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221.
Masao Tomoi Yasushi Arita Hiroshi Kakiuchi 《Journal of polymer science. Part A, Polymer chemistry》1987,25(9):2455-2467
Polymer-supported aminopyridine or imidazole catalysts were effective for acyl rearrangements of O-acylated substrates to C-acylated products. Some of the aminopyridine catalysts, which had much higher activity than the imidazole catalyst, exhibited high activity comparable to that of the corresponding soluble catalyst, 4-N, N-dimethylaminopyridine. The activity of the immobilized aminopyridines was studied as a function of the percentage of ring substitution, spacer-chain length, and solvents. The affinity of the substrates for the immobilized catalysts played an important role for the rearrangements. The increased catalytic activity resulted from the increased affinity of the substrates for the catalysts. The activity of the immobilized bases decreased gradually owing to the reaction of the active site with the products as the catalysts were used repeatedly. The treatment of the used catalysts with nucleophiles restored the activity to some extent. The activity decrease can be minimized by shortening a contact time between the catalysts and the products. 相似文献
222.
Kiyomi Kakiuchi Koichi MinatoKen Tsutsumi Tsumoru MorimotoHideo Kurosawa 《Tetrahedron letters》2003,44(9):1963-1966
Radical ring-opening reactions of bicyclo[4.2.0]octanones, its C6 alkyl derivatives, and tricyclic ketones promoted by SmI2 gave cyclohexanones via fission of the external cyclobutane bond. The CO2Me, CN, and phenyl derivatives led to the production of the eight-membered ring compounds through cleavage of the central cyclobutane bond. Using this regioselective reaction, the synthesis of (±)-acorenone was achieved. 相似文献
223.
Takao Iijima Yuhshi Sakamoto Hiroshi Kakiuchi 《Journal of polymer science. Part A, Polymer chemistry》1988,26(12):3189-3198
α-Methoxyphenylmethylium hexachloroantimonate was prepared from α-methoxybenzyl chloride and antimony pentachloride at 0°C and isolated for the first time, and its visible and 1H-NMR spectra were measured. This salt was used as a novel initiator for the polymerization of propylene oxide (PO) in the temperature range ?20 to 30°C with dichloromethane as solvent. PO polymerized spontaneously but a limit yield was observed. The microstructure of PO polymer is amorphous by 13C-NMR. The PO polymerization is thought to proceed in the conventional cationic mechanism on the basis of the polymerization behavior and the analyses of both the polymer structure and end groups attached to the PO polymer. 相似文献
224.
Mikio Hori Kiyomi Tanaka Tadashi Kataoka Hiroshi Shimizu Eiji Imai Kazuhiko Kimura Yoshinobu Hashimoto 《Tetrahedron letters》1985,26(10):1321-1322
5,7-Dimethyl[1,2,4]triazolo[1,5-a]pyrimidinio-3-phenacylide () generated by the reaction of an iminium salt () with 1 eq. of triethylamine, underwent a new thermal ring cleavage of the triazole moiety to give the pyrimidine derivative. However reaction of with 2 eq. of triethylamine afforded the 2-iminooxazoline derivative. The iminooxazoline reacted with nucleophiles such as alcohols or amines to give imidazoles. 相似文献
225.
Takao Iijima Hiroshi Kakiuchi 《Journal of polymer science. Part A, Polymer chemistry》1990,28(3):609-617
α-Thiomethoxyphenylmethylium hexachloroantimonate was prepared from α-chlorobenzyl methyl sulfide and antimony pentachloride and studied by visible spectroscopy. The salt is unstable at room temperature and used as in situ initiator for the polymerization of oxiranes in dichloromethane. Propylene oxide (PO) and cyclohexene oxide (CHO) were used as oxiranes. The microstructure of PO polymer is amorphous by 13C-NMR. The initiator was more effective for the polymerization of CHO than for that of PO. 相似文献
226.
Maeda Y Kakiuchi N Matsumura S Nishimura T Kawamura T Uemura S 《The Journal of organic chemistry》2002,67(19):6718-6724
A catalytic system consisting of vanadium oxyacetylacetonate [VO(acac)(2)] and 3 A molecular sieves (MS3A) in acetonitrile works effectively for the aerobic oxidation of propargylic alcohols [R(1)CH(OH)Ctbd1;CR(2)] to the corresponding carbonyl compounds under an atmospheric pressure of molecular oxygen. Although the reactivity of alpha-acetylenic alkanols (R(1) = alkyl) is lower compared to that of the alcohols of R(1) = aryl, alkenyl, and alkynyl, the use of VO(hfac)(2) as a catalyst and the addition of hexafluoroacetylacetone improve the product yield in these cases. A catalytic cycle involving a vanadium(V) alcoholate species and beta-hydrogen elimination from it has been proposed for this oxidation. 相似文献
227.
