The luminescence of CaYBO4 : RE3+ (RE=Eu, Gd, Tb, Ce) in VUV-visible region

Phosphors CaYBO4:RE3+ (RE = Eu, Gd, Tb, Ce) were synthesized with the method of solid-state reaction at high temperature, and their vacuum ultraviolet (VUV)-visible luminescent properties in VUV-visible region were studied at 20 K. In CaYBO4, it is confirmed that there are two types of lattice sites that can be substituted by rare-earth ions. The host excitation and emission peaks of undoped CaYBO4 are very weak, which locate at about 175 and 350-360nm, respectively. The existence of Gd3+ can efficiently enhance the utilization of host absorption energy and result in a strong emission line at 314 nm. In CaYBO4, Eu3+ has typical red emission with the strongest peak at 610 nm; Tb3+ shows characteristic green emission, of which the maximum emission peak is located at 542 nm. The charge transfer band of CaYBO4:Eu3+ was observed at 228 nm; the co-doping of Gd3+ and Eu3+ can obviously sensitize the red emission of Eu3+. The fluorescent spectra of CaYBO4:Ce3+ is very weak due to photoionization; the co-addition of Ce3+-Tb3+ can obviously quench the luminescence of Tb3+.

基于电化学电容检测的新型钙离子传感器

通过金-硫共价键,将巯基十六羧酸以自组装的方式固定到金电极表面。再通过EDC、NHS的活化作用,对钙调蛋白的氨基与巯基十六羧酸暴露于自组装层外的羧基进行共价键和,从而将钙调蛋白固定到电极表面,制成一种新型的钙离子电容传感器。首先对传感器进行了等效电路分析,并分别考察了不同浓度电解质溶液对基底电容的影响,确定了进行实验所需的合适电解质浓度。用本实验室自行开发研制的电化学电容分析仪研究了该传感器对钙离子的响应能力,并进一步考察了其再生能力及稳定性。实验结果表明,在10-8~3×10-6mol/L的较宽范围内,钙离子浓度的对数值与总电容信号值之间呈线性关系,而且检出限可以达到10-9mol/L。制备好的传感器浸泡在0.02 mol/L,pH 7.0的磷酸缓冲溶液中在4℃冰箱中可以保存一个月而其对钙离子的响应能力未发现有显著的下降,说明其具有良好的稳定性。使用过的传感器用EDTA进行再生后基底电容的变化不超过0.3%,说明其具有良好的再生可...

微观结构对溶胶-凝胶法合成的La_(0.67)Sr_(0.33)MnO_3电磁性能影响

采用溶胶-凝胶法制备了不同烧结温度的钙钛矿类锰氧化物La0.67Sr0.33MnO3样品。实验结果表明,在1573 K以上烧结的样品,晶粒出现异常长大,晶界效应明显。随着烧结温度的提高,磁化强度逐渐增大,但样品的居里温度基本不变。此外,在1173和1573 K温度下烧结的样品,均出现了低于居里温度的金属-半导体导电行为转变。在合适的烧结条件下,可以观察到隧道磁电阻(TMR)和超大磁电阻(CMR)2种磁电阻效应。实验表明,自旋电子的输运,不仅与样品平均粒径的大小和密度有关,而且与晶界的微观结构有密切关系。

一种手性性质随不同金属离子改变的共轭聚合物

化学传感器能识别一种特殊分子或一类分子的分子装置 ,基于共轭聚合物的化学传感器的设计原理一般都是利用其分子的电子效应和空间构象的变化 [1～ 4] ,而旋光分子的手性同样与其电子和空间结构相关 .本文试图建立一种依靠化合物手性 (如旋光度 )的变化检测金属离子的新方法 .由于含手性联萘结构的共轭聚合物具有较好的旋光热稳定性和高的旋光值 [5,6] ,以及聚合物主链上联吡啶基团可与许多过渡金属离子配位[4,7] ,我们设计合成了一种同时含有联吡啶和手性联萘基团的共轭聚合物 .结果表明 ,不同过渡金属离子与聚合物联吡啶单元的作用可引起聚合物吸收和发射光谱的变化 ,同时导致聚合物手性的变化 .1　实验部分1.1　仪器与试剂　 1 H NMR谱用 d-氯仿作溶剂 ,用四甲基硅烷作内标在 Varian3 0 0 MHz核磁仪上测定 ;红外光谱用 Bioard FTS-7傅里叶变换红外谱仪测定 ;凝胶凝透色谱 (GPC)用聚苯乙烯作标准 ,四氢呋喃作洗脱剂 ,在 Waters5 10仪器上测定 ;旋光度用 Perkin Elmer3 41LC型旋光仪测定 ;紫外 -可见光谱用 Varian Cray 5 0光谱仪测定 ;...

