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61.
Polynuclear mixed‐valent nickel oxide and nickel hexacyanoferrate hybrid film was prepared on glassy carbon electrode by multiple scan cyclic voltammetry. The film growth was monitored using electrochemical quartz crystal microbalance (EQCM). The cyclic voltammogram of the nickel hexacyanoferrate film is characterized by single redox couple whereas nickel oxide/nickel hexacyanoferrate hybrid film exhibits two redox couples. Cyclic voltammetric features suggest that the charge transfer process in both films resembles that of surface‐confined redox species. In stronger basic solution (pH ≥9), nickel hexacyanoferrate film was gradually converted into nickel oxide film during potentiodynamic cycling. The peak potential of nickel oxide redox couple moved into more negative side with increasing pH of contacting solution whereas the peak potential of nickel hexacyanoferrate redox couple remains the same. Electrocatalytic behavior of hybrid film coated electrodes toward ascorbic acid, hydrazine and hydroxylamine was investigated using cyclic voltammetry technique. Analytical application of nickel oxide/nickel hexacyanoferrate hybrid film electrode was tested in amperometry and flow injection analysis. 相似文献
62.
Peiguang Zhou H. L. Frisch 《Journal of polymer science. Part A, Polymer chemistry》1992,30(12):2577-2585
We have synthesized and characterized the graft copolymer of polymethyl methacrylate (PMMA)-graft-polycarbonate urethane (PCU) (designated PMMA-g-PCU) and the fully gelled mutually crosslinked network composed of both PMMA and PCU (designated as PMMA-PCU-N). Unlike the previously synthesized one phase PCU/PMMA simultaneous interpenetrating polymer networks (IPN's), both of these new materials exhibited two distinct Tg's (from DSC and DMA studies) at all compositions which we have studied. The two-phase nature of the graft and network polymer was confirmed by TEM with domain sizes smaller than those found in the blends of the linear PCU and PMMA chains. In comparison with the corresponding IPN's, the PMMA-g-PCU and the PMMA-PCU-N were thermally less stable and had a lower ultimate strength. © 1992 John Wiley & Sons, Inc. 相似文献
63.
Min-Hsien Liu Cheng Chen Yaw-Shun Hong Chuan-Wen Liu 《Theoretical chemistry accounts》2005,113(1):35-41
Calculation methods, based on hybrid density-functional theory with the basis sets of B3LYP/ 6-311+G (2d, p)//B3LYP/6-31G(d, p)and B3LYP/6-31+G(d)//B3LYP/6-31G(d, p), were applied to determine the thermodynamic characteristics of various energetic nitro compounds. A parametric modification equation and the least-squares approach were used to identify 21 of the energetic research compounds. The atomization energies of these 21 compounds have an average relative error of 0.21–0.25% of the experimental values. The enthalpy (H f) and the Gibbs energy (G f) of formation have mean absolute errors of 10.8–11.4 kJ/ mol (2.6–2.7 kcal/mol) and 10.0–10.3 kJ/mol (2.4 kcal/ mol), respectively. The enthalpy and the Gibbs energy of formation obtained exceed those in the literature obtained by semiempirical calculations. The calibrated least-squares parameters and parametric equations were used to predict H f and G f for the five newly developed energetic nitro compounds for further applications.Acknowledgements. The authors would like to thank the National Science Council of the Republic of China for financial support of this work under grant no. NSC-91-2113-M-014-003. The National Center for High-Performance Computing providing the computation facility is also acknowledged. 相似文献
64.
