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71.
Nakano M Takahata M Yamada S Yamaguchi K Kishi R Nitta T 《The Journal of chemical physics》2004,120(5):2359-2367
We investigate the exciton migration dynamics in a dendritic molecular model composed of pi-conjugation linear-leg units (acetylenes and diacetylene) and a benzene ring (branching point) using the quantum master equation approach with the ab initio molecular orbital (MO) configuration interaction (CI) method. The efficient migration of exciton from short-length linear legs (acetylenes) to long-length linear leg (diacetylene) via a benzene ring is observed. As predicted in previous studies, the exciton (electron and hole) distributions are relatively well localized in each generation segmented by the meta-branching point (meta-substituted benzene ring) though the electron and hole distributions are delocalized and are somewhat spatially different from each other within each generation. It is found that the excitons localized in the generation composed of short linear legs occupy in higher-lying exciton states, while those in the generation composed of long linear legs do in lower-lying ones. These features suggest the decoupling of pi-conjugation at the meta-branching point. On the other hand, the relaxation effect between exciton states is found to be caused by the exciton-phonon coupling, in which the existence of common configurations (electron-hole pairs) in CI wave functions between adjacent exciton states (having primary distributions on short and long linear-leg regions, respectively) is important for the relaxation between their exciton states. This feature indicates the importance of partial penetration of pi-conjugation through the meta-substituted benzene ring in excited states for such exciton migration. 相似文献
72.
An efficient method for the transfer hydrogenation of quinolines catalyzed by a Cp∗Ir complex was developed. A variety of 1,2,3,4-tetrahydroquinolines were obtained by regio- and chemoselective transfer hydrogenation of quinolines using 2-propanol as a hydrogen source. 相似文献
73.
A new catalytic system for beta-alkylation of secondary alcohols has been developed. In the presence of [CpIrCl(2)](2) (Cp = pentamethylcyclopentadienyl) catalyst and base, the reactions of various secondary alcohols with primary alcohols give beta-alkylated higher alcohols in good to excellent yields without any hydrogen acceptor or hydrogen donor. This reaction proceeds via successive hydrogen-transfer reactions and aldol condensation. [reaction: see text] 相似文献
74.
A new effective catalytic system consisting of [Cp*IrCl2]2/K2CO3 (Cp*=pentamethylcyclopentadienyl) for the N-alkylation of primary amines with alcohols has been developed. As an example, the reaction of aniline with benzyl alcohol in the presence of [Cp*IrCl2]2 (5.0 mol%Ir) and K2CO3 (5.0 mol%) in toluene at 110°C for 17 h gave benzylaniline in an isolated yield of 88%. 相似文献
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Ryohei Sugita Natsuko I. Kobayashi Atsushi Hirose Yoshimi Ohmae Keitaro Tanoi Tomoko M. Nakanishi 《Journal of Radioanalytical and Nuclear Chemistry》2013,298(2):1411-1416
We have developed a real-time radioisotope imaging system (RRIS) that can nondestructively trace 14C-labeled chemicals in plants. In an experiment, after feeding 14CO2 to a plant, the plant was fixed inside a box where lighting was regulated, and beta rays emitted from the 14C in the plant were intermittently imaged using the developed system. As a first step, using a series of standard sources of 14C, the data depth and detection limits of the 14C images captured by the RRIS were evaluated for various integral times. As a result, the linearity between the 14C activity and signal intensity was determined for the range 103. Next, the linearity was validated using plant (Arabidopsis thaliana) organs, resulting that the linearity was shown in the case of young leaf, but was not maintained in the thick organs, such as a flower, mature leaf, siliques, and stem. Considering the good correlation between the intensity by RRIS and the PSL value by an imaging plate (IP) as well as the relative low energy of beta rays emitted from 14C, the thickness of the organs would easily affect the quantitativity of the RRIS as well as an IP. Our findings prove that sequential images of 14C in a living plant sample in a regulated light and air environment can be nondestructively analyzed using the developed system, whose quantitativity is similar to that of an IP. 相似文献
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Toshifumi Satoh Masaki Tamaki Yoshikazu Kitajyo Takahiro Maeda Hiroyuki Ishihara Tomoko Imai Harumi Kaga Toyoji Kakuchi 《Journal of polymer science. Part A, Polymer chemistry》2006,44(1):406-413
A novel biodegradable unimolecular reversed micelle consisting of a poly(L ‐lactide) (PLA) shell and a hyperbranched D ‐mannan (HBM) core, that is, a chestnut‐shaped polymer (PLA–HBM), was synthesized by the polymerization of L ‐lactide on HBM with 4‐(dimethylamino)pyridine (DMAP) as the catalyst. The obtained polymers were soluble in dimethyl sulfoxide, tetrahydrofuran, and chloroform but insoluble in H2O. The molecular weights of the PLA chain on PLA–HBM tended to increase with increasing polymerization time. The number of PLA chains on PLA–HBM could be controlled by the ratio of DMAP to the sugar unit in HBM. The obtained copolymer, PLA–HBM, acted as a unimolecular reversed micelle with an encapsulation ability toward the hydrophilic molecule. In addition, the entrapped hydrophilic molecules were slowly released from the core of PLA–HBM, and the release rate was accelerated by the breaking of the PLA chains of the shell when proteinase K as a hydrolase of PLA was used. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 406–413, 2006 相似文献