ZnSe及ZnSe/GaAs异质结构中压力导致的直接禁带向间接禁带的转变

用经验赝势方法计算了体ZnSe以及ZnSe/GaAs单异质结系统中ZnSe外延层г、X、L等特殊对称点导带底能量随压力的变化。结果表明，同Si、Ge、GaAs等半导体材料不同，ZnSe的X点导带底具有正的压力系数，但比г点的压力系数小，这是ZnSe材料以及ZnSe基异质结构材料发生直接禁带向间接禁带的转变时所需转变压力较大的根本原因。研究了ZnSe/GaAs异质结构中晶格失配造成的应变对外延层г、X、L对称点压力系数的影响，表明这种晶格失配造成的应变可以极大地减小ZnSe外延层材料由直接禁带向间接禁带的转变压力。     

相对论平均场理论中各种有效相互作用对中子星性质的影响

基于相对论平均场理论，研究了各种相互作用参数组(NL1、NL3、NLSH、TM1和GL-97)对中子星物质的性质和中子星整体结构的影响．发现参数组NL1、NL3和NLSH所给出的中子星内部的介子场强度、物质的组成比例、物态方程和中子星的整体特点基本相同，但与TM1和GL-97之间有较大的差别．相对于其他参数组，GL-97给出的介子场强度最弱，中子星的相对数密度最大，物态方程也最软，同时采用GL-97参数组计算的中子星的最大质量也最小．     

Range-Renewal Processes: SLLNs and Power Laws*

Given n samples(viewed as an n-tuple) of a γ-regular discrete distribution π,in this article the authors concern with the weighted and unweighted graphs induced by the n samples. They first prove a series of SLLN results(of Dvoretzky-Erd¨os’ type). Then they show that the vertex weights of the graphs under investigation obey asymptotically power law distributions with exponent 1 + γ. They also give a conjecture that the degrees of unweighted graphs would exhibit asymptotically power law distribu...     

Fluorescence decay and quenching of pyrene labeled on sulfonate polyelectrolytes in salt-free aqueous solutions

Fluorescence decay and quenching of pyrene labels on copolymers of 2-acrylamido-2-methylpropanesulphonic acid (AMPS) and N,N-dimethylacrylamide were observed in dilute salt-free aqueous solutions as a function of the mole fraction F_AMPS of AMPS from 0 to 0.896. Monoexponential decay was found for the samples of F_AMPS<0.35 and biexponential decay for the samples of F_AMPS>0.35. The fast decay component is 80%, and the averaged lifetime 〈τ〉 and lifetime τ₁ of the fast decay is decreased with increasing F_AMPS. Quenching efficiency of Cu²⁺, I⁻, CH₃NO₂, and dinitrobenzene to the pyrene label was investigated in the framework of Stern-Volmer plot. With increasing F_AMPS the quenching efficiency of Cu²⁺ is increased while that of I⁻ decreased. For the neutral quenchers, the quenching rate constant k_q increases when F_AMPS<0.449 then decreases, showing a decline of accessibility to the pyrene label. These results were interpreted consistently with the counterion condensation concept, where condensed counterions caused the polyelectrolyte chains to aggregate. The existence of less-polar “temporal aggregated domain” in highly charged polyelectrolytes appears to lead to the slower decay and lower accessibility of the pyrene labels.     

聚环氧乙烷(PEO)与聚醋酸乙烯酯(PVA)的共混研究

动态力学谱研究表明熔融共混PVA/PEO体系的无定形态中存在着纯PEO及PVA/PEO的相容或部分相容相。相容或部分相容相的T_g随共混物组成的变化远高于按照FOX方程的计算值。用结晶和分子间相互作用解释了这种对FOX方程的偏离。应用FTIR差示光谱技术对PVA/PEO共混物和PVA/DGDE浓溶液的研究证实了PVA分子链上酯基和PEO分子链存在着强的相互作用。     

THE PREPARATION AND STUDY ON THE NANO-TiO2/SILK FIBROIN COMPOSITE FILMS BY THE SOL-GEL METHOD

Based on the sol-gel technique using butyl titanate as oxide precursor, the regenerated SF (silk fibroin)/nano-TiO2 composite films were synthesized. Different amounts of butyl titanate to SF were used to verify this effect on the characteristics of the formed materials. Samples were characterized by thermogravimetric analysis, X-ray diffractometry, UV, AFM and FT-IR spectroscopy.The experimental results reveal that, compared to the pure silk fibroin films, the mechanical strength of these regenerated SF/nano-TiO2 composite films were increased and the dissolubility in water of SF/nano-TiO2 composite films in aqueous solution were decreased. The diameter of nano-TiO2 particle films was about 80nm through UV and AFM. The nano-TiO2 particles were well dispersed in the regenerated silk fibroin. It was found that the crystal structures of the composite films were transited from typical Silk Ⅰ to typical Silk Ⅱ by the XRD and FTIR. Furthermore, the crystallinity of the composite films was obviously improved. Through the TGA, it was demonstrated that the heat transition temperature of composite films was also enhanced.     

