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51.
A. V. Timoshok A. F. Bedilo A. M. Volodin 《Reaction Kinetics and Catalysis Letters》1996,59(1):165-171
Benzene dimer cation radicals were detected on sulfated zirconia at low temperature and benzene coverage. Two temperature regions for their transformations were observed. Below 473 K the radical concentration remained stable reflecting the amount of strong surface acceptor sites. Above 623 K it increased drastically. 相似文献
52.
提出了在四氢呋喃(THF)、H2O和乙醇三元体系中用一般的化学还原法在室温下制备高合金化Pt-Ru/CMK-3催化剂的新方法. 与在纯水中制得的商品化ETEK催化剂相比, 其Pt-Ru粒子的合金化程度高、平均粒径较小且相对结晶度低, 因此, 该催化剂对甲醇氧化的电催化活性远高于在纯水中制得的Pt-Ru催化剂. 高合金化程度的原因是H2PtCl6和RuCl3在THF、H2O和乙醇三元溶液体系中的起始还原电位相近. 此外, CMK-3以其规整的二维有序孔道结构, 为直接甲醇燃烧电池(DMFC)中电子和物质的传输提供了方便的路径, 其巨大的比表面积也为Pt-Ru 纳米粒子的均匀分散提供了良好的载体. 相似文献
53.
The oxidative polycondensation of 4-[(pyridin-3-ylimino)methyl]phenol (4-PIMP) with O2, H2O2, and NaOCl was studied in an aqueous alkaline medium between 50°C and 90°C. Oligo-4-[(pyridin-3-ylimino)methyl]phenol (O-4-PIMP)
prepared was characterized by 1H-NMR, 13C-NMR, FT-IR, UV-VIS, size-exclusion chromatography, and elemental and thermal analyses techniques. At the optimum reaction
conditions, the yield of O-4-PIMP was 18.9%, 39.4%, and 46.8% using H2O2, O2, and NaOCl oxidant, respectively. According to the TG analysis, the initial degradation temperature of O-4-PIMP was 218°C,
which was by 50°C higher than that of 4-PIMP. Thermal analyses of 4-PIMP and O-4-PIMP were carried out in N2 atmosphere at 15–1000°C. The highest occupied molecular orbital, the lowest unoccupied molecular orbital, and electrochemical
energy gaps of 4-PIMP and O-4-PIMP were determined from the onset potentials for n-doping and p-doping, respectively. Also, optical band gaps of 4-PIMP and O-4-PIMP were determined according to UV-VIS measurements. 相似文献
54.
Direct electrochemical and electrocatalytic behavior of hemoglobin (Hb) immobilized on glass carbon electrode (GCE) containing gelatine (Gel) films was investigated. The characteristics of Hb/Gel film modified GC electrode were performed by using SEM microscopy, UV-vis spectroscopy and electrochemical methods. The immobilized Hb showed a couple of quasi-reversible redox peak with a formal potential of −0.38 V (versus SCE) in 0.1 M pH 7.0 PBS. The formal potential changed linearly from pH 4.03 to 8.41 with a slope value of −52.0 mV pH−1, which suggested that a proton transfer was accompanied with each electron transfer (ET) in the electrochemical reaction. The Hb/gelatine/GCE displayed a rapid amperometric response to the reduction of H2O2 and nitrite. 相似文献
55.
rico Marlon de Moraes Flores Ana Paula Fleig Saidelles Eder Lisandro de Moraes Flores Mrcia Foster Mesko Mrcio Pozzobon Pedroso Valderi Luiz Dressler Celso Figueiredo Bittencourt Adilson Ben da Costa 《Microchemical Journal》2004,77(2):113-118
An alternative device for the direct solid analysis (DSA) for copper determination by flame atomic absorption spectrometry (FAAS) is proposed. Copper was directly determined in commercial medicinal plants used as dietary supplements. The determination of copper in solid samples by DSA–FAAS was made by using a conventional air–acetylene flame. Between 0.05 and 1.5 mg of each test, sample was weighed directly into a small polyethylene vial connected to the device used for solid introduction into the flame. Test samples were introduced into the flame as a dry aerosol using a T-quartz cell set between the burner and the optical path. The T-quartz cell has a slit in the superior part by which the solid aerosol passes to the flame. A transient signal, evaluated as integrated absorbance, is produced and it is totally integrated in 2 s. Background signals always presented absorbance values less than 0.1. It was found a characteristic mass of 0.8 ng Cu and absolute limit of detection of 1.2 ng (3 s), or 1.2 μg g−1 if a sample mass of 1 mg was used. Optimized conditions for air flow rate, flame stoichiometry, and so on were established as well. No excessive grinding of the samples was needed and samples with particle of size less than 80 μm were used throughout. No statistical difference between the results from the proposed system and those obtained by sample digestion and determination by conventional FAAS was observed. With the proposed procedure, more than 50 test samples can be analyzed in 1 h and it can be easily adapted to conventional spectrometers for FAAS. 相似文献
56.
