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1.
Spin-lattice relaxation mechanisms in kaolinite have been reinvestigated by magic-angle spinning (MAS) of the sample. MAS is useful to distinguish between relaxation mechanisms: the direct relaxation rate caused by the dipole-dipole interaction with electron spins is not affected by spinning while the spin diffusion-assisted relaxation rate is. Spin diffusion plays a dominant role in 1H relaxation. MAS causes only a slight change in the relaxation behavior, because the dipolar coupling between 1H spins is strong. 29Si relaxes directly through the dipole-dipole interaction with electron spins under spinning conditions higher than 2 kHz. A spin diffusion effect has been clearly observed in the 29Si relaxation of relatively pure samples under static and slow-spinning conditions. 27Al relaxes through three mechanisms: phonon-coupled quadrupole interaction, spin diffusion and dipole-dipole interaction with electron spins. The first mechanism is dominant, while the last is negligibly small. Spin diffusion between 27Al spins is suppressed completely at a spinning rate of 2.5 kHz. We have analyzed the relaxation behavior theoretically and discussed quantitatively. Concentrations of paramagnetic impurities, electron spin-lattice relaxation times and spin diffusion rates have been estimated. 相似文献
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Photooxygenations of 4-2H-anisole () and o-xylene () by 3-methylpyridazine 2-oxide () or pyridine 1-oxide () were studied in a variety of solvents at varying irradiation temperatures. Remarkable solvent effect on NIH-shift coupled with their hydroxylation processes was observed. 相似文献
4.
Kazuhiro Watanabe Noboru Akino Tetsuo Aoyagi Noboru Ebisawa Yukio Fujiwara Atsusi Honda Takashi Inoue Takao Itoh Mikito Kawai Minoru Kazawa Junichi Koizumi Masaaki Kuriyama Kenji Miyamoto Naoki Miyamoto Kazuhiko Mogaki Yoshihiro Ohara Tokumichi Ohga Yoshikazu Okumura Hiroshi Oohara Katsumi Ohshima Fujio Satoh Kazuhiko Shimizu Syunji Takahashi Hirotsugu Usami Katsutomi Usui Masahiro Yamamoto Takeshi Yamazaki 《Radiation Physics and Chemistry》1997,49(6):631-639
A negative-ion-based neutral beam injector (N-NBI) has been constructed for JT-60U. The N-NBI is designed to inject 500 keV, 10 MW neutral beams using two ion sources, each producing a 500 keV, 22 A D− ion beam. In the preliminary experiment using one ion source, a D− ion beam of 13.5 A has been successfully accelerated with an energy of 400 keV (5.4 MW) for 0.12 s at an operating pressure of 0.22 Pa. This is the highest D− beam current and power in the world. Co-extracted electron current was effectively suppressed to the ratio of Ie/ID− < 1. The highest energy beam of 460 keV, 2.4 A, 0.44 s has also been obtained. To realize 1 MeV class NBI system for ITER (International Thermonuclear Experimental Reactor), demonstration of ampere class negative ion beam acceleration up to 1 MeV is an important mile stone. To achieve the mile stone, a prototype accelerator and a 1 MV, 1 A test facility called MeV Test Facility (MTF) were constructed. Up to now, an H− ion beam was accelerated up to the energy of 805 keV with an acceleration drain current of 150 mA for 1 s in a five stage electrostatic multi-aperture accelerator. 相似文献
5.
