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11.
Shinichi Yamabe Noriko Tsuchida Tsutomu Minato Takahisa Machiguchi 《Theoretical chemistry accounts》2005,113(2):95-106
Cheletropic additions forming cyclopropane rings were studied theoretically. Ten addition paths were traced by means of density-functional-theory calculations. Two 1,4-dienes, 1,4-pentadiene, and tricyclo[5.3.1.04,9]undeca-2,5-diene were adopted as substrates. CO, SO2, C2H5PCl2, CCl2 and SiCl2 were employed as cheletropic reagents (Xs). An orbital correlation diagram of the Woodward–Hoffmann (W–H) rule and frontier molecular orbital (FMO) interactions between them were investigated in detail. The FMO interactions, HOMO (1,4-diene)lumo (X) and homo (X)LUMO (diene), work reasonably for the progress of the reactions. Those cause the formation of two C–X bonds and a cyclopropane ring, and alternation of double bonds to single bonds. All the additions are concerted. The easiness of the ring formation depends upon the energy gap between HOMO and lumo and that between homo and LUMO, and the spatial directions of HOMO and LUMO extensions. Symmetry conservation of the W–H rule does not hold necessarily for those addition paths. The symmetry-breaking was discussed in terms of FMO interactions.Acknowledgement This work was supported by a Grant-in-Aid for Scientific Research from the Ministry of Education, Science and Culture, Japan and by Nishida Memorial Foundation for Fundamental Chemical Research. 相似文献
12.
Hiroshi Nishikawa Ei-Ichi Terada Eishun Tsuchida Yoshimi Kurimura 《Journal of polymer science. Part A, Polymer chemistry》1978,16(10):2453-2463
The (alkyl)-bis(dimethylglyoximato)pyridinecobalt attached to polychloromethylstyrene by a cobalt–carbon bond was prepared by the reaction of Co(II)(DH)2Py with polychloromethylstyrene in benzene. The fraction of p-vinylbenzyl·Co(DH)2Py introduced to the polymer was 8.1 and 2.1 mole %. The photodecomposition of the polymer-bonded cobaloxime was investigated by following the change of the visible spectrum. The rate constant kdec of the polymer-bonded cobaloxime was 1.1 × 10?2 sec?1 in benzene; it is one-fourth of that of its monomeric analog, benzyl·Co(DH)2Py. The kdec values of the cobaloximes were also measured in benzene–dimethyl sulfoxide mixed solvents, and the polymer effects were discussed. The dependence of the photodecomposition on energy of the irradiation light was investigated, and it was found that the absorption band near 470 nm is important for the photodecomposition of the cobalt–carbon bond. Spectroscopic measurements of the ligand exchange reaction of polymer-bonded cobaloxime with pyridine in dimethyl sulfoxide gave a larger equilibrium constant (1.2 × 104 liter/mole) than that of benzyl·Co(DH)2Py (9.4 × 102 liter/mole). The kinetic data of the ligand exchange reaction indicated that the larger equilibrium constant for the polymeric system is due to the smaller rate constant of the reverse reaction. The thermodynamic parameters were also obtained. 相似文献
13.
Mitsunori Honda Yuichi Yamamoto Hideki Tsuchida Masahito Segi Tadashi Nakajima 《Tetrahedron letters》2005,46(38):6465-6468
Treatment of cyclopropylsilylmethanols derived from cyclopropyl silyl ketones with acid catalyst gives the corresponding silyl-substituted homoallyl derivatives in high yields with good stereoselectivity, independent of the substituents on the cyclopropyl ring. Cyclopropylsilylmethanols having a n-, s-butyl or phenyl group on the carbinyl carbon react to afford the E-homoallyl derivatives selectively. On the other hand, the reaction of cyclopropylsilylmethanols having a tert-butyl group gives Z-isomers exclusively. The following protiodesilylation of the resulting homoallyl derivatives proceeds with retention of configuration. 相似文献
14.
The organic acids in the urine and serum of diabetic patients with ketoacidosis and disturbance of consciousness were studied using acidification, extraction, evaporation, methoxime formation and trimethylsilylation, gas chromatographic separation and mass spectrometric identification procedures. The organic acid profile of 1 ml of serum ultrafiltrate was obtained with good separation using a gas chromatograph equipped with a glass capillary column and a splitless injector. 5-Hydroxyhexanoic acid and 3-hydroxyvaleric acid were identified for the first time in the urine of diabetic patients with ketoacidosis. Urinary excretion and serum concentrations of 2,3-dideoxypentonic acid were increased in diabetic patients. 相似文献
15.