Masafumi Kobayashi Tetsuya Inoguchi Takashi Iida Takashi Tanioka Hiroshi Kumase Yasushi Fukai 《Journal of fluorine chemistry》2003,120(2):2838-110
Direct fluorination of 1,3-dioxolan-2-one with elemental fluorine was successfully carried out to provide 4-fluoro-1,3-dioxolan-2-one, which was expected as an additive for lithium ion secondary battery. 4-Fluoro-1,3-dioxolan-2-one was also further fluorinated with elemental fluorine to give three isomers of difluoro derivatives by the same methodology. Another topic is the preparation of trifluoromethanesulfonyl fluoride, an intermediate of lithium battery electrolyte, by the reaction of methanesulfonyl fluoride with elemental fluorine. The use of perfluoro-2-methylpentane as a solvent gave satisfactory selectivity of trifluoromethanesulfonyl fluoride. 相似文献
57.
Chien-Hui Li Keh-Ying Hsu Teh-Chou Chang 《Journal of polymer science. Part A, Polymer chemistry》1993,31(5):1119-1124
Three series of polymers containing p-phenylene diacrylic group were prepared by direct polycondensation in the presence of diphenylchlorophosphate and pyridine. Series I was prepared from p-phenylene bis(acrylic acid) with various hydroquinones. Series II was prepared from p-phenylene bis (β-cyano acrylic acid) with methylhydroquinone. Series III was prepared from 3-methyl-4-aminophenol with p-phenylene bis(acrylic acid) or p-phenylene bis(β-cyano acrylic acid), respectively. The phase behavior of these polymers was studied by differential scanning calorimetry (DSC), optical polarizing microscopy equipped with a heating stage, and wide-angle x-ray diffraction (WAXD). It was found that these polymers, except IIIb , exhibit thermotropic liquid-crystalline properties and show threaded or Schlieren texture under the optical polarizing microscopic observation. Furthermore, the melting temperatures of these polymers were decreased in the range of 254–354°C by incorporating with p-phenylene diacrylic group into the main chain. © 1993 John Wiley & Sons, Inc. 相似文献
58.
59.
Ariel Fernández 《Theoretical chemistry accounts》1985,67(3):229-233
A structurally stable model of the standard adiabatic gradient field of the potential energy surface for certain pericyclic reactions is derived.These reactions are not subjected to the principles of orbital isomerism or to the Woodward-Hoffmann rules.Use is made of a principle established by Ariel Fernández and Oktay Sinanolu which precludes direct meta-IRC connections between transition states.It is shown that Jahn-Teller isomers of the singlet biradicals involved in the process are not interconvertible since the biradical configuration is not a transition state but a critical point with Hessian matrix with two negative eigenvalues.The topological features of the PES obtained by combinatorial methods are in full agreement with earlier results obtained from MINDO calculations. 相似文献
60.
Hans R. Kricheldorf Majdi Al Masri 《Journal of polymer science. Part A, Polymer chemistry》1995,33(15):2667-2671
Attempts were made to synthesize poly(ether-sulfone)s from aliphatic diols or bissilylated diols on the one hand, and 4,4′-dichlorodiphenylsulfone or 4,4′-difluorodiphenylsulfone on the other hand. The reaction conditions and the catalyst were varied. Polycondensations of silylated diols with 4,4′-difluorodiphenylsulfone and powdered K2 CO3 in N-methylpyr-rolidone proved to give the best results. Using silylated isosorbide and isomannide as mono-mers chiral poly(ether-sulfone)s were prepared. GPC measurements indicate weight-average molecular weights in the range of 27×103–200×103. © 1995 John Wiley & Sons, Inc. 相似文献