Johansson A Håkansson M Jagner S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(18):5311-5318
Stereochemically labile copper and zinc complexes with the N,N'-dimethylethylenediamine ligand (dmeda) have been shown to be promising precursors for the total spontaneous resolution of chiral covalent networks. (N,N')-[Cu(NO3)2(dmeda)]infinity crystallises as a conglomerate and yields either enantiopure (R,R)-1 or enantiopure (S,S)-1. A mixed-valence copper(I/II) complex, [{Cu(II)Br2(dmeda)}3(Cu(I)Br)2]infinity (2), which crystallises as a pair of interpenetrating chiral (10,3)-a nets, is formed from CuBr, CuBr2 and dmeda. One net contains ligands with solely (R,R) configuration and exhibits helices with (P) configuration while the other has solely (S,S)-dmeda ligands and gives rise to a net in which the helices have (M) configuration. The whole crystalline arrangement is racemic, because the interpenetrating chiral nets are of opposite handedness. With zinc chloride (R,S)-[ZnCl(dmeda)2]2[ZnCl4] (3) is obtained, which is a network structure, although not chiral. Total spontaneous resolution of stereochemically labile metal complexes formed from achiral or racemic building blocks is suggested as a viable route for the preparation of covalent chiral networks. Once the absolute structure of the compound has been determined by X-ray crystallography, a quantitative determination of the enantiomeric excess of the bulk product can be undertaken by means of solid-state CD spectroscopy. 相似文献
65.
Gaston Bocaz-BeneventiRosa Latorre Marta FarkováJosef Havel 《Analytica chimica acta》2002,452(1):47-63
The application of the combination of experimental design (ED) and artificial neural networks (ANNs) for the quantification of overlapped peaks in capillary zone electrophoresis is described. When the total separation cannot be achieved by separation techniques, the use of ED-ANN can be a suitable approach. The unstability of EOF causes peak shift that has to be corrected in order to apply ED-ANN methods. In this work, normalization procedure of electropherograms with consequent application of ANNs for quantification purpose was developed. Both, spectra and electropherograms can be used as multivariate data. In general, both kinds of data were found to be suitable for unresolved peaks quantification by ED-ANN approach. 相似文献
66.
研究了直流电场对含LiClO4的聚氧化乙烯(PEO)400与环氧树脂形成的液晶态互穿网络高分子忆禽子导体的电导率的影响。在室温至90℃范围内,电导率随外加电压增加面降低。外加电压越高,对电导率变化的影响越大。 相似文献
67.
68.
Bo Jiang Lixing Yang Yong Zhou Guanglin Huang Libin Lin 《Radiation Physics and Chemistry》2002,63(3-6):469-473
The radiation-induced hybrid polymerization in the presence of the N-alkoxypyridinium salt having relatively stable nonnucleophilic anion (PF6−) has been investigated in the paper. Based on the analysis of experimental data and the GPC spectrum, the onium salts not only oxidize -alkoxyalkyl radicals, produced from IBVE in dichloromethane by irradiation, to the corresponding cations, but also give nonnucleophilic anions PF6− for the polymerization system. The experimental results clearly demonstrate that free radical and cationic polymerization mechanisms occurred simultaneously in IBVE/EMP+PF6−/CH2Cl2 systems on irradiation with γ-ray. 相似文献
69.
Two series of interpenetrating sulfonic acid resins (ISAR), 10×n and n×10, were prepared by means of the wet method, and the physicochemical, thermodynamic and kinetic properties of the ISAR were measured. The results show: 10×n resins exhibit better properties than n×10 ones, mainly in higher apparent degree of crosslinking and larger conformational entropy effect, among which, 10×1 resin exhibits the best thermodynamic and kinetic properties. In the DTA graphs of n×10 resins, there are two T_g and two T_(ox), but in those of 10×n, only one T_g and one T_(ox). This result well supports the conclusion that 10×n resins have much better interpenetrating structural aspects. 相似文献
70.
Karim Adil Gilles Dujardin Marc Leblanc Vincent Maisonneuve 《Journal of fluorine chemistry》2004,125(11):1709-1714
Tren amine cations and carbonate anions adopt a ternary symmetry while tetra amine cations are tetrahedral. The symmetry of these constitutive ions influences strongly the nature of the solids which crystallise from solutions. Large fluorinated aluminate polyanions with tetrahedral symmetry appear in the presence of tren amine, while infinite chains of AlF6 octahedra are observed with tetra amine and that noncentrosymmetric structures are frequently encountered in rare earth fluoride carbonates. 相似文献