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101.
Masaharu Okazaki Taizo Ono Kenji Komaguchi Nobuaki Ohta Haruhiko Fukaya Kazumi Toriyama 《Applied magnetic resonance》2009,36(1):89-95
Room temperature fluorine electron nuclear double resonance (ENDOR) has been successfully observed for several superstable
fluorocarbon radicals ·C(C2F4R)(i-C3F7)2 in solution. Three radicals were employed in which CF3, F, and O-c-C6F10SO3C2F5 were introduced as R, and all the hyperfine couplings (hfcs) obtained by ENDOR were assigned with the help of ESR simulation
and ab initio MO calculation. In case of ·C(i-C3F7)3 large 13C and considerable β-fluorine couplings suggest the nonplaner arrangement for the central and three carbons at the β-position, in spite of the
fact that all the methyl fluorine show the same hfc. Therefore, a rapid puckering motion along the C3 axis together with the methyl rotation should average the hfc’s of the 18 fluorine nuclei to give the same value. When one
of the CF3 groups is substituted with an F nucleus, the five CF3 groups give two hfc values, suggesting some dynamics still exists for the molecular frame. When a large group, O-c-C6F10SO3C2F5, is substituted for CF3, all the five CF3 groups become nonequivalent and the ENDOR signal becomes intensive and sharp even at 290 K, indicating that the molecular
frame becomes rigid. The relation between the ENDOR spectra of these systems and the intramolecular dynamics is discussed. 相似文献
102.
103.
We give some structure to the Brown–Peterson cohomology (or its p-completion) of a wide class of spaces. The class of spaces are those with Morava K-theory even-dimensional. We can say that the Brown–Peterson cohomology is even-dimensional (concentrated in even degrees) and is flat as a BP*-module for the category of finitely presented BP*(BP)-modules. At first glance this would seem to be a very restricted class of spaces but the world abounds with naturally occurring examples: Eilenberg-Mac Lane spaces, loops of finite Postnikov systems, classifying spaces of most finite groups whose Morava K-theory is known (including the symmetric groups), QS2n, BO(n), MO(n), BO, Im J, etc. We finish with an explicit algebraic construction of the Brown–Peterson cohomology of a product of Eilenberg–Mac Lane spaces and a general Künneth isomorphism applicable to our situation. 相似文献
104.
A metal-support interaction between Pd and various kinds of zeolite and metal oxide supports was studied, which were active in the catalytic combustion and selective reduction of NO. The acid-base properties of supports affected the oxidation state, structure and catalytic activity of Pd. The acid sites of zeolite played the role to anchor the dispersed PdO as evidenced by the dynamic structural change of Pd. It was found that the metal-support interaction is an important factor, affecting the oxidation state, structure and catalytic performance of Pd. 相似文献
105.
Adelir A Saczk Leonardo L Okumura Marcelo F De Oliveira Maria Valnice B Zanoni Nelson R Stradiotto 《Analytical sciences》2005,21(4):441-444
The cyclic voltammetric behavior of acetaldehyde and the derivatized product with 2,4-dinitrophenylhydrazine (DNPHi) has been studied at a glassy carbon electrode. This study was used to optimize the best experimental conditions for its determination by high-performance liquid chromatographic (HPLC) separation coupled with electrochemical detection. The acetaldehyde-2,4-dinitrophenylhydrazone (ADNPH) was eluted and separated by a reversed-phase column, C18, under isocratic conditions with the mobile phase containing a binary mixture of methanol/LiCl(aq) at a concentration of 1.0 x 10(-3) M (80:20 v/v) and a flow rate of 1.0 mL min(-1). The optimum condition for the electrochemical detection of ADNPH was +1.0 V vs. Ag/AgCl as a reference electrode. The proposed method was simple, rapid (analysis time 7 min) and sensitive (detection limit 3.80 microg L(-1)) at a signal-to-noise ratio of 3:1. It was also highly selective and reproducible [standard deviation 8.2% +/- 0.36 (n = 5)]. The analytical curve of ADNPH was linear over the range of 3-300 mg L(-1) per injection (20 microL), and the analytical recovery was > 99%. 相似文献
106.
A series of experiments were carried out to study the degradation of methylene blue by the irradiation of ultrasound onto TiO(2) in aqueous solution. A statistically significant decrease in the concentration of methylene blue was observed after 60 min irradiation. While the reduction was 22% of the initial concentration without H(2)O(2), addition of H(2)O(2) significantly enhanced the degradation of methylene blue for the TiO(2) containing system (85% reduction of the initial concentration). The addition of H(2)O(2) had no effect on the methylene blue degradation when the system contained Al(2)O(3). The degradation ratio of methylene blue was dependent on the amount of TiO(2) and also the specific surface area of TiO(2) in the solution. The effects of radical scavenging agents on the degradation of methylene blue were also investigated for the system with TiO(2). It was found that the radical scavenging agents dimethyl sulfoxide (DMSO), methanol, and mannitol suppressed the degradation, with DMSO being the most effective. The effect of pH on the degradation of methylene blue was further investigated. An U-shaped change in the concentration of methylene blue in the presence of TiO(2) was observed along with the change in pH values (pH 3-12), and the highest degradation ratio was observed at around pH 7. In conclusion, ultrasound irradiation of TiO(2) in aqueous solution resulted in significant generation of hydroxyl radicals, and this process may have potential for the treatment of organic dyes in wastewater. 相似文献
107.
Influence of the Solvent on the “Casting” Methodology for MWCNT‐Modified Glassy Carbon and Platinum Electrodes
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Ana Carolina Ângelo Dorim Herbert Aleixo Edilton de Souza Barcellos Leonardo Luiz Okumura 《Electroanalysis》2015,27(11):2663-2669
The choice of electrode material and surface preparation method are usually dictated by the suitability of the electrode to observe an electrochemical parameter, such as heterogeneous electron transfer rate, surface coverage, or redox potential. Thus, the glassy carbon (GC) and platinum (Pt) electrodes were modified with multiwalled carbon nanotubes (MWCNT) by direct “casting” modification using nine different aliquots of solvents. After drying at room temperature, the modified electrode showed distinct redox peaks corresponding to ferrocyanide oxidation/reduction. Using chemometrics, the cyclic voltammograms with higher current intensity were obtained for those in which ethanol, water and acetone as dispersing agents were used for GCE and dimethylformamide, water and acetone for Pt electrode modification. 相似文献
108.
109.
Vibronic Structures in Absorption and Fluorescence Spectra of Firefly Oxyluciferin in Aqueous Solutions
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Miyabi Hiyama Yoshifumi Noguchi Hidefumi Akiyama Kenta Yamada Nobuaki Koga 《Photochemistry and photobiology》2015,91(4):819-827
To elucidate the factors determining the spectral shapes and widths of the absorption and fluorescence spectra for keto and enol oxyluciferin and their conjugate bases in aqueous solutions, the intensities of vibronic transitions between their ground and first electronic excited states were calculated for the first time via estimation of the vibrational Franck–Condon factors. The major normal modes, overtones and combination tones in absorption and fluorescence spectra are similar for all species. The theoretical full widths at half maximum of absorption spectra are 0.4–0.7 eV and those for the fluorescence spectra are 0.4–0.5 eV, except for phenolate‐keto that exhibits exceptionally sharp peak widths due to the dominance of the 0–0′ or 0′–0 band. These spectral shapes and widths explain many relevant features of the experimentally observed spectra. 相似文献
110.