Stereoselective polymerization of rac-lactide with a bulky aluminum/Schiff base complex

An aluminum/Schiff base complex {[2,2-dimethyl-1,3-propylenebis(3,5-di-tert-butylsalicylideneiminato)](isopropanolato)aluminum(III) (2)} based on a bulky ligand and aluminum isopropoxide was prepared and employed for the stereoselective ring-opening polymerization (ROP) of rac-lactide (rac-LA). The initiator was characterized with nuclear magnetic resonance (NMR), crystal structure measurements, and elemental analysis. It contained a five-coordinate aluminum atom that was trigonal bipyramidal in the solid state according to the crystal structure measurements. The two conformational stereoisomers of 2 exchanged quickly on the NMR scale. Compound 2 polymerized rac-LA into a crystalline polymer that was characterized with H-1 NMR, wide-angle X-ray diffraction, electrospray ionization mass spectrometry, and gel permeation chromatography. The kinetics of the polymerization were first-order in both the monomer and initiator, and there was a linear relationship between the rac-LA conversion and the number-average molecular weight of poly(rac-LA) with a narrow molecular distribution (1.04-1.08). These features showed that the polymerization was well controlled. The high melting temperature (196-201 degreesC) and isotacticity of poly(rac-LA) indicated that complex 2 was a highly stereoselective initiator for the ROP of rac-LA.

Sulfonated poly(arylene-co-naphthalimide)s synthesized by copolymerization of primarily sulfonated monomer and fluorinated naphthalimide dichlorides as novel polymers for proton exchange membranes

A novel sulfonated aromatic dichloride monomer was successfully prepared by the reaction of 2, 5-dichlorobenzophenone with fuming sulfuric acid. Copolymerization of this monomer in the form of sodium salt (1) with N-(4-chloro-2-trifluoromethylphenyl)-5-chloro-1,8-naphthalimide (2) or bis(N-(4-chloro-2-trifluoromethylphenyl)1,4,5,8-naphthalimide (3) generated two series of novel poly(arylene-co-naphthalimide) s I-x and II-x where x represents the content of the sulfonated monomer. The synthesized copolymers with the -SO3H group in the side chains possessed high molecular weights revealed by their high viscosity and the formation of tough and flexible membranes. The copolymers exhibited excellent stability toward water and oxidation due to the introduction of the hydrophobic CF3 groups. The sulfonated copolyimides that incorporated with 1,8-naphthalimide (I-x) exhibited better hydrolytic and oxidative stabilities than those with 1,4,5,8-naphthalimide. Copolymer I-50 membrane endured for more than 83 h in Fenton's reagent at room temperature. The mechanical properties of I-50 membrane kept almost unchanged after immersing membrane in boiling water for 196 h. The proton conductivities of copolymer films increased with increasing IEC and temperature, reaching values above 6.8 x 10(-1) S/cm at 80 degrees C.

Sudies on non-isothermal melt crystallization kinetics in PET/PEN/DBS blends

Macrokinetic models, namly the modified Avrami, Ozawa and Zibicki models, were applied to study the non-isothermal melt crystallization process of PET/PEN/DBS blends by DSC measurement. The modified Avrami model was found to describe the experimental data fairly well. With the cooling rates in the range from 5 to 20 K/min, Ozawa model could be well used to describe the early stages of crystallization. However, Ozawa model did not fit the polymer blends during the late stages of crystallization, because it ignored the influence of secondary crystallization. The crystallization ability of the blends decreases with increasing the DBS content from analysis by using Ziabicki kinetic model, which is similar to the results based on calculation of the effective energy barrier of the blends.

Synthesis, properties and structural characterization of an intermolecular photosensitive complex: (HGly-Gly)(3)PMo12O40 center dot 4H(2)O

The first heteropoly acid-dipeptide complex, (HGly-Gly)(3)PMo12O40.4H(2)O, was synthesized and characterized by elemental analysis, IR, UV, H-1 NMR and single crystal X-ray diffraction. The X-ray crystallographic study showed that the crystal structure was constructed from N-H...O and O-H...O hydrogen bonds among the (HGly-Gly)(+), H2O and PMo12O403- units. This structure represents a model interaction between polyoxometalates and proteins. The complex has photosensitivity under irradiation by sunlight. The fluorescent activity of this compound is also reported.