A new photomorphogenesis was found in the plasmodium of the true slime mold Physarum polycephalum: the plasmodium broke temporarily into equal-sized spherical pieces, each containing about eight nuclei, about 5 h after irradiation with light. Action spectroscopic study showed that UVA, blue and far-red lights were effective, while red light inhibited the far-red-induced fragmentation. Difference absorption spectra of both the living plasmodium and the plasmodial homogenate after alternate irradiation with far-red and red light gave two extremes at 750 and 680 nm, which agreed with those for the induction and inhibition of the fragmentation, respectively. A kinetic model similar to that of phytochrome action explained quantitatively the fluence rate-response curves of the fragmentation. Our results indicate that one of the photoreceptors for the plasmodial fragmentation is a phytochrome. 相似文献
228.
Laforge FO Kakiuchi T Shigematsu F Mirkin MV 《Journal of the American Chemical Society》2004,126(47):15380-15381
The rates of electron transfer (ET) reactions at the water/ionic liquid (IL) interface have been measured for the first time using scanning electrochemical microscopy. The standard bimolecular rate constant of the interfacial ET between ferrocene dissolved in 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide and aqueous ferricyanide (0.4 M-1 cm s-1) was found to be approximately 30 times higher than the corresponding rate constant measured at the water/1,2-dichloroethane interface. The driving force dependence of the ET rate was investigated over a wide range of the interfacial potential drop values (>200 mV). The observed Butler-Volmer-type dependence is discussed in terms of the interfacial model. The ET was also probed at the interface between aqueous solution and the mixture of the IL and 1,2-dichloroethane. The mole fractions in this mixture were varied systematically to investigate the transition from the water/organic to the water/IL interface. The observed decrease in the rate constant with increasing mole fraction of 1,2-dichloroethane is in contrast with the previously reported direct correlation between the electrochemical rate constant and the diffusion coefficient of redox species in solution. 相似文献
229.
Kapoor MP Inagaki S Ikeda S Kakiuchi K Suda M Shimada T 《Journal of the American Chemical Society》2005,127(22):8174-8178
The bridged allylorganosilanes 1,4-bis(diallylethoxysilyl)benzene and 1,4-bis(triallylsilyl)benzene are presented as new precursors for the surfactant-assisted synthesis of ordered mesoporous organosilica with pore walls having crystal-like molecular-scale periodicity. This approach provides a new route to the formation of periodic mesostructures with crystal-like pore walls. The synthesis method presented is applicable to the preparation of mesoporous organosilica with bulky organic groups, the precursors of which are typically impossible to obtain in high purity. 相似文献
230.
Y. Ohtsuka T. Iyogi H. Kakiuchi Y. Takaku S. Hisamatsu J. Inaba 《Journal of Radioanalytical and Nuclear Chemistry》2004,261(3):625-630
The background distributions of 239+240Pu and 137Cs fallout in agricultural soil were investigated in Rokkasho where Japan's first commercial nuclear fuel reprocessing plant
is now being constructed. The mean inventories of 239+240Pu and 137Cs in three fields with non-yam-cultivation history were 116 Bq·m−2 and 3.4 kBq·m−2, respectively. The mean atomic ratio of 240Pu/239Pu for all studied fields was 0.18±0.04, and was similar to that of global fallout. The 239+240Pu concentrations correlated very well with 137Cs (r = 0.97) in spite of heavy disturbance of the soil, and the activity ratio of 239+240Pu/137Cs was 0.037±0.007, which is a typical value for global fallout. These results showed that the nuclides had similar behavior
in agricultural upland fields in Rokkasho. Since 210Pb is steadily deposited from the atmosphere to the land, this nuclide could be an index for the degree of disturbance of
a field and of soil lost from the field. The ratio of excess 210Pb inventory in the soil to the equivalent inventory of atmospheric 210Pb deposition was 96%, and indicated that soil was not lost from the cultivated fields.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献