Fluorescence observations on complex formation between linear and hyperbranched polyelectrolytes in dilute aqueous solutions

The complexation between poly(ethylene imine) (PEI) and poly(2-acrylamido-2-methylpropanesulfonic acid) (PAMPS) or AMPS copolymers was investigated with the relative excimer emission intensity I_E/I_M of a cationic probe 1-pyrenemethylamine hydrochloride (PyMeA · HCl), fluorescence nonradiative energy transfer (NRET) I_Py/I_Np of naphthalene to pyrene labels, the fluorescence anisotropy r and I_E/I_M of pyrene labels. PEI was a hyperbranched weak polycation in acid solution, which formed complex with anionic polyelectrolytes due to the electrostatic attraction. The I_E/I_M of PyMeA · HCl probe decreased to zero, the intra-, intermolecular NRET I_Py/I_Np and I_E/I_M of pyrene labels on the AMPS copolymers reached their maxima when χ was increased from 0 to 2.4, which was defined as the mole ratio of the amino group in PEI to the AMPS group in the polyanion. These facts indicated the formation of nonstoichiometric complex of the oppositely charged polyelectrolytes when χ = 2.4 at the concentration much lower than their overlap concentrations. The intermolecular aggregate appeared as indicated by an increase in the intermolecular I_Py/I_Np and r with χ up to 2.4 due to neutralizing and hydrophobizing the polyelectrolytes and the bridging effect of the PEI chain bound on different polyanion chains. At high pH, PEI became a neutral polymer and did not bind with the AMPS anion to form the complex as illustrated by the constant value of r for the pyrene labels attached to the AMPS polyanion as that without addition of PEI. The amino group in PEI quenched pyrene and naphthalene emission, resulting a decrease in both I_Np and I_Py.     

Grignard condensation routes to 1,3‐disilacyclobutane‐containing cyclolinear polycarbosilanes

Alkylene‐ and arylene‐bridged cyclolinear polycarbosilanes (CLPCS) with 1,3‐disilacyclobutane (DSCB) rings incorporated in the main chain of the polymer were prepared by polycondensation between corresponding di‐functional DSCB derivatives and di‐Grignard reagents. Well‐defined, low molecular weight (M_n = 3–5K; DP = 17–26), hexylene‐ and phenylene‐bridged CLPCS polymers were obtained without appreciable ring opening of the DSCB rings. Large exothermic peaks were observed in the DSC for these CLPCSs, which indicated, along with the IR spectra, that crosslinking occurred on heating to about 250 °C via the ring opening of the embedded, alternating, DSCB rings. Moreover, PB‐CLPCS undergoes photochemically induced crosslinking on UV irradiation to form crosslinked polycarbosilane network films. The spin‐cast, cured, films of these CLPCSs exhibit relatively low dielectric constants and promising thermal and mechanical properties for applications in electronics, for example, directly UV‐photoimprinted low‐k dielectrics. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1547–1557     

ThH5: An Actinide-Containing Superhalogen Molecule

Thorium and its compounds have been widely investigated as important nuclear materials. Previous research focused on the potential use of thorium hydrides, such as ThH₂, ThH₄, and Th₄H₁₅, as nuclear fuels. Here, we report studies of the anion, ThH₅⁻, by anion photoelectron spectroscopy and computations. The resulting experimental and theoretical vertical detachment energies (VDE) for ThH₅⁻ are 4.09 eV and 4.11 eV, respectively. These values and the agreement between theory and experiment facilitated the characterization of the structure of the ThH₅⁻ anion and showed its neutral counterpart, ThH₅ to be a superhalogen. ThH₅⁻, which exhibits a C_4v structure with five Th−H single bonds, possesses the largest known H/M ratio among the actinide elements, M. The adaptive natural density partitioning (AdNDP) method was used to further analyze the chemical bonding of ThH₅⁻ and to confirm the existence of five Th−H single bonds in the ThH₅⁻ molecular anion.     

Higher alcohol synthesis over Cu-Fe composite oxides with high selectivity to C2+OH

Cu-Fe composite oxides were prepared by co-precipitation method and tested for higher alcohol synthesis from syngas. The selectivity to C2+OH and C6+OH in alcohol distribution was very high while the methane product fraction in hydrocarbon distribution was rather low, demonstrating a promising potential in higher alcohols synthesis from syngas. The distribution of alcohols and hydrocarbons approximately obeyed Anderson-Schulz-Flory distribution with similar chain growth probability, indicating alcohols and hydrocarbons derived from the same intermediates. The effects of Cu/Fe molar ratio, reaction temperature and gas hourly space velocity (GHSV) on catalytic performance were studied in detail. The sample with a Cu/Fe molar ratio of 10/1 exhibited the best catalytic performance. Higher reaction temperature accelerated water-gas-shift reaction and led to lower total alcohols selectivity. GHSV showed great effect on catalytic performance and higher GHSV increased the total alcohol selectivity, indicating there existed visible dehydration reaction of alcohol into hydrocarbon.