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51.
Adschiri Tadafumi Hakuta Yukiya Sue Kiwamu Arai Kunio 《Journal of nanoparticle research》2001,3(2-3):227-235
Hydrothermal synthesis of CeO2 and AlO(OH) were conducted using a flow type apparatus over the range of temperature from 523 to 673 K at 30 MPa. Nanosize crystals were formed at supercritical conditions. The mechanism of nanoparticle formation at supercritical conditions was discussed based on the metal oxide solubility and kinetics of the hydrothermal synthesis reaction. The reaction rate of Ce(NO3)3 and Al(NO3)3 was evaluated using a flow type reactor. The Arrhenius plot of the first order rate constant fell on a straight line in the subcritical region, while it deviated from the straight line to the higher values above the critical point. The solubility of Ce(OH)3 and AlO(OH) was estimated by using a modified HKF model in a wide range of pH and temperature. In acidic conditions, where hydrothermal synthesis reaction is concerned, solubility gradually decreased with increasing temperature and then drastically dropped above the critical point. The trend of the solubility and the kinetics around the critical point could be explained by taking account of the dielectric constant effect on the reactions. There are two reasons why nanoparticle are formed at supercritical conditions. Larger particles are produced at subcritical conditions due to Ostwald ripening; that could not be observed in supercritical water because of the extremely low solubility. Second reason is the faster nucleation rate in supercritical water because of the lower solubility and the extremely fast reaction rate. 相似文献
52.
Shun‐ichi Kawahara Chojiro Kojima Kazunari Taira Tadafumi Uchimaru 《Helvetica chimica acta》2003,86(10):3265-3273
trans‐Hydrogen‐bond hyperfine splitting via magnetic interaction, which is observed as J‐coupling in NMR experiments, was theoretically studied. trans‐Hydrogen‐bond hyperfine splitting should be closely related to the orbital interaction between the lone‐pair orbital of the H‐bond acceptor and the antibond orbital of the H‐bond donor. A linear relationship was observed between magnetic interaction hyperfine splitting through a H‐bond and the H‐bond strength. The relationship was dependent on the type of the nucleus forming the H‐bond; linear correlation was observed in N H⋅⋅⋅O/N type or O H⋅⋅⋅N type H‐bonded complexes, but not in O H⋅⋅⋅O type H‐bonded complexes. 相似文献
53.
Kenji Kawada Akinori Arimura Tatsuo Tsuri Masahiro Fuji Tadafumi Komurasaki Shuji Yonezawa Akira Kugimiya Nobuhiro Haga Susumu Mitsumori Masanao Inagaki Takuji Nakatani Yoshinori Tamura Shozo Takechi Teruhiko Taishi Junji Kishino Mitsuaki Ohtani 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》1998,110(7):1015-1017
54.
Kenji Kawada Akinori Arimura Tatsuo Tsuri Masahiro Fuji Tadafumi Komurasaki Shuji Yonezawa Akira Kugimiya Nobuhiro Haga Susumu Mitsumori Masanao Inagaki Takuji Nakatani Yoshinori Tamura Shozo Takechi Teruhiko Taishi Junji Kishino Mitsuaki Ohtani 《Angewandte Chemie (International ed. in English)》1998,37(7):973-975
Regioselective halogenations and Suzuki reactions ensure proper linkage of the aromatic rings in two total syntheses of terprenin ( 1 ). Both routes make it possible to prepare 1 efficiently and in large quantity. 相似文献
55.
Kodai Murai Tadafumi Daitoku Takashi Tsuruda 《Proceedings of the Combustion Institute》2021,38(3):3987-3994
In this research, microscopic visualization of pyrolysis in woody biomass was conducted by using the BL20B2 beamline at “SPring-8,” a large synchrotron radiation facility. Changes in shape and internal structure of the woody biomass were visualized by ultra high-speed CT. The samples were made of Japanese cypress wood; they had a height and a diameter of 5 mm. We used radiation as the heat source to achieve a high heat flux. When the heat flux was high, the samples expanded. Gaps were observed inside the samples. By comparing our results with the experimental results obtained under a low heat flux in a previous study, we could observe an entirely different aspect. Considering that the increase in pressure due to the rapid generation of pyrolysis gas created gaps in the samples, the samples were drilled, and experiments were performed on them. The hole in the center of the wood alone did not create an escape route for the pyrolysis gas, and the pyrolysis behavior was the same as that observed in the unprocessed wood. 相似文献
56.
Hirokazu Hayashi Masahide Takano Haruyoshi Otobe Tadafumi Koyama 《Journal of Radioanalytical and Nuclear Chemistry》2013,297(1):139-144
Curium trichloride was synthesized by the solid state reaction of curium nitride with cadmium chloride heated up to 748 K in a dynamic vacuum. The product was hexagonal 244CmCl3, of which lattice parameters were determined to be a = 0.7385 ± 0.0005 and c = 0.4201 ± 0.0005 nm. The melting temperature of the 244CmCl3 sample was determined to be 970 ± 3 K by differential thermal analyses using a gold crucible. These values are close to those reported in literature. The results show that mg-scale CmCl3 samples for thermochemical measurements were prepared from the purified oxide sample without the use of corrosive reagents. 相似文献
57.
