全文获取类型
收费全文 | 1116篇 |
免费 | 49篇 |
国内免费 | 2篇 |
专业分类
化学 | 932篇 |
晶体学 | 15篇 |
力学 | 9篇 |
数学 | 78篇 |
物理学 | 133篇 |
出版年
2023年 | 12篇 |
2022年 | 10篇 |
2021年 | 36篇 |
2020年 | 28篇 |
2019年 | 32篇 |
2018年 | 13篇 |
2017年 | 11篇 |
2016年 | 41篇 |
2015年 | 41篇 |
2014年 | 39篇 |
2013年 | 70篇 |
2012年 | 75篇 |
2011年 | 97篇 |
2010年 | 58篇 |
2009年 | 55篇 |
2008年 | 68篇 |
2007年 | 70篇 |
2006年 | 61篇 |
2005年 | 54篇 |
2004年 | 49篇 |
2003年 | 45篇 |
2002年 | 24篇 |
2001年 | 19篇 |
2000年 | 13篇 |
1999年 | 15篇 |
1998年 | 17篇 |
1997年 | 12篇 |
1996年 | 22篇 |
1995年 | 7篇 |
1994年 | 11篇 |
1993年 | 7篇 |
1992年 | 3篇 |
1991年 | 3篇 |
1990年 | 5篇 |
1989年 | 7篇 |
1986年 | 3篇 |
1985年 | 7篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1978年 | 2篇 |
1977年 | 1篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1974年 | 1篇 |
1973年 | 3篇 |
1969年 | 1篇 |
1967年 | 1篇 |
排序方式: 共有1167条查询结果,搜索用时 31 毫秒
1.
2.
E. Baggio Saitovitch F. J. Litterst I. Souza Azevedo R. B. Scorzelli 《Hyperfine Interactions》1989,50(1-4):529-535
The Mössbauer spectra of YBa2(Cu1?x Fe x )3O7 at room temperature show several doublets attributed to Fe in Cu(1) sites with different oxygen configurations. Here we present a systematic study performed at 4.2 K forx=0.005, 0.01, 0.03, 0.05, 0.10, 0.15. To obtain information about the magnetic ordered state two samples, withx=0.005 andx=0.15, have been studied at 4.2 K underB ext=5 T. The Mössbauer spectra indicate that the iron moments are polarized forx=0.005, while in the ordered state (x=0.15) they have an antiferromagnetic or spin-glass-like arrangement with high anisotropy. 相似文献
3.
I. Souza Azevedo E. Baggio Saitovitch M. Hücker B. Büchner H. Micklitz 《The European Physical Journal B - Condensed Matter and Complex Systems》1998,6(3):313-315
57Fe M?ssbauer effect studies of La1.65Eu0.20Sr0.15CuO4 doped with 0.5 at% 57Fe performed in the temperature region 300 K >
T
> 4.2 K give an onset temperature for magnetic ordering of K. This temperature practically is the same as that found in Nd doped La2-xSrxCuO4. It indicates that the magnetic ordering temperature in the LTT phase of rare earth (RE) doped La2-xSrxCuO4 is independent of the RE moment. The direction of the 57Fe magnetic moment in the magnetically ordered state is within the CuO2 plane, while it has been found to be parallel to the c-axis in Nd doped La2-xSrxCuO4.
Received: 23 June 1998 / Accepted: 14 July 1998 相似文献
4.
5.
Ricardo Baggio Juan Carlos Muoz Mireille Perec 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(10):m498-m500
The title compound, [Dy2(C2H3O2)6(H2O)4]·4H2O, crystallizes in the form of dimeric units related by an inversion centre. Each cation is nine‐coordinate, binding to two water molecules and three acetate groups, two of which are bidentate and the third tridentate. This last acetate group acts as a bridge between neighbouring metal atoms, leading to an intradimer Dy?Dy separation of 4.170 (1) Å. 相似文献
6.
Elisa Brivio Alessandro Ceriotti Roberto Della Pergola Luigi Garlaschelli Mario Manassero Mirella Sansoni 《Journal of Cluster Science》1995,6(2):271-287
Redox condensation of [Ru3H(CO)11]- with Ni(CO)4, in tetrahydrofuran solution, under a nitrogen atmosphere, yields the tetranuclear anion [NiRuH(CO)11)-. Subsequent deprotonation with Bu'OK in acetonitrile solution leads to the formation of the related dianion. Both anions have been characterized by spectroscopic techniques, elemental analysis and single crystal X-ray diffraction. [PPh4][NiRu3H(CO)12] crystallizes in the triclinic space group PI with unit cell dimensionsof a = 11.842(2) Å,b = 12.335(3) Å, c = 13.3080) Å,a = 91.89(2)°, = 93.35(1)°,y = 96.41(2)°, Z = 2, V= 1926.9(7) Å'. The NiRu3, metal core of the molecule defines a distorted tetrahedron with nine terminal and three edge bridging carbonyl groups. The hydrido ligand was located by difference Fourier techniques and was found to bridge the NiRu2 basal triangle at a distance of 0.88(6) A from this plane. Selected average distances and angles are: Ru-Ru = 2.839 Å, Ru-Ni = 2.640 Å, Ru-C, = 1.910 A,Ru-C
b
= 2.084 Å, Ni-C
b
= 2.022 Å, Ru-H = 1.77 Å, C-0, = 1.135 Å, C-O
b
= 1.159 Å, M-C-O, = 176.3°,M-C--O
b
= 139.3°;other distances are: Ni-C1 = l.758(7) Å, Ni-H= 1.85(7) Å. [NEt4]2[NiRu3(CO)12] crystallizes in the orthorhombic space group Pnma (no. 62) with unit cell dimensions ofa=20.247(5) Å,b = 15.038(4)Å,c = 12.079(3) Å, Z=4, V=3678(2) A'. The molecule contains a tetrahedral NiRu3 core with eight terminal and four edge bridging carbon monoxide groups which bridge the three Ni-Ru and one Ru-Ru bond. Average distances and angles are: Ru -Ru =2.3050A Ru-Ni 2.648 Å, Ru-C
t
= 1.878 Å, Ru-C
b
2.045 Å, Ni-C
b
= 2.055 Å, C-O
t
= 1.145 Å, C-01,=1.157 Å, M-C-O,= 176.9°, M-C-O
b
= 138.6°; other distance is: Ni-C
t
= 1.754(10) Å,t = terminal,b = bridging. 相似文献
7.