Relationship between chemical bond parameters and superconducting temperature in HgBa2Can-1CunO2n+2+delta (n=1, 2, 3, 4)

Bond covalency and valence of elements in HgBa2Can-1CunO2n+2+delta (n = 1, 2, 3, 4) were calculated and their relationship with T-c was discussed. For both oxygen and argon annealed samples, the results indicated that with the increase of n, the trend of bond covalency of Hg-O and Cu-O was the same or opposite compared with that of superconducting temperature. This may suggest that the magnitudes of Cu-O and Hg-O bond covalency are important in governing the superconducting temperature. For the highest T-c sample, Hg had the lowest valence, implying that lower valence of Hg was preferred in order to produce higher T-c. For fixed n, the valence of Cu in oxygen annealed samples was larger than that in argon annealed samples, indicating that oxygen annealed samples produced more carriers than argon annealed samples.

Study on the integrated membrane processes of dehumidification of compressed air and vapor permeation processes

Blend modified polyimide (PI) hollow fiber membranes were used in vapor permeation for gas phase dehydration of ethanol. Dry air sweeping operation was used and the dry air was supplied by a dehumidification membrane module of compressed air. An integrated membrane process was composed. The effects of some factors, such as the modification of membrane materials, the humidity and current velocity of sweeping air, the operation temperature, on the efficiency of dehydration were discussed.

两种ω-二茂铁羧酸的改进合成及其电化学行为

利用 Zn(Hg) /HCl分别对 3-二茂铁甲酰基丙酸和 4-二茂铁甲酰基丁酸进行 Clemmensen还原 ,在温和条件下高收率 (93%以上 )合成了 4-二茂铁丁酸和 5 -二茂铁戊酸。新的合成方法避免了文献中采用 40 5 .3k Pa H2 还原的苛刻条件。以FT-IR、1HNMR、13CNMR和 L D-MS确证了产物的结构。利用循环伏安技术研究了这两种 ω-二茂铁羧酸的电化学行为。

电喷雾串联质谱法鉴定桔梗皂苷D

改进了桔梗皂苷D的提取、分离及鉴定方法 .首次利用大孔树脂脱糖脱色及薄层硅胶作色谱系介质 ,并首次利用电喷雾质谱对目标化合物进行跟踪分析 ,使高纯度的目标化合物的分离和鉴定工作得以简化

Synthesis and crystal structure of a novel amino-acid-containing polyoxometalate: K-6[Cu (Ala)(2) (H2O)(2)](2)[ CU4 (H2O)(2) (AsW9O34)(2)] center dot 16H(2)O

The novel amino-acid-containing polyoxometalate Ka(6) [Cu(Ala)(2) (H2O)(2)](2) [Cu-4 (H2O)(2) . (AsW9O34)(2)] . 16H(2)O was synthesized from the reaction of K-10[Cu-4(H2O)(2)(AsW9O34)(2)] . 20H(2)O with beta -alanine, Its structure has been determined by single crystal X-ray diffraction. It crystallizes in the triclinic space group P (1) over bar, with a=1. 196 3(2) nm, b=1. 536 5(3) nm, c=1. 591 4(3) nm, alpha =93. 97(3)degrees, beta= 110. 88(3)degrees, gamma =101. 07(3)degrees, V=2. 651 8(9) nm(3) and Z=1. Least-squares refinement of the structure leads to R and R-w factors of 0. 067 3 and 0. 162 8, respectively. An unusual structural feature of the compound is that the polyanion [Cu-4(H2O)(2) (AsW9O34)](10-) is linked with the amino-acid complex of Cu2+ by a mu -oxygen atom.

稀土基汽车尾气催化剂的催化活性研究

利用浸渍法制备了一系列含Ce La稀土助剂改性的Pt Rh三效催化剂 ,采用各种表征手段和高温抗硫水热老化实验 ,考察了Ce La稀土对Al2 O3 载体的热稳定性和催化剂活性的影响 .研究结果表明 ,稀土La2 O3 的添加主要改善了载体Al2 O3 的高温高比表面性能 ;而CeO2 的引入则明显地提高了CO和NO的催化转化活性 ,但对HC的转化几乎无影响 ,也促进了催化剂的抗硫水热老化性能 ,并且显著地拓宽了催化剂的三效窗口 .这主要归因于CeO2的添加 ,它改善了催化剂上CO ,HC和NO间的相互作用以及CeO2 所特有的储氧功能