(R)-1，1′-联萘手性单元通过溶胶凝胶法合成杂化硅干凝胶(英)

Precursor molecule (R)-6,6′-bis(triethoxysilylethen-2-yl)-2,2′-di(methoxyethoxymethyloxy)-1,1′-binaphthyl (R-2) was synthesized by Pd-catalyzed Heck reaction of (R)-6,6′-dibromo-2,2′-di(methoxyethoxymethyloxy)-1,1′-binaphthyl (R-1) intermediate with vinyltriethoxysilane. The hydrolysis and polycondensation of the precursor R-2 produced the corresponding xerogel. Both precursor and xerogel were analysed by NMR, FTIR, UV, CD spectra, fluorescent spectroscopy, polarimetry and elemental analysis. The precursor and xerogel can emit strong blue fluorescence and are expected to have a potential application in the separation of chiral molecules as fluorescent sensor. The precursor exhibits strong Cotton effect in its circular dichroism (CD) spectrum indicating a highly rigid structure.     

Synthesis and magnetic properties of μ-phenolato copper (Ⅱ) binuclear complexes with different exogenous bridges

The syntheses and magnetic properties are reported for a series of copper(Ⅱ) complexes prepared from a pentadentate binucleating ligand 2,6-diformyl-4-methylphenol di(benzoyl-hydrazone) (H3L). These complexes incorporate different exogenous ions (X-) into a bridging position to form copper(Ⅱ) binuclear complexes of the formula [Cu2(H2L)X]2+, where X-= Br-(1), Cl-(2), HO-(3), C2H5O-(4) and C3H3N2- (5). The complexes have been characterized with variable temperature magnetic susceptibility (4.2-300 K) and the observed data were fit to those from a modified Bleaney-Bowers equation by least-squares method, giving the exchange integral 2J = -6.2 cm-1 for 1, -76.4 cm-1 for 2, -241.9 cm-1 for 3, -231.1 cm-1 for 4 and -343.8 cm-1 for 5. This suggested that there is an antiferromagnetic interaction between the Cu(Ⅱ) ions and the sequence of the effect of some exogenous bridging ligands on magnetic coupling is corresponding to that in spectrochemical series.     

酚醛基活性炭纤维孔结构及其电化学性能研究

利用水蒸汽活化法制备了酚醛基活性炭纤维(ACF-H2O), 对其比表面积、孔结构与在LiClO4/PC(聚碳酸丙烯酯)有机电解液中的电容性能之间的关系进行了探讨. 用N2(77 K)吸附法测定活性炭纤维的孔结构和比表面积, 用恒流充放电法和交流阻抗技术测量双电层电容器(EDLC)的电容量及内部阻抗. 研究表明, 在LiClO4/PC有机电解液中, ACF-H2O电极的可用孔径(d)应在0.7 nm以上. 随着活化时间的延长, ACF-H2O的孔容和比表面不断增大, 但微孔(0.7 nm ＜ d ＜ 2.0 nm)和中孔(d ＞ 2.0 nm)率变化很小, 活化过程中孔的延伸和拓宽同步进行, 但过度活化则造成孔壁塌陷, 孔容和比表面迅速下降. 因此, 除活化过度的样品外, 电容量随比表面积呈线性增长, 最高达到109. 6 F•g-1. 但中孔和微孔的孔表面对电容的贡献不同, 其单位面积电容分别为8.44 μF•cm-2和4.29 μF•cm-2, 中孔具有更高的表面利用率. ACF-H2O电极的电容量、阻抗特性和孔结构密切相关. 随着孔径的增大, 时间常数减小, 电解液离子更易于向孔内快速迁移, 阻抗降低, 电极具有更好的充放电倍率特性. 因此, 提高孔径和比表面积, 减少超微孔(d ＜ 0.7 nm), 是提高 EDLC能量密度和功率密度的重要途径. 然而仅采用水蒸汽活化, 只能在小中孔以下的孔径范围内进行调孔, ACF-H2O电极电容性能的提高受限.     

Ion Recognition and Analytical Application of a Fibroin Modified Electrode

A novel fibroin modified electrode with ion recognition was reported. The membrane with isoelectric point of pH 4.5, was modified on graphite and carbon fiber electrodes. The pH-responsive ion recognition of the modified electrode was investigated by use of some neurocompounds. The fibroin carbon fiber electrode has been used for in-vivo determination.     

