全文获取类型
收费全文 | 861篇 |
免费 | 40篇 |
国内免费 | 4篇 |
专业分类
化学 | 727篇 |
晶体学 | 7篇 |
力学 | 6篇 |
数学 | 45篇 |
物理学 | 120篇 |
出版年
2023年 | 4篇 |
2022年 | 4篇 |
2021年 | 6篇 |
2020年 | 20篇 |
2019年 | 16篇 |
2018年 | 11篇 |
2017年 | 5篇 |
2016年 | 15篇 |
2015年 | 20篇 |
2014年 | 20篇 |
2013年 | 39篇 |
2012年 | 40篇 |
2011年 | 51篇 |
2010年 | 35篇 |
2009年 | 43篇 |
2008年 | 66篇 |
2007年 | 54篇 |
2006年 | 66篇 |
2005年 | 52篇 |
2004年 | 53篇 |
2003年 | 35篇 |
2002年 | 39篇 |
2001年 | 14篇 |
2000年 | 9篇 |
1999年 | 5篇 |
1998年 | 6篇 |
1997年 | 11篇 |
1996年 | 10篇 |
1995年 | 9篇 |
1994年 | 11篇 |
1993年 | 8篇 |
1992年 | 13篇 |
1991年 | 7篇 |
1990年 | 4篇 |
1989年 | 4篇 |
1988年 | 4篇 |
1987年 | 7篇 |
1986年 | 8篇 |
1985年 | 6篇 |
1984年 | 13篇 |
1983年 | 4篇 |
1982年 | 9篇 |
1981年 | 11篇 |
1980年 | 8篇 |
1979年 | 4篇 |
1978年 | 5篇 |
1977年 | 3篇 |
1973年 | 2篇 |
1938年 | 2篇 |
1927年 | 7篇 |
排序方式: 共有905条查询结果,搜索用时 0 毫秒
81.
Dr. Yoji Horii Dr. Keiichi Katoh Dr. Kunihisa Sugimoto Dr. Ryo Nakanishi Dr. Brian K. Breedlove Prof. Dr. Masahiro Yamashita 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(12):3098-3104
In the research field of single-molecule magnets (SMMs), lanthanoid–lanthanoid interactions, so-called f–f interactions, are known to affect the SMM properties, although their magnitudes are small. In this article, an SMM with very weak f–f interactions is reported, and the effects of the interactions on the SMM properties are discussed. X-ray structural analysis of the DyIII-CdII-phthalocyaninato sextuple-decker complex (Dy2Cd3) reveals that the intramolecular Dy−Dy length in Dy2Cd3 is more than 13 Å, which is longer than the intermolecular Dy−Dy length. Even though the two DyIII ions are far apart, intermolecular ferromagnetic dipole–dipole interactions are observed in Dy2Cd3. From detailed analysis of ac magnetic susceptibilities, quantum tunneling of the magnetization (QTM) in Dy2Cd3 is partially suppressed owing to the existence of very weak Dy−Dy interactions. Our results show that even very weak Dy−Dy interactions act as a dipolar bias, suppressing QTM. 相似文献
82.
Hidenori Okuzaki Takayoshi Kuwabara Toshio Kunugi 《Journal of Polymer Science.Polymer Physics》1998,36(12):2237-2246
Polypyrrole films containing perchlorate were electrochemically synthesized and the bending and recovery motion of the films obtained has been investigated. It was found that the thickness of the film and ambient relative humidity (RH) were crucial to the motion of film: An increase of the film thickness decreased the displacement of the bending but increased the bending stress. On the other hand, an increase of the ambient RH decreased both functions. The motion of film was caused by the difference of expansion on both sides of the film owing to anisotropic sorption of water vapor, which could be expressed by the diffusion-limited bending model. The diffusion coefficients calculated from the bending and recovery motion at 25°C, RH 50% were 12.2 × 10−8 cm2 s−1 and 3.5 × 10−8 cm2 s−1, respectively. The maximum expansion of the film surface calculated from the bending curve was about 0.36%. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2237–2246, 1998 相似文献
83.