Takafumi Sato Tadafumi Adschiri Kunio Arai 《Journal of Analytical and Applied Pyrolysis》2003,70(2):735-746
The decomposition of 2-propylphenol (PP) at 673 K and a water density of 0–0.5 g cm−3 yielded 2-isopropylphenol (IPP), phenol and 2-cresol. Gas products were methane, carbon dioxide, ethylene and propene. The decomposition was found to occur through rearrangement and alkylation, that is, (1) rearrangement of the propyl functional group from PP to IPP, (2) dealkylation of PP to phenol, (3) dealkylation of PP to 2-cresol. The decomposition probably occurred by a free-radical mechanism. The reaction rate constants of each pathway were determined and it was found that these were invariant over all the water densities studied at the given temperature. 相似文献
58.
Sciji Tsuzuki Tadafumi Uchimaru Kazutoshi Tanabe 《Journal of Molecular Structure》1993,280(2-3):273-281
The intermolecular interaction potential of the H2-H2 system was calculated by an ab initio molecular orbital method using several basis sets (up to 6-31 lG(3pd)) with inclusion of the electron correlation correction of the Møller-Plesset perturbation method and the basis set superposition error (BSSE) correction of the counterpoise method in order to evaluate the basis set effect. The calculated interaction energies depend strongly on the basis set used. Whereas the interaction energies of the repulsive and coulombic energy components calculated at the Hartree-Fock level are not affected by a change of basis set, the dispersion energy component depends strongly on the basis set used. Parameters of an exp-6-1 type non-bonding interaction potential were optimized on the basis of the MP4(SDTQ)/6-311G(3p) level intermolecular interaction energies of the H2-H2 system. 相似文献
59.
Transparent CoAl2O4 hybrid nano pigment by organic ligand-assisted supercritical water 总被引:1,自引:0,他引:1
Rangappa D Naka T Kondo A Ishii M Kobayashi T Adschiri T 《Journal of the American Chemical Society》2007,129(36):11061-11066
Transparent types of inorganic pigments are important as they can be used in a variety of applications, such as metallic finishing, contrast enhancing luminescent pigments, high-end optical filters, and so on. Currently, the difficulty in producing monodisperse and stable binary metal oxide nano pigments at low temperature hampers the applicability and realization of transparent blue nano pigments. Here, for the first time, we report organic ligand capped CoAl2O4 hybrid transparent nano pigment, which has a particle size less than 8 nm with well-stabilized single nanocrystals, using organic ligand-assisted supercritical water as the reaction medium. The organic ligand capping could effectively inhibit the particle growth and also control the size of nanocrystals. This helps to diminish the scattering effect of the nano blue pigment, realizing a transparent cobalt blue nano pigment without any postheat treatment. 相似文献
60.
Hayashi Y Gotoh H Honma M Sankar K Kumar I Ishikawa H Konno K Yui H Tsuzuki S Uchimaru T 《Journal of the American Chemical Society》2011,133(50):20175-20185
Diphenylprolinol silyl ether was found to be an effective organocatalyst for promoting the asymmetric, catalytic, intramolecular [6 + 2] cycloaddition reactions of fulvenes substituted at the exocyclic 6-position with a δ-formylalkyl group to afford synthetically useful linear triquinane derivatives in good yields and excellent enantioselectivities. The cis-fused triquinane derivatives were obtained exclusively; the trans-fused isomers were not detected among the reaction products. The intramolecular [6 + 2] cycloaddition occurs between the fulvene functionality (6π) and the enamine double bond (2π) generated from the formyl group in the substrates and the diphenylprolinol silyl ether. The absolute configuration of the reaction products was determined by vibrational circular dichroism. The reaction mechanism was investigated using molecular orbital calculations, B3LYP and MP2 geometry optimizations, and subsequent single-point energy evaluations on model reaction sequences. These calculations revealed the following: (i) The intermolecular [6 + 2] cycloaddition of a fulvene and an enamine double bond proceeds in a stepwise mechanism via a zwitterionic intermediate. (ii) On the other hand, the intramolecular [6 + 2] cycloaddition leading to the cis-fused triquinane skeleton proceeds in a concerted mechanism via a highly asynchronous transition state. (iii) The fulvene functionality and the enamine double bond adopt the gauche-syn conformation during the C-C bond formation processes in the [6 + 2] cycloaddition. (iv) The energy profiles calculated for the intramolecular reaction explain the observed exclusive formation of the cis-fused triquinane derivatives in the [6 + 2] cycloaddition reactions. The reasons for the enantioselectivity seen in these [6 + 2] cycloaddition reactions are also discussed. 相似文献