presence of iodosylbenzene. The oxidations were carried out in acetonitrile solution, affording the corresponding aldehydes or ketones in high substrate conversion and high selectivities under mild reaction conditions. The catalyst can be easily prepared and can be recycled.     

几种新的聚合物冠醚的合成及其络合与催化性能

由一、二、三和四缩乙二醇双钠盐与带有活泼卤原子的聚β-氯乙基缩水甘油醚进行环化反应,制备了四种新的聚合物冠醚(Ⅰ、Ⅱ、Ⅲ、Ⅳ)。络合容量测定结果表明,它们对K~+、Na~+均有较好的络合能力。在催化Wolff-Kishner(二苯甲酮腙还原为二苯甲烷)和正溴辛烷的碘代反应中,它们是有效的相转移催化剂。其中以Ⅱ最好,它的催化活性与小分子冠醚18-C-16和DB18-C-6相似,且易于回收,重复使用。     

微孔配位聚合物作为新型储氢材料的研究

微孔配位聚合物性质独特、结构多样，具有广泛的应用前景，它已成为近几年来一个热门的研究领域。本文简要介绍该类化合物作为一种新型的储氢材料，在合成、结构和储氢性能方面的研究进展。     

直接甲醇燃料电池中的涉水传递现象及数值模拟

直接甲醇燃料电池（DMFC）的开发设计日渐成为燃料电池领域的研究热点。利用数学模型对内部传递现象进行数值模拟，不仅具有很强的理论意义，而且对结构设计和操作条件优化有很强的指导意义。本文基于两相流模型和CFD（computer fluid dynamics）技术的应用，综述了电池内部绝大多数的传递过程，特别是近些年开发的电池内部与水相关的传递过程的物理模型和数学模型，并以二者的相互联系加以组织。这些模型思想综合考虑了微观传递机理，描述了电池内复杂的传递现象并提供了相应的数值模拟方法和模型验证方法。这些方法能够加深人们对电池内部传质现象的理解，而其实用意义在于能够指导设计和优化电池结构、提高电池的体积和重量比能量密度和缩短开发周期和大幅度降低开发成本。     

Self-assembling of helical poly(phenylacetylene) carrying L-valine pendants in solution, on mica substrate, and on water surface

In the present work, we investigated self-assembling of a poly(phenylacetylene) carrying L-valine pendants (PPA-Val) in a water/methanol solution, upon evaporation of the solution on mica, and on the water surface. With intercalation of a fluorescence probe of Ru(phen)2(dppx)2+ (phen = 1,10-phenanthroline, dppx=7,8-dimethyldipyridophenazine) into the hydrophobic cavities associated by the PPA-Val chains, their helical structures were directly detected in solution with an in situ fluorescence microscope. Helical aggregates were observed with AFM upon evaporation of the solvents, suggesting that the helical structures in the solution are the building blocks of the helical aggregates. Self-assembling structures of PPA-Val on the water surface were, however, very different from that formed upon evaporation of its THF solution on the mica surface. The polymer chains associated into a monolayer of extended fibers on the water surface, whereas superhelical fibers formed on the mica surface. Water molecules play a critical role in inducing the polymer to form diverse morphological structures in its bulk solution and on its surface. In solution, the isotropic hydrophobic effect drove the polymer chains to form superhelical aggregates, while on the water surface, the hydrophobic effect concentrated mainly on the lateral part of the polymer, thus giving a monolayer of extended fibers.     

溶胶—凝胶合成（Mg,Ca）O—SiO2：Eu^3＋,Bi^3＋发光体及其发光行为

以Ｍｇ（ＮＯ３）２，Ｃａ（ＮＯ３）２，Ｅｕ（ＮＯ３）３，Ｂｉ（ＮＯ３）３和Ｓｉ（ＯＣ２Ｈ５）４为反应物，采用溶胶－凝胶法，在比较低的温度，首次合成０．７０１ｍｏｌＭｇＯ－０．１７５ｍｏｌＣａＯ－１．２５ｍｏｌＳｉＯ２：０．０６ｍｏｌＥｕ＾３＋，０．００２ｍｏｌＢｉ＾３＋（加入Ｌｉ＾＋作为电荷补偿剂）发光体，得到了最佳合成条件，研究了由溶胶向凝胶转变和凝胶向发光晶体的转变过程，探讨了发光体在不同激光     

长链脂肪酸LB膜的X射线衍射研究

利用Langmuir-Blodgett技术制备了硬脂酸、花生酸及其混合酸的多层LB膜。用低角X射线衍射研究了它们的周期结构,硬脂酸和花生酸的LB膜在2θ=0.8°～23°的范围内分别出现13个和12个布拉格衍射峰,由此计算了它们的等同周期。用模型计算了它们衍射峰的强度,得到了与实验一致的衍射强度奇偶起伏的结果。在混合酸的LB膜中,可以观察到等同周期随混合比变化的规律。