Kiyotaka Shigehara Haruo Matsunaga Eishun Tsuchida 《Journal of polymer science. Part A, Polymer chemistry》1978,16(8):1853-1863
Some polymeric azine or thiazine dyes were prepared by radical polymerization of dye monomers or by polymer reactions between dyes and suitable prepolymers, and their photoredox reactivities were studied. The thionine polymers containing labile ? OH groups exhibited photochromism and thermochromism, which were extremely sensitive to the moisture content of the polymer film. The reversibility of the photochromism and thermochromism increased with the water content in the film. The water-soluble polymeric dyes were photobleached under the influence of suitable reducing agents. The degree of photobleaching was smaller than for the monomeric systems except for the dye polymers containing ? OH groups, probably because of the large steric hindrance of the polymers. 相似文献
16.
Kenji Miyatake Mitsutoshi Jikei Junya Katoh Kimihisa Yamamoto Hiroyuki Nishide Eishun Tsuchida 《先进技术聚合物》1994,5(4):216-220
Poly(2,5-dimethylphenylene sulfide) was prepared by oxidative polymerization of sulfur chloride with p-xylene using 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) as an oxidizing agent. The reaction proceeded efficiently under atmospheric pressure and at room temperature. The polymer formed had a high melting temperature and linear structure which was confirmed by spectroscopies. The effects of reaction time, solvent, temperature and oxidizing agent on polymerization are also discussed. 相似文献
17.
Synthesis of two naturally occurring 3-methyl-2,5-dihydro-1-benzoxepin carboxylic acids 总被引:1,自引:0,他引:1
[structures: see text] Two naturally occurring 3-methyl-2,5-dihydro-1-benzoxepin carboxylic acids, 6-hydroxy-3-methyl-8-(phenylethyl)-2,5-dihydro-1-benzoxepin-9-carboxylic acid (radulanin E) (1) and 9-hydroxy-3-methyl-2,5-dihydro-1-benzoxepin-7-carboxylic acid (2), were synthesized using Stille coupling followed by Mitsunobu cyclization. 相似文献
18.
Drying dissipative structural patterns formed in the course of drying colloidal crystals of silica spheres (110 nm in diameter)
in water, methyl alcohol, ethyl alcohol, 1-propyl alcohol, diethyl ether, and in the mixtures of ethyl alcohol with the other
solvents above have been studied on a cover glass. The macroscopic broad rings were formed in the outside edges of the dried
film for all the solvents examined. Furthermore, much distinct broad rings appeared in the inner area when the solvents were
ethyl alcohol, methyl alcohol, and their mixtures. Profiles of the thickness of the dried films were sensitive to the organic
solvents and explained well with changes in the surface tensions, boiling points, and viscosities of the solvents. The macroscopic
and microscopic spoke-like crack patterns formed. The drying area (or the drying time) increased (or decreased) as the surface
tension of the solvent decreased. However, the absolute values of these drying parameters are determined also by the boiling
points of the solvents. Importance of the fundamental properties of the solvents is supported in addition to the characteristics
of colloidal particles in the drying dissipative pattern formation. 相似文献
19.
Komatsu T Hayakawa S Tsuchida E Nishide H 《Chemical communications (Cambridge, England)》2003,(1):50-51
alpha-Cyclodextrin (alpha CD)-penetrating 2-methyl-1-phenethylimidazole coordinates to the zinc(II) and iron(II) complexes of meso-tetrakis[o-(N-methyl)pyridinium] porphyrinate, giving non-covalently linked alpha CD-porphyrin ensembles; the iron(II) complex can reversibly bind and release dioxygen in aqueous DMF solution. 相似文献
20.
Eishun Tsuchida Kunio Mishima Kiwamu Kitamura Isao Shinohara Setsuo Mimashi 《Journal of polymer science. Part A, Polymer chemistry》1972,10(12):3627-3637
In order to clarify the kinetic features of the styrene (A)–methyl methacrylate (B)–CCl4(S) cooligomerization system, a computer simulation was carried out. The experimental data on the degree of polymerization and the deviation of the cooligomer composition from the statistical steady-state composition were comparatively well explained by calculations based on the kinetic equations derived from the assumed reaction scheme and the values of the velocity coefficients, although the values of the four velocity coefficients in the initiation step and the velocity coefficient of the termination by the coupling of two solvent radicals were estimated. The results of the calculation of the rate of each component reaction show that the following two reactions are the most important in the initiation and in the transfer and termination steps when the [S]/([A] + [B]) ratio is large: where, A, A*, and P are styrene, polystyryl radical, and the cooligomer, respectively. Moreover, it was concluded that the deviation of the cooligomer composition from the statistical steady-state composition was caused by these two reactions. 相似文献