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41.
Grumelli DE Forzani ES Morales GM Miras MC Barbero CA Calvo EJ 《Langmuir : the ACS journal of surfaces and colloids》2004,20(6):2349-2355
The sulfonation of polyaniline (PANI) films by nucleophilic addition of sulfite ion has been controlled through the polymer oxidation state under electrochemical control. The process was monitored by in situ electrochemical quartz crystal microbalance (EQCM), and the polymer oxidation was accomplished by electrode potential steps in sulfite aqueous solutions. The nucleophilic addition of sulfite to PANI only takes place on the oxidized polymer. From the ratio of added mass to the injected charge, the degree of sulfonation has been obtained with a yield as high as 50%. It has been observed that the ion-exchange mechanism during the oxidation-reduction process in the resulting sulfonated polymer is analogous to the polymer produced by electrophilic sulfonation of polyaniline or by copolymerization of aniline with aminosulfonic acids, unlike the ionic exchange observed for unmodified PANI. 相似文献
42.
Two ferrates, K2FeO4 and BaFeO4, had been prepared and characterized by XRD, IR and SEM. The electrochemical tests of the samples were carried out in the voltage range of 0.8~2.0 V and current density of 0.5~3.0 mA·cm-2. The results indicated that performance of Zn-BaFeO4 battery was superior to that of Zn-MnO2 and Zn-K2FeO4 batteries. Nanometer SrTiO3 prepared by Sol-gel methode with different ratio was added to the BaFeO4 cathode in order to improve the discharge performance. The discharge capacity of the BaFeO4 cathode was increased from 224 mAh·g-1 to 246 mAh·g-1 by addition of 5% nanometer SrTiO3. The reason of enhancing BaFeO4 electrochemical performance was discussed. 相似文献
43.
以正硅酸乙酯(TEOS)为硅源,十六烷基三甲基溴化铵(CTAB)为表面活性剂,仲钨酸铵为钨源,采用水热晶化法一步合成了不同钨含量(以Si、W物质的量比nSi/nW表示)的WO3-MCM-48,然后经甲烷/氢气(V/V=1/4)混和气体程序升温还原碳化(TPC),制备出了WxC-MCM-48(x=1、2)催化剂,采用XRD、N2吸附-脱附和NH3-TPD对样品的结构进行了表征,用噻吩作为模型化合物,对WxC-MCM-48催化剂的加氢脱硫催化活性进行了评价。结果表明,在一定钨含量的条件下,WO3-MCM-48和WxC-MCM-48样品仍然保持MCM-48的三维立方有序介孔结构,nSi/nW=30~15时,碳化钨的物相为W2C;nSi/nW=7.5时,碳化钨为W2C和WC物相,WxC-MCM-48催化剂表现出了良好的加氢脱硫催化性能。 相似文献
44.
单核铁(Ⅲ)双卟啉配合物在溶液中的构象平衡及其对环己烷羟化反应的催化活性的影响 总被引:1,自引:0,他引:1
合成及表征了一系列以柔韧碳氢链相连不同长度的p/p型单核铁(Ⅲ)双卟啉配合物,以可见光谱首次观察到该系列配合物在氯仿溶液中开放式及闭合式构象的平衡,发现680nm处吸收峰强度与这种构象平衡有关,烷氧链越长,该吸收峰强度越大.利用该类配合物模拟了细胞色素P450单加氧酶对环己烷的羟化作用,催化结果表明,在以分子氧为氧源及还原剂存在的温和条件下,该类配合物的催化活性显著高于单核铁卟啉(FeTPPCl),随着柔韧碳氢链长度的增加,双卟啉的催化活性依次增加.高的催化活性与双卟啉配合物在溶液中的构象平衡,即闭合式构象引起的立体位阻及电子转移有关. 相似文献
45.
金属络合物的相转移催化分析与分离 总被引:2,自引:0,他引:2
以可简单分离回收、可反复使用为目标,详细介绍了相转移催化的变化发展过 程.通过对溶剂的选择,使得催化剂选择性地溶解在某一液相中,而使产物溶解在 另一液相中,如水-有机两相催化体系;通过温度的变化,简单地实现了在较高温 度下反应为均相体系以提高催化剂的活性,而在较低温度下实现了催化剂与产物不 相溶使得催化剂得以简单分离,如温控型水-有机两相催化体系、氟-有机两相催化 体系、温控型含氟催化剂、温控型有机金属催化剂等. 相似文献
46.