Takayoshi Suzuki 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(4):e118-e119
The title compound [Co(C5H7O2)2(C13H13P)(CH4O)]PF6·H2O, (I), which was converted from trans‐[Co(acac)2(PMePh2)(H2O)]PF6 (acac is pentane‐2,4‐dionato) by recrystallization from aqueous methanol, has been confirmed as have a coordinated methanol ligand. The molecular structure of the complex cation, trans‐[Co(acac)2(PMePh2)(MeOH)]+, is similar to that of the above aqua complex found in the ClO4 salt [Kashiwabara et al. (1995). Bull. Chem. Soc. Jpn, 68 , 883–888]. The Co—O bond length for the coordinated methanol is 2.059 (3) Å. There is an intermolecular hydrogen bond between the OH group of the coordinated methanol and one of the O atoms of the acac ligands in an adjacent complex cation [O5?O3′ = 2.914 (4) Å], giving a centrosymmetric dimeric dicationic complex. 相似文献
84.
[reaction: see text] Polymer-supported bisBINOL ligands were successfully utilized for the immobilization of multicomponent asymmetric catalysts. The polymer-supported Al-Li-bis(binaphthoxide) (ALB) catalyst was more effective than the dendrimer-supported ALB in the Michael reaction of 2-cyclohexen-1-one with dibenzyl malonate affording the adduct in 91% yield with 96% ee. The polymer was also effective for the immobilization of a mu-oxodititanium complex that promoted carbonyl-ene reaction of ethyl glyoxalate with alpha-methyl styrene to provide the adduct with up to 98% ee. 相似文献
85.
Kazunori Takada Hiroya Sakurai Fujio Izumi Takayoshi Sasaki 《Journal of solid state chemistry》2004,177(1):372-376
Monolayer hydrate (MLH) NaxCoO2·y′H2O was obtained from superconducting bilayer hydrate (BLH) NaxCoO2·yH2O by partial extraction of H2O molecules between the CoO2 layers. Magnetization measurements indicated that electron densities in the CoO2 layer of the MLH phase remained unchanged after the water extraction. Nevertheless, superconductivity was completely suppressed in the MLH phase. This strongly suggests that the highly 2D nature in the BLH phase due to its thick insulating layers consisting of H2O molecules and Na+ ions plays an important role for inducing superconductivity. 相似文献
86.
The full nine-dimensional vibrational Hamiltonian for H5 + described in the literature [Kraemer et al., J. Mol. Spectrosc. 164, 500 (1994)] is adopted here for an approximate evaluation of the spectral linewidths of the observed H-H stretching modes of the H5 + ion and the corresponding modes of its D5 + isotopomer. In this approximation the high dimensionality of the original Hamiltonian is reduced to a three-dimensional model Hamiltonian which takes only the H-H stretching modes and the molecular dissociation mode into consideration assuming that they are adiabatically separable from the remaining modes. To make the calculations numerically feasible, the molecular degenerate ("skeletal") vibrations are assumed to take place in harmonic potentials, and the effect of the internal propeller rotation is completely disregarded. The linewidths calculated in this approximation are too small to explain the broad shapes of the observed spectral transitions. It can thus be argued that the failure to resolve rotational structure in the observed bands is mainly due to spectral congestion and only partly due to predissociation of the H5 + cluster. 相似文献
87.
Sakurai J Oguchi T Watanabe K Abe H Kanno S Ishikawa M Katoh T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(3):829-837
Biologically important and structurally unique marine natural products avarone (1), avarol (2), neoavarone (3), neoavarol (4) and aureol (5), were efficiently synthesized in a unified manner starting from (+)-5-methyl-Wieland-Miescher ketone 10. The synthesis involved the following crucial steps: i) Sequential BF(3)Et(2)O-induced rearrangement/cyclization reaction of 2 and 4 to produce 5 with complete stereoselectivity in high yield (2 --> 5 and 4 --> 5); ii) strategic salcomine oxidation of the phenolic compounds 6 and 8 to derive the corresponding quinones 1 and 3 (6 --> 1 and 8 --> 3); and iii) Birch reductive alkylation of 10 with bromide 11 to construct the requisite carbon framework 12 (10 + 11 --> 12). An in vitro cytotoxicity assay of compounds 1-5 against human histiocytic lymphoma cells U937 determined the order of cytotoxic potency (3 > 1 > 5 > 2 > 4) and some novel aspects of structure-activity relationships. 相似文献
88.
