Effect of the pore surface modification of an inorganic substrate on the plasma‐grafting behavior of pore‐filling‐type organic/inorganic composite membranes

We have investigated the effect of the surface state and surface treatment of the pores of an inorganic substrate on the plasma‐grafting behavior of pore‐filling‐type organic/inorganic composite membranes. Shirasu porous glass (SPG) was used as the inorganic substrate, and methyl acrylate was used as the grafting monomer. The grafting rate increased as the density of silanol on the SPG substrate increased. This result suggests that radicals are generated mainly at the silanol groups on the pore surface by plasma irradiation. The SPG substrates were treated with silane coupling agents used to control the mass of organic material bonded to the pore surface. The thickness of the grafted layer became thinner as the mass of organic material bonded to the pore surface of SPG increased. This decrease in the thickness of the grafted layer could be explained by the decrease in the penetration depth of vacuum ultraviolet rays contained in plasma having a wavelength of less than 160 nm that generated radicals in the pores of the substrate. The thickness of the grafted layer inside the SPG substrates could be controlled through the control of the mass of organic material bonded to the pore surface of the SPG substrate. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 846–856, 2006     

Investigation of sulfonated poly(ether ether ketone sulfone)/heteropolyacid composite membranes for high temperature fuel cell applications

The sulfonated poly(ether ether ketone sulfone) (SPEEKS)/heteropolyacid (HPA) composite membranes with different HPA content in SPEEKS copolymers matrix with different degree of sulfonation (DS) were investigated for high temperature proton exchange membrane fuel cells. Composite membranes were characterized by Fourier transfer infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). FTIR band shifts suggested that the sulfonic acid groups on the copolymer backbone strongly interact with HPA particles. SEM pictures showed that the HPA particles were uniformly distributed throughout the SPEEKS membranes matrix and particle sizes decreased with the increment of copolymers' DS. The holes were not found in SPEEKS‐4/HPA30 (consisting of 70% SPEEKS copolymers with DS = 0.8 and 30% HPA) composite membrane after composite membranes were treated with boiling water for 24 h. Thermal stabilities of the composite membranes were better than those of pure sulfonated copolymers membranes. Although the composite membranes possessed lower water uptake, it exhibited higher proton conductivity for SPEEKS‐4/HPA30 especially at high temperature (above 100 °C). Its proton conductivity linearly increased from 0.068 S/cm at 25 °C to 0.095 S/cm at 120 °C, which was higher than 0.06 S/cm of Nafion 117. In contrast, proton conductivity of pure SPEEKS‐4 membrane only increased from 0.062 S/cm at 25 °C to 0.078 S/cm at 80 °C. At 120 °C, proton conductivity decreased to poor 0.073 S/cm. The result indicated that composite membranes exhibited high proton conductivity at high temperature. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1967–1978, 2006     

基于褐藻酸钠-纳米金复合物作非酶标记的新型电化学免疫传感器的研制

比较了用三碘甲状腺氨酸抗体(T3抗体)、褐藻酸钠(AS)标记T3抗体及褐藻酸钠-纳米金复合物(ASN)标记的T3抗体,在通过免疫反应结合到免疫电极表面后,引起的电极表面微环境发生改变的程度;用Fe(CN)3-/4-6为电化学探针,用循环伏安法获取金电极表面微环境改变的电流信息来检测 T3抗体,检测的线性范围为100～1 600ng·ml-1,检出限为45ng·ml-1.     

非线性光学材料──水草酸铵

一水草酸铵（简称ＡＯＭ）是一种优良的电光晶体￣［１］。文献￣［１，２］报道了该晶体的晶体结构，化学式为（ＮＨ＿４）＿２Ｃ＿２Ｏ＿２·Ｈ＿２Ｏ，属正交晶系，Ｐ２２２空间群，晶胞参数ａ＝０．８０３５ｎｍ，ｂ＝１。０３１ｎｍ，ｃ＝０．３８０１ｎｍ，ｚ＝２。本文拟报道ＡＯＭ单晶生长，热化学分析，透过波段以及非线性光学性质的初步研究。     

Some developments in reaction and solution microcalorimetry,with particular reference to its use in biochemistry and cellular biology

The field of isothermal microcalorimetry as applied to systems of interest for aqueous solution chemistry, biochemistry and in cellular biology is briefly reviewed. Some techniques recently developed in the author's laboratory are described.     

