全文获取类型
收费全文 | 4516篇 |
免费 | 175篇 |
国内免费 | 622篇 |
专业分类
化学 | 4368篇 |
晶体学 | 36篇 |
力学 | 9篇 |
综合类 | 27篇 |
数学 | 314篇 |
物理学 | 559篇 |
出版年
2024年 | 7篇 |
2023年 | 140篇 |
2022年 | 99篇 |
2021年 | 137篇 |
2020年 | 236篇 |
2019年 | 181篇 |
2018年 | 167篇 |
2017年 | 231篇 |
2016年 | 224篇 |
2015年 | 137篇 |
2014年 | 264篇 |
2013年 | 885篇 |
2012年 | 385篇 |
2011年 | 279篇 |
2010年 | 218篇 |
2009年 | 235篇 |
2008年 | 237篇 |
2007年 | 252篇 |
2006年 | 230篇 |
2005年 | 196篇 |
2004年 | 195篇 |
2003年 | 125篇 |
2002年 | 28篇 |
2001年 | 22篇 |
2000年 | 16篇 |
1999年 | 23篇 |
1998年 | 20篇 |
1997年 | 22篇 |
1996年 | 16篇 |
1995年 | 15篇 |
1994年 | 13篇 |
1993年 | 18篇 |
1992年 | 8篇 |
1991年 | 14篇 |
1990年 | 7篇 |
1989年 | 3篇 |
1988年 | 6篇 |
1987年 | 3篇 |
1985年 | 2篇 |
1984年 | 4篇 |
1983年 | 2篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1977年 | 1篇 |
1976年 | 2篇 |
1974年 | 1篇 |
排序方式: 共有5313条查询结果,搜索用时 15 毫秒
121.
Naïma Khiri 《Tetrahedron letters》2005,46(35):5807-5810
Enantiomerically pure (E)-β-sulfinylenones are smoothly prepared from β-ketoesters in three steps with good overall yield. Since they can be the substrates of many diastereoselective reactions, they represent versatile precursors of a wide range of chiral building blocks. We propose a rationale to explain the formation of (E)-β-sulfinylenones from the corresponding δ-enol-methylethers. 相似文献
122.
123.
Iván da Silva Cristina González-Silgo Juan Rodríguez-Carvajal Lourdes Mestres 《Journal of solid state chemistry》2005,178(5):1601-1608
The crystal structure of potassium, rubidium and caesium fluoroberyllates have been re-examined by neutron powder diffraction at room temperature and at 1.5 K. Previously, their structures, obtained from X-ray data, were described in the Pn21a space group. However, the results obtained from Rietveld refinements, using powder neutron diffraction, at both temperatures, indicated that all structures are orthorhombic with space group Pnma. The known phase transition at high temperature is probably related to the appearance of a hexagonal pseudo-symmetry instead of the elimination of the mirror plane between the above mentioned orthorhombic space groups. A possible phase transition, at very low temperature, was discarded considering the stereochemical criteria concerning the structural stability of A2BX4 compounds. This was confirmed by thermal analysis. On the other hand, a modulated background has been detected in all samples during the refinements. This is compatible with the presence of an amorphous phase, coexisting with the crystalline phase, or with a disordered component within the main crystalline phase. Instead of using a polynomial function, the background was modelled by Fourier filtering improving the fit for all patterns. The radial distribution function (RDF) was obtained from the analysis of the calculated background and compared with the RDF from the average crystal structure. The advantages of neutron with respect to X-ray diffraction were evidenced for this type of compound with β-K2SO4-type structure. 相似文献
124.
The chemoselective and stereoselective synthesis of gem-difluoro-β-aminoesters or gem-difluoro-β-lactams was investigated from ethylbromodifluoroacetate and imines during Reformatsky reaction. Influence of various reaction parameters, such as nature of the amine part, nature of the chiral auxiliary, was evaluated. High levels of stereoselectivity (up to 98%) were obtained for gem-difluoro-β-aminoesters and gem-difluoro-β-lactams using either (R)-phenylglycinol or (R)-methoxyphenylglycinol. 相似文献
125.
Michael D. Swift 《Tetrahedron letters》2007,48(22):3771-3773
A new approach for the stereoselective synthesis of (2R,3S)-2-amino-3,4-dihydroxybutyric acid, an α-amino acid from Lyophyllum ulmarium, has been accomplished using an ether directed aza-Claisen rearrangement. On investigation of optimal conditions for this key step it was shown for the first time that Au(I) can be used to catalyse this transformation. 相似文献
126.
In the research on metallic glass, there are arguments against the "rigid band charge transfer", model which assumes a charge transfer from metalloid atoms to transition metal atoms to explain the experimental evidence of linear reduction of average atomic magnetic moment with the increasing concentration of metalloid atoms, but they could not explain the experimental relation of the reduction. In the present work, spin-polarized SCC-DV-X_a calculation for atomic clusters for metallic glass Co-B has been empoloyed to investigate the local electronic structure and magnetic property of the metallic glass. As opposed to the "rigid band charge transfer" model, calculation in the present work indicates that charge transfers from Co4s to both B and Co3d. It is found that there is Co3d4s-B2p hybird bonding in Co-B, which leads to the linear reduction of average atomic magnetic moment. Thus the explanation removes the above controversy. 相似文献
127.
128.
129.
130.
Poly(L -lactide-co-β-malic acid) was obtained after the hydrogenolysis of the copolymer of L -lactide (L-LA) and β-benzyl malate (MA). 1H-NMR demonstrated that the composition of the copolymer was identical to the feeding dose. Thermal property study revealed the morphology of the copolymer could be changed from semi-crystalline to amorphous with increasing hydrophilic β-malic acid content. The copolymers with 8 and 13 mol% β-malic acid content possessed enough mechanical property for fabricating cell scaffold. Degradation result demonstrated that most of the hydrophilic β-malic acid units broke down from the copolymer within 1 week and the ester bond between L -lactide and β-malic acid hydrolyzed prior to the inner ester bond of poly(L -lactide) (PLLA). Copyright © 2003 John Wiley & Sons, Ltd. 相似文献