The paper shows the ability of the fluorochrome tris(2,2'-bipyridine) ruthenium (II) (Rubipy) to detect heparan sulfate, heparin, and heparinase activity of M3 murine mammary adenocarcinoma cells as well as bacterial heparinases I, II, and III in native polyacrylamide gel electrophoresis (PAGE). The technique is based on the electrophoretic mobility of high molecular weight heparins and subsequent staining with Rubipy (50 micrograms/mL). The minimum content of heparin detected by fluorescence in a UV transilluminator was 25-50 ng. The number of Rubipy molecules bound to heparin, determined in relationship to the number of disaccharide units (DU), showed that two to six heparin disaccharide units are bound by each fluorochrome molecule. Scatchard plot analysis showed one Rubipy-binding site (Kd = (8.56 +/- 2.97) x 10(-5) M). Heparinase activity was determined by densitometric analysis of the fluorescence intensity of the heparin-containing band of the gel. While heparinase I (EC 4.2.2.7.) degraded heparin and, to a lower degree, partially N-desulfated N-acetylated heparin (N-des N-Ac), heparinase II (no EC number) could efficiently degrade heparan sulfate (HS) and partially N-des N-Ac heparin. Finally, heparinase III (EC 4.2.2.8.) degraded HS almost exclusively. Only heparin and N-des N-Ac heparin were substrates for M3 tumor cell heparinases. We describe a qualitative, sensitive and simple method to detect heparinase activity and determine its substrate specificity using Rubipy fluorescence with heparin and heparan sulfate in multiple biological samples tested in parallel. 相似文献
47.
Pérez J Padilla A Herrebout WA Van der Veken BJ Hernández AC Bulanin MO 《The Journal of chemical physics》2005,122(19):194507
We report an experimental study of the rotovibrational fundamental PQR-band shapes in the IR absorption spectra of HCl dissolved in condensed rare gases in a wide range of temperatures. The effective vibrational frequencies are determined from analysis of the fine rotational structure partially resolved in the band wings. The central Q-branch components appear redshifted with respect to the effective vibrational frequencies, their shifts in different solvents found to match the HCl stretching mode shifts in binary Rg...HCl van der Waals heterodimers. Theoretical quasi-free rotor and modified rotor models are applied to describe evolution of the band profiles at changing thermodynamic conditions. Both models are shown to reproduce equally well the observed spectral density distributions in the band wings. However, the modified rotor formalism that accounts for depopulation of the lower-energy rotational solute states provides better agreement with the experiment in the range of the P- and R-branch maxima. We surmise that the Q branches separated from the measured spectral profiles are formed by transitions between rotationally hindered states of diatomic molecules coupled to the solvent by the local anisotropy of the interaction potential. 相似文献
48.
肝素化聚甲基硅氧烷-聚氧乙烯接枝物的合成及其体外抗凝血性能评价 总被引:5,自引:0,他引:5
以二甲基硅油接枝端羟基聚氧乙烯(PDMS g PEO OH)为基材,用二环己基碳二亚胺(DCCI)作脱剂,研究了羟基(OH)与肝素上的羧基(—COOH)之间的脱水缩合反应,制备出肝素化的抗血栓材料PDMS g PEO Hep,并对其涂覆表面的肝素含量和体外抗凝血性能进行了初步评价.实验结果表明,肝素接枝的共聚物具有优良的抗凝血性能和一定的应用前景. 相似文献
49.
Angel Alberola Luis Calvo Teresa Rodríguez Rodríguez Carmen Saudo 《Journal of heterocyclic chemistry》1992,29(2):445-450
The reactivity of 3-methyl-5-phenylisoxazole against electrophilic compounds in the presence of different bases is studied. With n-BuLi, alkylated products at C-4 position and C-3 methyl group, and, in a few cases, dialkylated isoxazoles are obtained. When the reactions are carried out with LICA, the nature of the alkylated products depends on the alkyl halide used. By using LICA-TMEDA, as deprotonating system, regio-selective reaction at the C-3 methyl group is found. 相似文献
50.
以硫醇为螯合剂, 在溶剂热条件下合成了两种层状硫代亚碲酸盐KAgTeS3 (1)和RbAgTeS3 (2). X射线单晶解析表明, 1和2是类质同晶化合物. 在晶体结构中, 银硫四面体通过共用顶点形成无限的平行链, 在相邻链中银硫四面体取向相反, 这些链与链由三角锥配位的碲互相连接形成阴离子层状结构, 阳离子在阴离子层间. 1的结晶学数据为: Mr=370.75, P21/c, a=0.73639(6) nm, b=1.06468(8) nm, c=0.85203(6) nm, β=106.4640(10)°, V=0.64062(8) nm3, Z=4, R(F)=4.44%, wR(F2)=11.66%. 2的结晶学数据: Mr=417.12, P21/c, a=0.75531(12) nm, b=1.07076(7) nm, c=0.8583(2) nm, β=106.497(6)°, V=0.66558(19) nm3, Z=4, R(F)=6.00%, wR(F2)=15.43%. DSC及紫外-可见漫反射光谱研究表明, 这两种化合物为半导体, 并具有很好的热稳定性. 相似文献