Vinylic MIDA Boronates: New Building Blocks for the Synthesis of Aza‐Heterocycles

A two‐step synthesis of structurally diverse pyrrole‐containing bicyclic systems is reported. ortho‐Nitro‐haloarenes coupled with vinylic N‐methyliminodiacetic acid (MIDA) boronates generate ortho‐vinyl‐nitroarenes, which undergo a “metal‐free” nitrene insertion, resulting in a new pyrrole ring. This novel synthetic approach has a wide substrate tolerance and it is applicable in the preparation of more complex “drug‐like” molecules. Interestingly, an ortho‐nitro‐allylarene derivative furnished a cyclic β‐aminophosphonate motif.     

面心立方晶体外延膜沉积生长中失配位错的结构与形成过程

用分子动力学方法对5%负失配条件下面心立方晶体铝薄膜的原子沉积外延生长进行了三维模拟.铝原子间的相互作用采用嵌入原子法(EAM)多体势计算.模拟结果再现了失配位错的形成现象.分析表明，失配位错在形成之初即呈现为Shockley扩展位错，即由两个伯格斯矢量为〈211〉/6的部分位错和其间的堆垛层错组成，两个部分位错的间距、即层错宽度为1.8 nm,与理论计算结果一致；外延晶体薄膜沉积生长中，位错对会发生滑移，但其间距保持稳定.进一步观察发现，该扩展位错产生于一种类似于“局部熔融-重结晶”的表层局部无序紊乱- 关键词： 失配位错 外延生长 薄膜 分子动力学 铝     

Fabrication of material-independent morphology gradients for high-throughput applications

Gradient surfaces allow rapid, high-throughput investigations and systematic studies in many disparate fields, including biology, tribology and adhesion. We describe a novel method for the fabrication of material-independent morphology gradients, involving a two-step process of particle erosion followed by a chemical polishing procedure that preferentially removes features with a small radius of curvature as a function of time. Gradients are fabricated on aluminium surfaces, but they may be readily transferred to other materials via a replication technique, which allows for the production of identical roughness gradient samples with any chosen surface chemistry. The gradients have been characterized by means of scanning electron microscopy and optical profilometry. Standard roughness parameters (Ra, Rq, Rz, Sm and Sk) were calculated from optical profilometry data. The roughness has also been assessed over different wavelength windows by means of a fast Fourier transformation approach.     

Enantioselective hydrogenation of diaryl-substituted α,β-unsaturated nitriles

α,β-Unsaturated nitriles can be hydrogenated with enantioselectivities up to 88% ee using chiral ruthenium-diphenylphosphino bisaryl and bisheteroaryl complexes such as ruthenium(II)-BINAP and ruthenium(II)-BINP. Mechanistic investigations indicate that conversion is accelerated by electron-rich ligands and that an additional coordinative group needs be present in order to promote conversion. The chiral products are useful building blocks for the synthesis of histamine H₂ agonists of the arpromidine type.     

Analytic continuation and identities involving heat,Poisson, wave and Bessel kernels

In this article we use classical formulas involving the K–Bessel function in two variables to express the Poisson kernel on a Riemannian manifold in terms of the heat kernel. We then use the small time asymptotics of the heat kernel on certain Riemannian manifolds to obtain a meromorphic continuation of the associated Poisson kernel to all values of complex time with identifiable singularities. This result reproves in a different setting by different means a well–known theorem due to Duistermaat and Guillemin [DG 75]. Also, we develop analytic expressions for the heat kernel beyond asymptotic expansions. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)