Dr. Yoji Horii Prof. Dr. Keiichi Katoh Prof. Dr. Yuji Miyazaki Dr. Marko Damjanović Tetsu Sato Prof. Dr. Liviu Ungur Prof. Dr. Liviu F. Chibotaru Prof. Dr. Brian K. Breedlove Prof. Dr. Motohiro Nakano Prof. Dr. Wolfgang Wernsdorfer Prof. Dr. Masahiro Yamashita 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(36):8076-8082
Gd3+ complexes have been shown to undergo unusual slow magnetic relaxation processes similar to those of single-molecule magnets (SMMs), even though Gd3+ does not exhibit strong magnetic anisotropy. To reveal the origin of the slow magnetic relaxation of Gd3+ complexes, we have investigated the magnetic properties and heat capacities of two Gd3+-phthalocyaninato triple-decker complexes, one of which has intramolecular Gd3+–Gd3+ interactions and the other does not. It was found that the Gd3+–Gd3+ interactions accelerate the magnetic relaxation processes. In addition, magnetically diluted samples, prepared by doping a small amount of the Gd3+ complexes into a large amount of diamagnetic Y3+ complexes, underwent dual magnetic relaxation processes. A detailed dynamic magnetic analysis revealed that the coexistence of spin–lattice relaxation and phonon-bottleneck processes is the origin of the dual magnetic relaxation processes. 相似文献
89.
Nakamura K Zhang X Kuramitsu Y Fujimoto M Yuan X Akada J Aoshima-Okuda M Mitani N Itoh Y Katoh T Morita Y Nagasaka Y Yamazaki Y Kuriki T Sobel A 《Journal of chromatography. A》2006,1106(1-2):181-189
Two-dimensional gel electrophoresis (2-DE) and tandem mass spectrometry were successfully used for determination of a phosphorylation site of stathmin induced by heat stress to Jurkat cells of a human T lymphoblastic cell line. The cells were incubated for 30 min at 41 degrees C up to 45 degrees C in a serum free 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) buffered culture medium. The intracellular soluble proteins were separated by 2-DE, and some of the proteins increased their abundance by heat stress. Those proteins were identified to be calmodulin, protein kinase C substrate, thymosin beta-4 and F-actin capping protein beta-subunit by peptide mass fingerprinting (PMF) with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). On the contrary, protein phosphatase 2C gamma-isoform, nucleophosmin, translationally controlled tumor protein, Rho GDP-dissociation inhibitor-1, eukaryotic translation initiation factors 5A and 3A subunit 2, ubiquitin-like protein SMT 3B and chloride intracellular channel protein-1 were decreased their abundance. A protein spot of M(r) 18,000 and pI 5.9 was markedly increased at temperatures higher than 43 degrees C at which the cells were led to apoptosis. The spot was identified to be stathmin of a signal relay protein which has a function of sequestering microtubule. MALDI-quadrupole ion trap (QIT)-TOF-MS/MS and immunoblotting with a monoclonal antibody specific for a phosphorylation site of stathmin showed that the spot was a phosphorylated stathmin at serine 37 (Ser 37). The phosphorylation was suppressed by treatment of cells with olomoucine of an inhibitor specific for cyclin dependent kinase (Cdk-1). These results strongly suggest that heat stress activates Cdk-1 which phosphorylates Ser 37 on the stathmin molecule. The phosphorylation may cause the functional loss of stathmin for dynamic microtubule assembly and leads Jurkat cells to cell cycle arrest and apoptosis. 相似文献
90.
Takayoshi Fujii Tomoyoshi Takano Hiroyuki Morita Toshiaki Yoshimura 《Tetrahedron》2006,62(41):9622-9627
The fluorination of 10-oxo-10H-5λ4,10λ4-thianthren-5-ylideneamine (2) with Selectfluor™ affords 5-fluoro-10-oxo-5,10-dihydro-5λ6,10λ4-thianthren-5-nitrile (4). The amination of 4 with morpholine gives 5-morpholino-10-oxo-5,10-dihydro-5λ6,10λ4-thianthren-5-nitrile (5). The stereochemical course of both reactions has been studied, while the configurations of their products, cis-isomer 4 and trans-5-morpholino-10-oxo-5,10-dihydro-5λ6,10λ4-thianthren-5-nitrile (trans-5) are elucidated by the use of X-ray crystallographic analyses. 相似文献