吡咯亚胺配体与过渡金属的反应性及其催化烯烃聚合

在经典的Brookhart吡啶双亚胺后过渡金属烯烃聚合催化剂基础上,用吡咯五元环代替吡啶六元环骨架可得到具有不同电子效应的新型吡咯亚胺配体.通过吡咯环特殊的电子效应和位阻效应可设计出种类繁多的有别于吡啶亚胺配体的配合物.综述了吡咯亚胺配体与前过渡金属(Ti,Zr等)、后过渡金属(Fe,Co,Ni,Pd等)、稀土金属(Y...     

A particle swarm pattern search method for bound constrained global optimization

In this paper we develop, analyze, and test a new algorithm for the global minimization of a function subject to simple bounds without the use of derivatives. The underlying algorithm is a pattern search method, more specifically a coordinate search method, which guarantees convergence to stationary points from arbitrary starting points. In the optional search phase of pattern search we apply a particle swarm scheme to globally explore the possible nonconvexity of the objective function. Our extensive numerical experiments showed that the resulting algorithm is highly competitive with other global optimization methods also based on function values. Support for Luís N. Vicente was provided by Centro de Matemática da Universidade de Coimbra and by FCT under grant POCI/MAT/59442/2004.     

Mechanical instabilities of bubble clusters between parallel walls

We have carried out a systematic study of buckling-like mechanical instabilities in simple two- (2D) and three-dimensional (3D) symmetric foam clusters sandwiched between parallel planar walls. These instabilities occur when the wall separation w is reduced below a critical value, w^*, for which the foam surface energy E reaches its minimum, E^*. The clusters under investigation consist of either a single bubble, or of twin bubbles of fixed equal sizes (areas A in 2D or volumes V in 3D), which are either free to slide or pinned at the confining walls. We have numerically obtained w^* for both free and pinned 2D and 3D clusters. Furthermore, we have calculated the buckled configurations of 2D twin bubbles, either free or pinned, and of 3D free twin bubbles, whose energy is independent of w and equal to the minimum energy E^* of the unbuckled state. Finally, we have also predicted the critical w_t^* at which the terminal configurations under extension of 2D and 3D single and twin bubbles are realised. Experimental illustrations of these transitions under compression and extension are presented. Our results, together with others from the literature, suggest that a bubble cluster bounded by two parallel walls is stable only if the normal force it exerts on the walls is attractive, i.e., if dE/dw > 0; clusters that cause repulsion between the walls are unstable. We correlate this with the distribution of film orientations: films in a stable cluster cannot be too parallel to the confining walls; rather, their average tilt must be larger than for a random distribution of film orientations.     

Direct observation of domain-wall configurations transformed by spin currents

Direct observations of current-induced domain-wall propagation by spin-polarized scanning electron microscopy are reported. Current pulses move head-to-head as well as tail-to-tail walls in submicrometer Fe20Ni80 wires in the direction of the electron flow, and a decay of the wall velocity with the number of injected current pulses is observed. High-resolution images of the domain walls reveal that the wall spin structure is transformed from a vortex to a transverse configuration with subsequent pulse injections. The change in spin structure is directly correlated with the decay of the velocity.     

Doppler power spectrum from a Gaussian sample volume

A closed-form expression for the Doppler power spectrum due solely to the range of blood velocities passing through a Gaussian sample volume placed anywhere in a vessel under conditions of axisymmetric flow, uniform backscatter and negligible intrinsic spectral broadening has been derived. The formulation presented here allows the independent specification of the sample volume position and width, in the three dimensions, and enables simple estimations of spectral shape for pulsed wave Doppler systems. Simpler expressions were derived for the cases of symmetric sample volume projections onto the vessel cross-section and/or sample volumes centred in the vessel. Closed form expressions were derived for mean frequency and spectral width in the case of a symmetric sample volume projection centred in the vessel. The effects of sample volume size and position on the Doppler spectral width and mean frequency are shown for a range of velocity profiles.     

Stability constants of chloro-complexes of cadmium(II) in sea-water medium

Potentiometry with ion-selective electrodes and anodic stripping voltammetry were used to measure the stability constants for cadmium chloro-complexes at 20 +/- 0.1 degrees in synthetic sea-water and at an ionic strength of 0.700 (NaClO(4) + NaCl). The values of beta(ML) and beta(ML(2)) obtained by the two methods are in good agreement.     

Reactivity of muonium atoms in aqueous solution

A beam of surface muons (4.1 MeV) was used to generate thermalised muonium atoms (μ⁺e^?) in aqueous solutions. From measurements of the muonium atom relaxation time in the presence of various solutes, bimolecular rate constants were determined and compared with the corresponding reactions of the much heavier isotope, the hydrogen atom.     

Magnetic domain confinement by anisotropy modulation

The spin configuration in a magnet is in general a "natural" consequence of both the intrinsic properties of the material and the sample dimensions. We demonstrate that this limitation can be overcome in a homogeneous ferromagnetic film by engineering an anisotropy contrast. Substrates with laterally modulated single-crystal and polycrystalline surface regions were used to induce selective epitaxial growth of a ferromagnetic Ni film. The resulting spatially varying magnetic anisotropy leads to regular perpendicular and in-plane magnetic domains, separated by a new type of magnetic wall---the "anisotropy constrained" magnetic wall.     

时频方法分析长骨中的超声导波及皮质骨厚度

超声导波在长骨中传播时,接收信号中含有相互叠加的多个导波模式。本文提出将希尔伯特-黄变换(HHT)用于分析叠加的多模式导波信号,将其分解成许多单个独立的模式,然后对分解出的模式求得其对应频率下的群速度,并与短时傅里叶变换所得的结果进行比较。通过与理论计算结果比较,可得到长骨皮质骨的厚度。研究结果表明,实验得到的厚度与实际厚度一致。说明通过测量导波模式的速度可以评价皮质骨的厚度,也说明HHT方法是一种识别叠加多模式导波信号的有效方法。      

Non-isothermal polymer melt flow in sudden expansions

This paper presents numerical results for laminar, incompressible and non-isothermal polymer melt flow in sudden expansions. The mathematical model includes the mass, momentum and energy conservation laws within the framework of a generalized Newtonian formulation. Two constitutive relations are adopted to describe the non-Newtonian behavior of the flow, namely Cross and Modified Arrhenius Power-Law models. The governing equations are discretized using the finite difference method based on central, second-order accurate formulas for both convective and diffusive terms. The pressure–velocity coupling is treated by solving a Poisson equation for pressure. The results are presented for two commercial polymers and demonstrate that important flow parameters, such as pressure drop and viscosity distribution, are strongly affected by heat transfer features.