An eight-degree-of-freedom, time-dependent quantum dynamics study for the H2+C2H reaction on a new modified potential energy surface

An eight-dimensional time-dependent quantum dynamics wave packet approach is performed for the study of the H2+C2H-->H+C2H2 reaction system on a new modified potential energy surface (PES) [L.-P. Ju et al., Chem. Phys. Lett. 409, 249 (2005)]. This new potential energy surface is obtained by modifying Wang and Bowman's old PES [J. Chem. Phys. 101, 8646 (1994)] based on the new ab initio calculation. This new modified PES has a much lower transition state barrier height at 2.29 kcal/mol than Wang and Bowman's old PES at 4.3 kcal/mol. This study shows that the reactivity for this diatom-triatom reaction system is enhanced by vibrational excitations of H2, whereas the vibrational excitations of C2H only have a small effect on the reactivity. Furthermore, the bending excitations of C2H, compared to the ground state reaction probability, hinder the reactivity. The comparison of the rate constant between this calculation and experimental results agrees with each other very well. This comparison indicates that the new modified PES corrects the large barrier height problem in Wang and Bowman's old PES.     

Efficiency of methacrylate monolithic columns in reversed-phase liquid chromatographic separations

Butyl-methacrylate-based porous monoliths were prepared inside fused-silica capillaries as reversed-phase separation media for liquid chromatography (LC) and capillary electrochromatography (CEC). During our previous research on methacrylate-based monoliths for reversed-phase separations, we noticed that a separation efficiency of up to 300,000 plates/m can easily be obtained in the CEC mode for unretained compounds. However, the efficiencies for retained compounds were much lower in reversed-phase systems, especially in pressure-driven LC. In this work methacrylate-based columns were prepared and characterized in terms of efficiency and retention in reversed-phase (pressure-driven) LC and in CEC. Much attention has been paid to the mass-transfer mechanism in the stationary phase. Factors that affect the plate heights for specific compounds have been investigated. A possible explanation for the relatively low separation efficiency of retained compounds and suggestions to improve molecular mass transfer are provided.     

A novel method of protein extraction from perennial Bupleurum root for 2-DE

The perennial Bupleurum root is thick and woody and contains high levels of interfering compounds. Common protein extraction methods have proved refractory towards the isolation of proteins suitable for 2-DE, due to the presence of interfering compounds. A novel method for extracting proteins suitable for 2-DE was established to overcome these problems. The main characteristic of this protocol is the partitioning of the proteins into the aqueous (fraction A-2), chloroform and isoamyl alcohol phases (A-3), and the interphase (A-1). The proteins are then extracted from each of these phases. From A-1, 85% (extracted protein against total proteins) proteins could be extracted and purified. For fraction A-2, a novel phenol extraction step is employed for the extraction of proteins. Based on the well-resolved 2-DE patterns, our protein preparation is free of interfering compounds. Using these methods (A-1, A-2, and A-3-3), a total of 3662 (1526 + 1128 + 1008) spots could be separated, and a protein yield of about 1.41 mg per 1.0 g fresh root material was obtained. To our knowledge, this is the first time that a protocol for protein extraction from perennial Bupleurum root has been reported that gives reproducible results. The protocol is expected to be applicable to other recalcitrant plant tissues as well.     

有限厚度板穿透裂纹前缘附近三维弹性应力场分析

通过三维有限元计算来研究有限宽度、有限厚度含有穿透裂纹板的裂纹前缘应力场，从中找出应力强度因子与板的厚度、裂纹长度之间的关系，同时还分析了裂尖的三维约束程度和三维约束区的大小。分析结果表明：应力强度因子沿厚度的分布是不均匀的，应力强度因子的最大值及其位置与厚度有关；有限厚度板中面应力强度因子(KI)m-p及最大应力强度因子(KI)max均大于平面应力或平面应变的应力强度因子。对有限厚度裂纹问题，按平面应力或平面应变来考虑是不安全的；板中面的应力强度因子(KI)m-p及最大应力强度因子(KI)max是厚度B／a的函数；板的中面离面约束系数Tx最大，自由面(z=B)Tx=0。沿厚度方向裂尖附近的离面约束系数Tx也是z／B和B／a的函数，随着厚度的增加离面约束系数Tx增大，离中面越近离面约束系数Tx越大。Tx随着x的增大急剧减小，三维约束影响区域大小大约为板厚的一半，且裂纹长度a／W对应力强度因子沿厚度变化规律及Tx影响区域大小影响较小。     

EXTENSION OF POINCARÉ’S NONLINEAR OSCILLATION THEORY TO CONTINUUM MECHANICS (Ⅱ)-APPLICATIONS

This is a continuation of [1]. In [1] we suggested a method of direct perturbation of partial differential equation and weighted integration to calculate the periodic solution for continuum mechanics. In this paper, by using the above method we calculate the resonant and nonresonant periodic solutions of beam with fixed span and different boundary conditions and the resonant periodic solution of square plate under the action of concentrated periodic load. Besides, the influences of nonprincipal mode upon periodic solution and of static load upon amplitudefrequency curve are given.     