二芳基乙烯类光致变色材料的合成概述

由于具有多种潜在的应用价值, 光致变色化合物作为高级功能材料的研究在国内外广受关注. 在众多的有机光致变色化合物中, 二芳基乙烯特别是二噻吩乙烯, 由于其具有良好的热稳定性和优良的耐疲劳度而成为这类化合物的杰出代表. 近年来, 有关二芳基乙烯类光致变色化合物的各种合成及性能方面的报道已涉及到信息存储、分子开关、逻辑电路、液晶显示、磁性材料等众多领域. 主要是从有机合成的角度, 对这类材料的合成进行了较为全面的概括, 对各种合成方法分别加以介绍和分析, 对其发展趋势予以探索和展望.     

Theq-harmonic oscillator and the Al-Salam and Carlitz polynomials

One more model of aq-harmonic oscillator based on theq-orthogonal polynomials of Al-Salam and Carlitz is discussed. The explicit form ofq-creation andq-annihilation operators,q-coherent states and an analog of the Fourier transformation are established. A connection of the kernel of this transform with a family of self-dual biorthogonal rational functions is observed.     

Comprehensive DFT and MO studies on glyoxilic acid oxime and related ions in gas phase and solution: Conformations,basicities and acidities

Density functional (BLYP, B3LYP and BHLYP) and highly correlated MP2 and CCSD(T) calculations have been performed to investigate conformers, energy barriers, intramolecular H-bond strength, gas-phase basicity and deprotonation energies of glyoxilic acid oxime (gao) and related ions in gas phase and in aqueous solution (SCRF-PCM method). BHLYP/6-311G(d,p) and B3LYP/6-31++G(d) predictions for the global minimum conformer of gao were consistent with experiment. BLYP level overestimated the H-bond and stabilized incorrectly the H-bonded conformer. The calculations in solution indicated destabilization of H-bonded conformers due to the small polarizability and weaken of the H-bond. The same global minimum structures in gas phase and aqueous solution were found for gao-neutral (ectt) and gao-dianion (e⁻²), whereas they were different for gao-anion because of the strong decrease of the conformational energies in solution. The global minimum structures of the neutral, anion and dianion of gao, obtained in solution, are in agreement with experiment. The gas-phase basicity (GB) and molecular electrostatic potential (MEP) calculations revealed the same sites for electrophilic attack, supported by the nature of HOMO: the carbonylic oxygen for the neutral, the carboxylic oxygen for the anion and the oxime nitrogen for the dianion. MEP results in gas phase and in solution suggested a region between the two atoms, but not on one atom in accordance with bidentate binding of gao ions to a metal. The BHLYP/6-31++G(d,p) molecular properties of gao were in best consistent with CCSD(T) results. The thermodynamical properties (GB and bond deprotonation energy) of gao were better estimated at B3LYP level.     

电化学合成铜配合物的研究

采用金属铜为"牺牲"阳极,首次在无隔膜电解槽中,电化学溶解金属铜一步制备了纳米CuO前体Cu(OEt)2, Cu(OBu)2, Cu(acac)2, Cu(OEt)(acac), Cu(OBu)(acac) (acac为乙酰丙酮基).产物通过红外光谱(FT-IR)、拉曼光谱(Raman spectrum)进行表征.同时讨论了影响电合成铜醇盐及其配合物的关键因素.实验表明,防止阳极钝化,温度控制在30～50 ℃,采用有机胺溴化物为导电盐, 电极电位控制在0.8～1.2 V之间,可以提高电合成效率.实验同时表明Cu(acac)2, Cu(OEt)(acac), Cu(OBu)(acac)可作为制备含铜纳米材料前驱体.