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171.
Iwamoto T Sato K Ishida S Kabuto C Kira M 《Journal of the American Chemical Society》2006,128(51):16914-16920
The first dialkyl-substituted silicon-chalcogen doubly bonded compounds [R2Si=X; R2=1,1,4,4-tetrakis(trimethylsilyl)butane-1,4-diyl, X = S (4), Se (5), and Te (6)]were synthesized by the reactions of an isolable dialkylsilylene R2Si: (3) with phosphine sulfide, elemental selenium, and elemental tellurium, respectively. Systematic changes of characteristics of silicon-chalcogen double bonds are elucidated by X-ray analysis, UV-vis spectroscopy, and DFT calculations. In the solid state, the unsaturated silicon atom in 4-6 adopts planar geometry and the extent of the shortening of Si=X double bonds from the corresponding Si-X single bonds decreases in the order 4 > 5 > 6. In the absorption spectra of 4-6, pi -->pi* transition bands are observed distinctly in addition to n -->pi* transition bands. Both the n -->pi* and pi -->pi* transitions are red-shifted in the order 4 < 5 < 6, and the difference between the energies of the two transitions is kept almost constant among 4-6. The tendency is explained using the qualitative perturbation theory and is reproduced by the DFT calculations for model silanechalcogenones. Addition reactions of water, methanol, and isoprene to 4-6 are reported. 相似文献
172.
The first intermolecular reactions of the excited state of a silicon divalent compound (silylene) with benzene derivatives were discovered. Typically, when a benzene solution of an isolable silylene is irradiated with light of wavelengths longer than 420 nm at room temperature, the corresponding silacyclohepta-2,4,6-triene (silepin) is yielded quantitatively. The photochemical insertion of the silylene toward substituted benzenes occurs in general to give the corresponding substituted silepins. The insertion reaction is highly sensitive to the steric hindrance at a reacting C-C double bond in benzene; during the reactions of the silylene with substituted benzenes, only unsubstituted C-C double bonds in the benzene ring reacted selectively. The irradiation of the silylene in the presence of mesitylene afforded the insertion product to a benzylic C-H bond, indicative of the biradical nature of the excited-state silylene. 相似文献
173.
Iwamoto T Okita J Kabuto C Kira M 《Journal of the American Chemical Society》2002,124(39):11604-11605
The proton abstraction (sila-metalation) of trialkylsilyl-substituted dihydridosilanes with t-BuLi or LDA in THF was found to be a convenient route to the corresponding silyllithiums (RR'SiHLi; 1a, R, R' = t-BuMe(2)Si; 1b, R, R' = Me(3)Si; 1c, R, R' = i-Pr(2)MeSi; 1d, R = t-BuMe(2)Si, R' = 4-methylphenyl). Hydridosilylithium 1a was isolated as air- and moisture-sensitive, but thermally stable, colorless crystals. X-ray analysis has shown that 1a is dimeric in the solid state, where two lithium atoms bridge between anionic silicon atoms forming a parallelogram, each lithium atom is coordinated by one THF molecule, and the Si-H hydrogen atoms are in the plane of the parallelogram. X-ray analysis has shown that (t-BuMe(2)Si)(2)GeHLi (5) has a dimeric structure similar to that of 1a. 相似文献
174.
Muneo?ChōEmail author Tadasi?Huruya Takeaki?Yamazaki 《Integral Equations and Operator Theory》2004,48(3):295-304
The purpose of this paper is to introduce mosaic and principal
functions of log-hyponormal operators associated with Aluthge transformation
and discuss determining sets. 相似文献
175.
Akiyoshi Shioura Takeaki Uno 《Journal of Algorithms in Cognition, Informatics and Logic》1997,23(2):281-290
Given a tree containingnvertices, consider the sum of the distance between all vertices and ak-leaf subtree (subtree which contains exactlykleaves). Ak-tree core is ak-leaf subtree which minimizes the sum of the distances. In this paper, we propose a linear time algorithm for finding ak-tree core for a givenk. 相似文献
176.
177.
Dr. Koki Ikemoto Kanato Takahashi Prof. Dr. Takeaki Ozawa Prof. Dr. Hiroyuki Isobe 《Angewandte Chemie (International ed. in English)》2023,62(14):e202219059
“How do we decide the stoichiometry of host–guest complexes?” This question has long been answered by the Job plot since its first report in 1928. However, as the Job plot was claimed to be misleading in 2016, the question became an open question again and called for renewed investigations. An information-theoretic approach, called Akaike's information criterion, is introduced in this study to select the best model of host–guest complexes, which can rank the models with weight of evidence. A few test cases with unique cylindrical hosts were examined to demonstrate the applicability of the information-theoretic method. Consequently, reasonable views over the thermodynamic behaviors of dumbbell-and-cylinder complexes were obtained. Akaike's information criterion can be a useful and superior alternative to statistical null hypothesis testing, which was proposed as a remedy in place of the Job plot. 相似文献
178.
Haruyuki Okamura Masahiko Minoda Takeshi Fukuda Takeaki Miyamoto Koichi Komatsu 《Macromolecular rapid communications》1999,20(2):37-40
Four samples of C60‐(PS)2, i. e., C60 fullerenes with two low‐polydispersity PS arms at the 1,4‐positions, were studied with respect to their solubility and dispersion state in a PS (polystyrene) matrix by the UV spectroscopic method. C60‐bearing polymers were found to be dispersed, in a blend film or a bulk film of itself, either monomolecularly or in aggregates, depending on the chain length of the polymer moiety and blend composition. 相似文献
179.
Okiko Miyata Kanami Muroya Tomoko Kobayashi Rina Yamanaka Seiko Kajisa Junko Koide Takeaki Naito 《ChemInform》2002,33(42):211-211
180.