On the Three Phase Mixtures in Martensitic Transformations of Shape Memory Alloys: Thermodynamical Modeling and Characteristic Temperatures

We study here the thermally-induced martensitic transformation process of shape memory alloys. Taking the internal energy of phase mixtures as the potential function and introducing coherency energies between martensite and austenite and between different variants of the martensitic phase, we are able to use thermodynamical arguments to obtain hysteresis diagrams which could be measured experimentally. The characteristic temperatures for martensitic transformation, (martensite start and finish) and (austenite start and finish) can be identified explicitly and are closely related to the coherency parameters of the coherency energies. Received September 12, 1997     

One-pot synthesis,crystal structure,and fluorescence property of a cadmium(II) complex based on mono salicylaldehyde Schiff base ligand

A new cadmium(II) complex [Cd(NO₂-Salen)₂] containing Schiff base ligand (NO₂-Salen = N-mono-5-nitro-salicylideneamino ethanato) has been prepared through facile condensation reaction of sub-stituted salicylaldehyde with ethylene-diamine and has been structurally characterized by elemental analysis, IR spectra and X-ray diffraction. It is formulated as C₁₈H₂₀CdN₆O₆ crystallizes in the orthorhombic system, space group of Pccn. The ligand of 5-nitrosalicylaldehyde-ethylene-diamine exhibits unusual mono asymmetry tridentate mode. The Cd²⁺ ion has a coordination number of six and assumes a distorted octahedral geometry. It exhibits an offset π-π stacking interaction between the substituted benzene ligands of adjacent mononuclear complexes. The neutral monomeric units of [Cd(NO₂-Salen)₂] are linked into a one-dimensional (1D) array via the intermolecular hydrogen bonds and π-π stacking interactions. The complex exhibits strong emission in visible region with the maximum wavelength of 428 nm, which is tentatively assigned to the π → π* intraligand fluorescence.     

Effect of Electrical Contact on the Performance of Bi2S3 Single Nanowire Photodetectors

Bi₂S₃ single‐crystalline nanowires are synthesized through a hydrothermal method and then fabricated into single nanowire photodetectors. Due to the different contact barrier between the gold electrode and Bi₂S₃ nanowires, two kinds of devices with different electrical contacts are obtained and their photoresponsive properties are investigated. The non‐ohmic contact devices show larger photocurrent gains and shorter response times than those of ohmic contact devices. Furthermore, the influence of a focused laser on the barrier height between gold and Bi₂S₃ is explored in both kinds of devices and shows that laser illumination on the Au?Bi₂S₃ interface can greatly affect the barrier height in non‐ohmic contact devices, while keeping it intact in ohmic contact devices. A model based on the surface photovoltage effect is used to explain this phenomenon.     

Facile synthesis and luminescence properties of europium(III)-doped silica nanotubes

Photoluminescent nanomaterials had emerged as an amazing field in a wide range of applications during the past few decades. In this article, fibrous europium tartrates and photoluminescent silica nanotubes were conveniently synthesized by using sol–gel method, in which europium ions entered silica matrix. Scanning electron microscopy, transmission electron microscopy, X-ray diffraction analysis, fourier transform infrared spectra, energy-dispersive X-ray spectroscopy and photoluminescence (PL) spectra analysis were used to characterize the growth, structure, morphology and optical property of the products. The results indicated that europium tartrates nanofibers as a template can transform tetraethylorthosilicate into silica nanotubes effectively. Meanwhile, europium(III) was transferred from the fibers to the tubes successfully. A hard template mechanism was proposed to explain the formation process of europium(III)-doped silica nanotubes. Moreover, different morphologies of silica-based nanomaterials were obtained due to varying NH₄OH addition or stirring time. PL spectra from nanofiber and nanotube show a typical emission of europium(III), and 13 % is the quenching concentration of europium(III) in silica matrix for this system. The novel silica nanotubes can be applied potentially in optical and biological areas.