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51.
Nakao Y Chen J Imanaka H Hiyama T Ichikawa Y Duan WL Shintani R Hayashi T 《Journal of the American Chemical Society》2007,129(29):9137-9143
Stable and reusable tetraorganosilicon reagents, alkenyl-, aryl-, and silyl[2-(hydroxymethyl)phenyl]dimethylsilanes, undergo 1,4-addition reactions to alpha,beta-unsaturated carbonyl acceptors under mild rhodium-catalysis. The reaction tolerates a diverse range of functional groups and is applicable to gram-scale synthesis. Use of a chiral diene ligand allows the achievement of the corresponding enantioselective transformations using the tetraorganosilicon reagents, providing the silicon-based approach to optically active ketones and substituted piperidones that serve as synthetic intermediates of pharmaceuticals. A rhodium alkoxide species is suggested to be responsible for a transmetalation step on the basis of the observed kinetic resolution of a racemic chiral phenylsilane in the enantioselective 1,4-addition reaction under the rhodium-chiral diene catalysis. 相似文献
52.
Doi H Kikuchi E Takagi S Shikano S 《Rapid communications in mass spectrometry : RCM》2007,21(6):997-1002
We conducted experiments to determine isotope changes in the deposit-feeding chironomid larvae Chironomus acerbiphilus during feeding, starvation and metamorphosis. Isotope changes in chironomid larvae occurred mainly during growth and rarely afterward. This finding indicates that chironomid isotope turnover mainly occurs in conjunction with growth and suggests that chironomid larvae only break down newly assimilated food for energy during periods of no growth. Chironomid delta(13)C values significantly increased throughout the starvation experiment, indicating that chironomids preferentially break down components with lower delta(13)C content during starvation. We found significant changes in chironomid isotope ratios ((15)N enrichment) during pupation. This evidence suggests that the physiological condition of animals (such as during an active growth phase or pre- or post-molting) is important to their stable isotope ratios. 相似文献
53.
K. Shikano K. Masumoto T. Ohtsuki M. Katoh 《Journal of Radioanalytical and Nuclear Chemistry》1999,241(1):75-82
We studied the production of nine typical organic analytical reagents labeled with11C,13N and18F by irradiation with charged particles and bremsstrahlung and the purification of labeled compounds with HPLC and sublimation.
As a result, we found that six reagents, α-naphthol, β-naphthol, quinoline, α-nitroso-β-naphthol, 8-hydroxyquinoline, and
1,10-phenanthroline H2O could be labeled with11C by bombarding a mixture of each reagent and boron with protons. More than 10% of the11C was successfully exchanged with carbon atoms in the original reagents. We also found that sublimation is useful for purifying
8-hydroxyquinoline labeled with11C. The extraction property of11C-labeled 8-hydroxyquinoline between water and chloroform could be easily monitored by radioactivity measurement. 相似文献
54.
55.
New C2-symmetric bicyclo[2.2.1]hepta-2,5-dienes bearing methyl and phenyl substituents at the 2 and 5 positions were prepared enantiomerically pure through a two-step sequence starting from the readily available bicyclo[2.2.1]hepta-2,5-dione. Due to the instability or volatility of these dienes, their isolation was achieved through the formation of the corresponding stable [RhCl(diene)]2 complexes. These chiral rhodium complexes displayed high activity and enantioselectivity (up to 99% ee) in the rhodium-catalyzed 1,4-addition and 1,2-addition of phenylboronic acid to cyclic enones and N-sulfonylimines, respectively. 相似文献
56.
A Pd-catalyzed asymmetric synthesis of Si-stereogenic dibenzosiloles is developed through enantioselective C-H bond functionalization of prochiral 2-(arylsilyl)aryl triflates. High chemo- and enantioselectivities are achieved by employing a Josiphos-type ligand under mild conditions. 相似文献
57.
Takeshi Matsumoto Akitami Ichihara Mitsutoshi Yanagiya Tamio Yuzawa Akiyoshi Sannai Hideaki Oikawa Sadao Sakamura Conrad Hans Eugster 《Helvetica chimica acta》1985,68(8):2324-2331
By a simple process, 3-methoxyjuglone (= 8-hydroxy-2-methoxy-1,4-naphthoquinone; 9 ) has been synthesized from 1,2,4-trimethoxybenzene ( 5 ) and converted, after prenylation, to α-caryopterone ( 1 ; Scheme 1), a pyranojuglone pigment from Caryopteris clandonensis. On the other hand, juglone (= 5-hydroxy-1,4-naphthoquinone; 12 ) was regioselectively prenylated at C(2) via its 1-methoxy-cyclohexa-1,3-diene adduct 15 (Scheme 2). The 2-prenyljuglone ( 4 ) thus formed led to 1 after oxidation and other reactions. 相似文献
58.
[reaction: see text] The first catalytic asymmetric synthesis of 2-aryl-2,3-dihydro-4-quinolones has been developed by way of a rhodium-catalyzed 1,4-addition of arylzinc reagents to 4-quinolones. These 1,4-adducts can be obtained with high enantioselectivity by the use of (R)-binap as a ligand, and high yields are realized by conducting the reactions in the presence of chlorotrimethylsilane. 相似文献
59.
K. Shikano H. Yonezawa T. Shigematsu 《Journal of Radioanalytical and Nuclear Chemistry》1996,207(2):413-423
Oxygen was determined in three kinds of ZrF4-based fluoride glass [ZrF4–BaF2–GdF3–AlF3 (ZBGA), ZrF4–BaF2–LaF3–YF3–AlF3–LiF–NaF (ZBLYALN) and ZrF4–BaF2–LaF3–YF3–AlF3–LiF (ZBLYAL)] used for fabricating optical fiberby18O(p, n)18F reaction without significant nuclear interference. The main long life96Nb nuclide was produced by the96Zr(p,n) reaction in a non-destructive analysis of ZBGA-fluoride glass and reduced by using a coincidence system with Ge(Li) and NaI(T1) detectors. Substoichiometric separation of18F was also used to determine oxygen in fluoride glass, especially in glass containing yttrium as a component element because the89Zr produced by the89Y(p,n) reaction is a positron emitter, the same as18F. It was confirmed that the oxygen concentration in fluoride glass was 13–2460 ppm related to the loss by scattering. 相似文献
60.