Ueda J Takeshita K Matsumoto S Yazaki K Kawaguchi M Ozawa T 《Photochemistry and photobiology》2003,77(2):165-170
The reaction of singlet oxygen (1O2) generated by ultraviolet-A (UVA)-visible light (lambda > 330 nm) irradiation of air-saturated solutions of hematoporphyrin with phenolic compounds in the presence of a spin trap, 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), gave an electron spin resonance (ESR) spectrum characteristic of the DMPO-hydroxyl radical spin adduct (DMPO-*OH). In contrast, the ESR signal of 5,5-dimethyl-2-pyrrolidone-N-oxyl, an oxidative product of DMPO, was observed in the absence of phenolic compounds. The ESR signal of DMPO-*OH decreased in the presence of either a *OH scavenger or a quencher of *O2 and under anaerobic conditions, whereas it increased depending on the concentration of DMPO. These results indicate both 1O2- and DMPO-mediated formation of free *OH during the reaction. When DMPO was replaced with 5-(diethoxyphosphoryl)-5-methyl-1-pyrroline-N-oxide (DEPMPO), no DEPMPO adduct of oxygen radical species was obtained. This suggests that 1O2, as an oxidizing agent, reacts little with DEPMPO, in which a strong electron-withdrawing phosphoryl group increases the oxidation potential of DEPMPO compared with DMPO. A linear correlation between the amounts of DMPO-*OH generated and the oxidation potentials of phenolic compounds was observed, suggesting that the electron-donating properties of phenolic compounds contribute to the appearance of *OH. These observations indicate that 1O2 reacts first with DMPO, and the resulting DMPO-1O2 intermediate is immediately decomposed/reduced to give *OH. Phenolic compounds would participate in this reaction as electron donors but would not contribute to the direct conversion of 1O2 to *OH. Furthermore, DEPMPO did not cause the spin-trapping agent-mediated generation of *OH like DMPO did. 相似文献
6.
An enantioselective total synthesis of (-)-lepadin B has been developed starting from (2S,4S)-2,4-O-benzylidene-2, 4-dihydroxybutanal. The key steps in the synthesis include the use of an aqueous intramolecular acylnitroso Diels-Alder reaction to afford the trans-1,2-oxazinolactam and Suzuki cross-coupling reaction to elaborate the (E,E)-octadienyl unit. 相似文献
7.
The three-component aminoallylation reaction of the activated olefins 2 with the phthalimide 1a and allyl chloride proceeded very smoothly in the presence of Pd(2)dba(3).CHCl(3) (5 mol %)/P(4-FC(6)H(4))(3) (40 mol %) and Cs(2)CO(3) (3 equiv against 2) in dichloromethane at room temperature to give the corresponding aminoallylated products, N-pent-4-enylphthalimides 3, in 58-99% yields. The reaction of oxazolidinone 1b also proceeded very smoothly to give N-(2,2-dicyano-1-phenylpent-4-enyl)oxazolidinone in a quantitative yield; however, the Tsuji-Trost-type allylation products 4 were obtained in the case of dibenzylamine, N-tosylaniline, and pyrrolidin-2-one. Further, 2 underwent cycloaddition with N-tosylvinylaziridine 9a in the presence of Pd(2)dba(3).CHCl(3) (5 mol %)/P(4-FC(6)H(4))(3) (40 mol %) in THF at room temperature, giving the corresponding pyrrolidines 11 in 69-99% yields. 相似文献
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9.
A variety of O-alkylperoxycarbonic acids () were conveniently prepared by utilizing alkyloxycarbonylimidazoles () as their precursors. Epoxidation of alkenes with such peroxy-acids was studied and their reactivities were compared with those of peroxycarboxylic acids. 相似文献
10.
The most widely used method for qualitative and quantitative analysis of carbonyl compounds is the 2,4-dinitrophenylhydrazine method through the formation of 2,4-dinitrophenylhydrazone derivatives. However, this method may cause an analytical error because 2,4-dinitrophenylhydrazones have both E- and Z-stereoisomers. Purified aldehyde-2,4-dinitrophenylhydrazone demonstrated only the E-isomer. However under UV irradiation and the addition of acid, both E- and Z-isomers were seen. The spectral patterns of Z-isomers were different from those of E-isomers and the absorption maximum wavelengths were shifted towards shorter wavelengths by 5-8 nm. An equilibrium Z/E isomer ratio was observed in 0.02-0.2% (v/v) phosphoric acid solutions. In the case of acetaldehyde- and propanal-2,4-dinitrophenylhydrazones, the equilibrium Z/E isomer ratios were 0.32 and 0.14, respectively. However, when irradiated with ultraviolet light at 364 nm, the isomer ratios were increased beyond this constant ratio and reached 0.55 and 0.33, respectively. Zero-order rates for decreases of aldehyde derivatives were observed under UV irradiation (364 nm), however the decreases of concentration were not observed in phosphoric acid solutions. The best method for the determination of aldehyde-2,4-dinitrophenylhydrazones by HPLC is to add phosphoric acid to both the sample and the standard solution, to form a 0.02-1% acid solution. 相似文献