铁系元素冠醚配合物的研究——Ⅱ. 铁系氯化物与4''-碘苯并-15-冠-5固态配合物的合成与性质

对碱金属、希土与苯并-15-冠-5冠醚配合物的研究指出,4′-取代单苯并冠醚的阳离子配合物的稳定性及其他性质,受取代基电子效应的影响,给电性取代基可增加芳醚氧原子上的电子密度,改变冠氧的极性,从而影响其配位能力,扩大希土配合物之间性质上的差别,达到分离的目的。对于铁系元素,文献报导甚少。我们继Ⅰ之后,又合成了三氯化铁水合物与4′-碘苯并-15-冠-5固态配合物,并研究了其性质。     

基于多肽的电化学传感器在蛋白质检测中应用的研究进展

生物体内的细胞通常会分泌各种各样的蛋白质,这些蛋白质在生物体中发挥着重要作用,尤其是可被用于诊断各种疾病的发生和发展。多肽具有良好选择性、空间适应能力和识别灵活的特点,可与不同类型的蛋白分子形成非共价键,用于蛋白质的生物检测。将多肽与电化学生物传感器结合用于蛋白质的广谱检测具有良好的发展前景。本文介绍了多肽修饰的电化学传感器在不同蛋白质检测方面的研究进展,分析了待测蛋白质的不同对多肽修饰的电化学传感器分类的影响及其优缺点,提出了基于多肽的电化学传感器在不同蛋白质检测中存在的问题,并展望了其未来发展。     

Ultraviolet emission of ZnO nano-polycrystalline films by modified successive ionic layer adsorption and reaction technique

Zinc oxide (ZnO) nano-polycrystalline films were successfully prepared by modified successive ionic layer adsorption and reaction at room temperature technique which was based on the alternate immersion of substrate in the alkaline zinc precursor and deionized water. ZnO films were formed through accumulation of ZnO crystal clusters. The synthesis, microstructure, and optical properties of ZnO nano-polycrystalline films were investigated. Prepared ZnO films exhibited wurtzite structure, with good surface morphology and optical properties. Ethanolamine was employed as a complex reagent, which improved the adsorption of zinc complex with substrate. Effects of technique parameters on the properties of ZnO nano-polycrystalline films were studied in detail. Some parameters, including cycle number of preparation, ratio of zinc to ethanolamine, pH value of precursor and zinc concentration, played key roles in the deposition of ZnO nano-polycrystalline films. Intensive and sharp ultraviolet emission peaks at about 400 nm could be observed in the photoluminescence spectra.     

阻抗障碍物声散射的反问题

研究了从声散射场的远场分布的信息来再现声阻抗障碍物形状的反问题,建立了求解这类反问题的一种非线性最优化模型,并提出了数值实现该非线性最优化模型的一种两步调整迭代算法.两步过程的应用使在确定未知障碍物形状的非线性最优化步中未知函数的个数达到了最少,而在调整迭代过程中,通过利用前一迭代步所得重构信息,使重构精度得到了相当大的改进.所建立的反演算法的一个特别吸引人的性质是,只需要远场分布的一个Fourier系数即可对未知声阻抗障碍物作几何物形的设别.对大量具有各种几何形状的二维障碍物的数值算例保证了本算法是实用和有效的.     

Planarity relations for the sextic centrifugal distortion constants of triangular triatomic molecules

Four linearly independent linear combinations of the ten sextic centrifugal distortion coefficients of triangular triatomic molecules are presented. These combinations are formed in such a way that the resulting expressions depend only on the equilibrium geometry and the harmonic force field parameters of the molecule, quantities which are ordinarily known to considerably better precision than the sextic constants. The relations obtained thus constitute a set of planarity constraints on the ten sextic coefficients which arise in connection with the Nielsen-Amat expansion of the Darling-Dennison Hamiltonian. The planarity expressions can be utilized to effect a reduction of the sextic portion of the Hamiltonian.     

Vortex-creep activation energy in YBa2Cu3O7/PrBa2Cu3O7 superlattices

YBa₂Cu₃O₇/PrBa₂Cu₃O₇ (YBCO/PBCO) superlattices with a different ratio of the superconducting and insulating layer thicknesses were prepared by high pressure dc sputtering. The vortex-creep activation energy U₀ was determined by analyzing the in-plane resistive transition of 200 μm wide bridges with the external magnetic field B oriented along the c axis. It was found that U₀ is proportional to the thickness of the YBCO layers, and does only weakly depend on the PBCO layer thickness, when the latter exceeds two unit cells. We observed a change in the variation of U₀ with the current I in the specimen: U₀ exhibits a plateau in the low-I region, then decreases significantly with increasing I. This behaviour is explained in terms of a crossover plastic vortex creep – elastic (collective) creep induced by the transport current.     

Assessment of collagen-based materials which are supports of cultural and historical objects

The thermal degradation of collagen-based materials, viz. collagen, recently manufactured parchments and tanned leathers, a heritage parchment and patrimonial (historical) leathers, was investigated by thermal analysis methods. With progressive heating, all these materials exhibit three main successive processes, associated with dehydration, protein denaturation and pyrolysis/oxidation. The analysis of both denaturation and thermo-oxidation revealed significant differences between aged leather, collagen, recently manufactured parchments and tanned leathers in terms of the number of overlapping processes (reflected in the number of peaks recorded at denaturation) and of the oxidative degradation rates, given by the normalised curves of differential thermal gravimetry (DTG). The various observations are proposed as qualitative indices for assessing the age and storage conditions of leather. A three-phase model was used for explaining the results. This consists of crystalline collagen filaments that are embedded in an amorphous matrix with an interface zone between the crystalline and amorphous regions. Solid-state ¹H NMR investigations corroborate the thermal analysis results and enhance the understanding of the ageing processes.     

Stereospecific Oxycyanation of Alkenes with Sulfonyl Cyanide

Oxycyanation of alkenes would allow the direct construction of useful β-hydroxy nitrile scaffolds. However, only limited examples of such reactions have been reported, and some problems including limited substrate scope and the lack of diastereocontrol in the case of the oxycyanation of internal alkenes have arisen. We herein report on the intermolecular oxycyanation of alkenes using p-toluenesulfonyl cyanide (TsCN) in the presence of tris(pentafluorophenyl)borane (B(C₆F₅)₃) as a catalyst, affording products that contain a sulfinyloxy group and a cyano group at the vicinal position. The reaction features a stereospecific syn-addition. The reaction also shows a broad substrate scope with good functional group tolerance. Mechanistic investigations by experimental studies and density functional theory (DFT) calculations revealed that the reaction proceeds via an unprecedented stereospecific mechanism through the electrophilic cyanation of alkenes, in which B(C₆F₅)₃ efficiently activates TsCN through the coordination of the cyano group to the boron center.     

Determination of primary aromatic amines using immobilized nanoparticles based surface-enhanced Raman spectroscopy

Primary aromatic amines(PAAs) are substances with toxicity and suspected human carcinogenicity. A facile method for highly sensitive detection of PAAs using surface-enhanced Raman spectroscopy(SERS)is reported. The immobilization of Au nanoparticles(AuNPs) on the glycidyl methacrylate–ethylene dimethacrylate(GMA-EDMA) materials makes the substrate a closely packed but not aggregated AuNP arrays which provides a prominent SERS enhancement. Four PAAs with different substituent groups,namely, p-toluidine, p-nitroaniline, benzidine and 4,4-methylene-bis-(2-chloroaniline) have been successfully identified and quantified. High sensitivity and good linear relationship between SERS signals and concentrations of PAAs are obtained for all four PAAs.