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11.
Keitaro Yoshihara Yutaka Nagasawa Arkadiy Yartsev Shigeichi Kumazaki Hideki Kandori Alan E. Johnson Keisuke Tominaga 《Journal of photochemistry and photobiology. A, Chemistry》1994,80(1-3):169-175
We have investigated the ultrafast intermolecular electron transfer (ET) from an electron-donating solvent (aniline (AN) or N, N-dimethylaniline (DMA)) to an excited dye molecule (oxazines (Nile blue and oxazine 1) or coumarins). A non-exponential time dependence was observed in AN and can be explained by solvent reorientation and nuclear motion of the reactants. However, in DMA, a single exponential process was observed for Nile blue (160 fs) and oxazine 1 (280 fs), which can be explained by assuming that the rate of ET is limited mainly by ultrafast nuclear motion. A clear substituent effect on intermolecular ET was observed for the 7-aminocoumarins. When the alkyl chain on the 7-amino group is extended and a hexagonal ring with the benzene moiety is formed, the rate of ET is reduced by three orders of magnitude. This effect can be explained by a change in the free energy difference of the reaction and by the vibrational motion of the amino group. 相似文献
12.
Hideki Nishimori Masahiro Tatsumisago Tsutomu Minami 《Journal of Sol-Gel Science and Technology》1997,9(1):25-31
Monodispersed silica particles up to ca. 1.2 μm in diameter were prepared by hydrolysis of tetraethoxysilane in the presence
of sodium dodecyl sulfate (SDS). The particle size was increased with an increase of SDS added. The geometrical standard deviation
of the particles was decreased with an increase of SDS. In the earlier reaction stage, double spherical particles by the coalescence
of the particles were frequently observed when large amounts of SDS were added. Particle size was gradually increased after
the coalescence occurred and spherical particles were finally obtained. The results of Nielsen’s chronomal analysis suggest
that the polynuclear layer growth took place after the coalescence of the particles in the presence of larger amount of SDS. 相似文献
13.
The first total synthesis of (+)?3-deoxyaphidicolin, a selective inhibitor of eukaryotic DNA polymerase α, has been completed efficiently and stereoselectively starting from 1-abietic acid. 相似文献
14.
1-Alkoxy-3-trimethylsilylmethyl- and 1-alkoxy-3-trimethylsilyl-l,3-butadienes () were newly prepared. The cycloaddition reactions of with various dienophiles including heterodienophiles were found to proceed very smoothly in a perfectly regiospecific mode. 相似文献
15.
16.
Nagaoka Y Inoue H el-Koussi N Tomioka K 《Chemical communications (Cambridge, England)》2002,(2):122-123
Upon treatment with lithium diisopropylamide achiral and chiral alpha,beta,psi,omega-unsaturated bisphosphine oxides underwent lithiation-conjugate addition tandem cyclization to afford the corresponding endo-alpha,beta-unsaturated cyclic bisphosphine oxides; sequential stereoselective reduction of the cyclized bisphosphine oxide gave the corresponding trans- and cis-bisphosphines that were successfully applicable in a catalytic asymmetric hydrogenation as chiral bisphosphine ligands. 相似文献
17.
A quantum chemical study of interchain hopping model of negatively charged solitons in polyacetylene
Akitomo Tachibana Shigeru Ishikawa Yoshihiro Asai Hideki Katagiri Tokio Yamabe 《International journal of quantum chemistry》1992,41(3):461-474
Phonon-assisted interchain hopping of negatively charged solitons in polyacetylene has been studied using a local chemical reaction model CH + CH4 → CH4 + CH. Quantum chemical characteristics of the electron transfer process have been analyzed in terms of the dynamic electron density and the mutual polarization moment. The CH stretching vibrational motion of CH4, which is a local model of the sp3 defect, has been found to play a significant role for the electron transfer. The excitation of the corresponding vibrational mode of the sp3 defect would promote the interchain hopping of the charged soliton. The electron transfer process has also been studied in terms of the “regional” density functional theory. It has been shown that the driving force of the electron transfer is represented by the regional chemical potentials. 相似文献
18.
Hideki Namba Okihiro Tokunaga Tadashi Tanaka Yoshimi Ogura Shinji Aoki Ryoji Suzuki 《Radiation Physics and Chemistry》1993,42(4-6):669-672
The fundamental research work with simulated coal-fired flue gas was performed in JAERI to get basic data for electron beam treatment of flue gas from thermal power plants in Japan. The standard condition of the experiments was set to be the same as that of next large scale pilot test in Nagoya. The concentrations of NOx and SOx were 225 ppm and 800 ppm, respectively. The temperature of the system was 65°C. The effect of multiple irradiation was observed for NOx removal. The target SOx and NOx removals (94% and 80%, respectively) with low NH3 leakage (less than 10 ppm) were achieved at 9 kGy irradiation with 0.9 NH3 stoichiometry during 7 hours continuous operation. The facility for the pilot plant (12,000 Nm3/hr) has just built at the site of Shin-Nagoya power plant of Chubu Electric Power Company and will be started in full operation in November 1992. 相似文献
19.
Takeo Ito Hideki Shirakawa Sakuji Ikeda 《Journal of polymer science. Part A, Polymer chemistry》1974,12(1):11-20
A direct method of simultaneously polymerizing and forming acetylene monomer to produce uniformly thin films of polyacetylene was investigated in terms of catalyst system, catalyst concentration, and polymerization temperature. The best catalyst was a Ti(OC4H9)4–Al(C2H5)3 system (Al/Ti = 3–4) and the critical concentration was 3 mmole/l. of Ti(OC4H9)4. Below the critical concentration, only a solid or a powder was obtained. The configuration of the polymers obtained depends strongly upon the polymerization temperature. Thus an all-cis polymer was obtained at temperatures lower than ?78°C, whereas an all-trans polymer resulted at temperatures higher than 150°C. Observations either in an electron microscope by direct transmission or in a scanning electron microscope showed that the film is composed of an accumulation of fibrils about 200–300 Å in width and of indefinite length. 相似文献
20.
Ohmiya H Tsuji T Yorimitsu H Oshima K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(22):5640-5648
Details of cobalt-catalyzed cross-coupling reactions of alkyl halides with allylic Grignard reagents are disclosed. A combination of cobalt(II) chloride and 1,2-bis(diphenylphosphino)ethane (DPPE) or 1,3-bis(diphenylphosphino)propane (DPPP) is suitable as a precatalyst and allows secondary and tertiary alkyl halides--as well as primary ones--to be employed as coupling partners for allyl Grignard reagents. The reaction offers a facile synthesis of quaternary carbon centers, which has practically never been possible with palladium, nickel, and copper catalysts. Benzyl, methallyl, and crotyl Grignard reagents can all couple with alkyl halides. The benzylation definitely requires DPPE or DPPP as a ligand. The reaction mechanism should include the generation of an alkyl radical from the parent alkyl halide. The mechanism can be interpreted in terms of a tandem radical cyclization/cross-coupling reaction. In addition, serendipitous tandem radical cyclization/cyclopropanation/carbonyl allylation of 5-alkoxy-6-halo-4-oxa-1-hexene derivatives is also described. The intermediacy of a carbon-centered radical results in the loss of the original stereochemistry of the parent alkyl halides, creating the potential for asymmetric cross-coupling of racemic alkyl halides. 相似文献