羟基中环二胺接枝壳聚糖的合成与表征

以具有环氧活性基的壳聚糖与3-羟基-1，5-二氮杂环庚烷或3-羟基1，5-二氮杂环辛烷反应，合成了两种含羟基的氮杂冠醚壳聚糖衍生物，其组成及结构经元素分析，IR，X-射线粉末衍射及^13C NMR等方法确证。     

羧甲基壳聚糖/聚乙烯醇/甘油环氧树脂蛇笼型复合螯合膜的制备及对金属离子的吸附性能

以交联甘油环氧树脂交联的聚乙烯醇(PVA)为笼树脂，羧甲基壳聚糖(CCTS)为蛇树脂制备了具有蛇笼结构的复合螯合膜，研究了其对Cu^2 、Ni^2 、Pb^2 、Fe^3 、Zn^2 ，Hg”^2 、Cd^2 等金属离子的吸附性能，研究表明，该树脂对Cu^2 、Ni^2 、Pb^2 有较好的吸附性能，其中PVA是对Cu^2 的吸附的主要贡献者，而CCTS则是在对Ni^2 的吸附中起主要作用。该树脂可以用于含Cu^2 废水的处理。     

新颖双核钐硫酚化合物[(THF)3I2Sm(m-SAr)]2 (Ar = Ph, 4-Me2NC6H4)的合成与化合物[(THF)3I2Sm(m-S-4-Me2NC6H4)]2的晶体结构

Reactions of SmI2 in THF with ArSSAr produced two binuclear samarium thiolate complexes [（THF）3I2- Sm（μ-SAr）]2 [Ar=Ph （1）, 4-Me2NC6H4 （2）] in high yields. The structure of 2 was characterized by single crystal X-ray crystallography. The crystal of 2 belongs to the triclinic system with space group P 1 and a=0.95705（13） nm, b= 1.22287（14） nm, c= 1.26450（14） nm, a=64.194（11）°, B=78.491（13）°, y=76.176（12）°, V= 1.2860（3） nm^3, Z= 1,μ=4.783 mm^-1, Dc= 1.964 Mg/m^3, M= 1521.19, S= 1.046, R1=0.0358, wR2=0.0910. X-ray analysis revealed that 2 is a thiolate-bridged dimer in which each Sm atom adopts a distorted pentagonal bipyramidal coordi- nation geometry.     

新手性配体(QN)2AQN的合成及其催化肉桂酸甲酯的不对称氨羟化反应研究

在AlCl₃和多聚磷酸的存在下, 以邻苯二甲酸酐和对二氟苯为原料, 通过Friedel-Crafts和环化反应, 用改进的方法以60%的产率生成1,4-二氟蒽醌. 然后通过奎宁锂与1,4-二氟蒽醌的亲核取代反应得到新型手性配体(QN)₂AQN, 产率85%. 在氧化-供氮试剂N-氯代氨基甲酸苄酯存在下, (QN)₂AQN与OsO₄原位生成的催化剂在五种肉桂酸甲酯的不对称氨羟化反应中表现出优异的对映选择性(90%～96% ee)和一般至优秀的区域选择性(75∶25～98∶2), 产率50%～70%, 高于文献报道的结果. 该手性配体易于合成, 成本低廉, 用于催化不对称氨羟化反应, 可以制备光学活性的α-氨基酸酯类化合物.     

有机-无机纳米复合材料光谱与电子性质研究进展

有机-无机纳米复合材料的研究在当前纳米科学技术的发展中占有重要地位，开创了材料与催化科学研究的新纪元。自从10年前首次合成纳米孔无机材料MCM-41至今，该领域研究不断深入，已展现出广阔的应用前景。当客体有机分子分散于纳米孔道内部时，其分子性质将产生明显变化。本文结合作者近期研究成果，力图从实验与理论两方面阐明在纳米复合体系中客体分子性质变化的原因。     

Ionic Liquid Based Electrolyte with Mesoporous Silica SBA-15 as Framework for Quasi-solid-state Dye-sensitized Solar Cells

Quasi-solid-state electrolytes were fabricated with mesoporous silica SBA-15 as a framework material. Ionic conductivity measurements revealed that SBA-15 can enhance the conductivity of the quasi-solid-state electrolyte. The diffusion coefficients of polyiodide ions such as Ⅰ3ˉ and Ⅰ5ˉ which were confirmed by Raman spectroscopic measurement, were about twice larger than that of I-. The optimized photoenergy conversion efficiency of dye-sensitized solar cells （DSSC） with the quasi-solid-state electrolyte was 4.3% under AM 1.5 irradiation at 75 mW·cm^-2 light intensity.