Boseggia E Gatos M Lucatello L Mancin F Moro S Palumbo M Sissi C Tecilla P Tonellato U Zagotto G 《Journal of the American Chemical Society》2004,126(14):4543-4549
A series of cis-cis-triaminocyclohexane Zn(II) complex-anthraquinone intercalator conjugates, designed in such a way to allow their easy synthesis and modification, have been investigated as hydrolytic cleaving agents for plasmid DNA. The ligand structure comprises a triaminocyclohexane platform linked by means of alkyl spacers of different length (from C(4) to C(8)) to the anthraquinone group which may intercalate the DNA. At a concentration of 5 microM, the complex of the derivative with a C(8) alkyl spacer induces the hydrolytic stand scission of supercoiled DNA with a rate of 4.6 x 10(-6) s(-1) at pH 7 and 37 degrees C. The conjugation of the metal complex with the anthraquinone group leads to a 15-fold increase of the cleavage efficiency when compared with the anthraquinone lacking Zn-triaminocyclohexane complex. The straightforward synthetic procedure employed, allowing a systematic change of the spacer length, made possible to gain more insight on the role of the intercalating group in determining the reactivity of the systems. Comparison of the reactivity of the different complexes shows a remarkable increase of the DNA cleaving efficiency with the length of the spacer. In the case of too-short spacers, the advantages due to the increased DNA affinity are canceled due to the incorrect positioning of the reactive group, thus leading to cleavage inhibition. 相似文献
8.
Hélder A. Santos Elisabete S. Ferreira Elisa J. Pereira Carlos M. Pereira Prof. Kyösti Kontturi Prof. Fernando Silva Prof. 《Chemphyschem》2007,8(10):1540-1547
The interaction between glucose oxidase (GOx) and phospholipid monolayers is studied at the 1,2-dichloroethane/water interface by electrochemical impedance spectroscopy. Electrochemical experiments show that the presence of GOx induces changes in the capacitance curves at both negative and positive potentials, which are successfully explained by a theoretical model based on the solution of the Poisson-Boltzmann equation. These changes are ascribed to a reduced partition coefficient of GOx and an increase of the permittivity of the lipid hydrocarbon domain. Our results show that the presence of lipid molecules enhances the adsorption of GOx molecules at the liquid/liquid interface. At low lipid concentrations, the adsorption of GOx is probably the first step preceding its penetration into the lipid monolayer. The experimental results indicate that GOx penetrates better and forms more stable monolayers for lipids with longer hydrophobic tails. At high GOx concentrations, the formation of multilayers is observed. The phenomenon described here is strongly dependent on 1) the GOx and lipid concentrations, 2) the nature of the lipid, and 3) the potential drop across the interface. 相似文献
9.
Elisa Paredes 《Tetrahedron》2007,63(18):3790-3799
Thermal reactions between nitronaphthalenes and butadienes were studied. It was demonstrated that these reactions are capable of undergoing the normal electron demand Diels-Alder reaction, with a variety of dienes affording the phenanthrene derivatives. The influence of the extension and type of substitution was also discussed. When the electron-withdrawing activation of the naphthalenic nucleus or the donor properties of the dienes were not enough, N-naphthylpyrroles were detected as main product, suggesting that a competitive reaction would probably take place. The results clearly confirmed the dienophilic nature of nitronaphthalenic double bonds and provided an alternative procedure for phenanthrene derivatives and N-naphthylpyrroles' synthesis. The relative reactivity of the reactants and the viability of the reactions were discussed from a theoretical point of view. 相似文献
10.
Summary A polarimetric study of the tungsten (VI)-gluconic acid system in an excess of metal reveals the formation of four stable complexes: two monomers with 1 : 2 and 2: 1 stoichiometries and two dimers of 2:2 composition. The pH ranges of these species, the amount of acid equivalents their formation requires, and their conditional stability constants have also been calculated.The probable coordination of the organic ligand to the metallic centre in solutions containing different metal : ligand ratios has been investigated by13C-n.m.r. spectroscopy. The results confirm the formation of different complexes depending on the reagent which is in excess. The behaviour of the system when the metal is in excess is related to that of other polyhydroxylic ligands such as mannitol and sorbitol. 相似文献