全文获取类型
收费全文 | 3555篇 |
免费 | 197篇 |
国内免费 | 267篇 |
专业分类
化学 | 1683篇 |
晶体学 | 41篇 |
力学 | 164篇 |
综合类 | 11篇 |
数学 | 858篇 |
物理学 | 689篇 |
综合类 | 573篇 |
出版年
2024年 | 3篇 |
2023年 | 28篇 |
2022年 | 112篇 |
2021年 | 83篇 |
2020年 | 59篇 |
2019年 | 75篇 |
2018年 | 71篇 |
2017年 | 64篇 |
2016年 | 76篇 |
2015年 | 68篇 |
2014年 | 90篇 |
2013年 | 156篇 |
2012年 | 144篇 |
2011年 | 239篇 |
2010年 | 216篇 |
2009年 | 352篇 |
2008年 | 311篇 |
2007年 | 210篇 |
2006年 | 242篇 |
2005年 | 191篇 |
2004年 | 202篇 |
2003年 | 155篇 |
2002年 | 178篇 |
2001年 | 93篇 |
2000年 | 68篇 |
1999年 | 75篇 |
1998年 | 60篇 |
1997年 | 53篇 |
1996年 | 44篇 |
1995年 | 40篇 |
1994年 | 40篇 |
1993年 | 35篇 |
1992年 | 42篇 |
1991年 | 20篇 |
1990年 | 18篇 |
1989年 | 18篇 |
1988年 | 14篇 |
1987年 | 8篇 |
1986年 | 6篇 |
1985年 | 11篇 |
1984年 | 6篇 |
1983年 | 8篇 |
1981年 | 9篇 |
1980年 | 6篇 |
1979年 | 5篇 |
1978年 | 4篇 |
1977年 | 4篇 |
1976年 | 3篇 |
1974年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有4019条查询结果,搜索用时 15 毫秒
81.
Shin-ichi NayaHisashi Miyama Kenji YasuTohru Takayasu Makoto Nitta 《Tetrahedron》2003,59(10):1811-1821
Three-step reactions starting from 2-chlorotropone with barbituric acid afforded novel 7,9-dimethylcyclohepta[b]pyrimido[5,4-d]furan-8(7H),10(9H)-dionylium tetrafluoroborate (9·BF4−), which is the isoelectronic compound of the 5-ethyl-3-methyllumiflavinium ion. The stability of cation 9 is expressed by the pKR+ value, which was determined spectrophotometrically, as ca. 6.0. The electrochemical reduction of 9 exhibited low reduction potential at −0.58 (V vs Ag/AgNO3), upon cyclic voltammetry (CV). In a search for the reactivity, reactions of 9·BF4− with some nucleophiles, hydroxide, hydride, amines, thiols, and methanol, were carried out to exhibit that the introduction of nucleophiles is dependent on the nucleophile itself. The photo-induced oxidation reactions of some alcohols catalyzed by 9·BF4− under aerobic conditions were carried out to give the corresponding carbonyl compounds in more than 100% yield [based on compound 9·BF4−], suggesting the oxidizing function of 9·BF4− toward alcohols in the autorecycling process. The UV-vis and fluorescence spectra of 9 were studied to suggest the electron transfer from alcohols to the excited 9. 相似文献
82.
The dimensional analyses of the position and momentum variances‐based quantum mechanical Heisenberg uncertainty measure, as well as the entropic information measures given by the Shannon information entropy sum and the product of Fisher information measures are carried out for two widely used nonrelativistic isotropic exponential‐cosine screened Coulomb potentials generated by multiplying the superpositions of (i) Yukawa‐like, ?Z(e?μr/r), and (ii) Hulthén‐like, ?Zμ(1/(eμr ? 1)), potentials by cos(bμr) followed by addition of the term a/r2, where a and b ≥ 0, μ are the screening parameters and Z, in case of atoms, denotes the nuclear charge. Under the spherical symmetry, all the information measures considered are shown to be independent of the scaling of the set [μ, Z] at a fixed value of μ/Z, a, and b and the other parameters defining the superpositions of the potentials. Numerical results are presented, which support the validity of the scaling properties. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
83.
The surface pressure-molecular area curve of the mixed monolayer of 16-(9-anthroyloxy) palmitic acid (16AP) and fatty acid (palmitic or stearic acids) showed various kink points which indicated the phase transitions of the monolayer. On the basis of the surface phase rule, the phase diagrams of the mixed monolayer were elucidated. The bifunctional molecule, 16AP, takes two orientations in a monolayer state, that is, horizontal and vertical ones. Horizontally oriented 16AP and vertically oriented fatty acid form a mixed monolayer but this exhibits deviation from the ideal mixing, which was interpreted in terms of the surface regular solution theory. On the other hand, the 16AP molecule in the vertical state was found to be immiscible with the fatty acid molecule in a monolayer de spite both molecules being vertical to the surface and parallel to each other. This was caused by the participation of the 9-anthroyloxy moiety of 16AP in the interaction of 16AP and fatty acid in the hydrophobic region of the monolayer. 相似文献
84.
Summary A sensitive LC method for the detection of amino acids and oligopeptides with pre-column fluorescence derivatization has been
developed. Glycine, glycylglycine, triglycine, glutathione, glutamic acid, and cysteine were separated on a reversed-phase
C18 column with methanol-water-triethylamine eluent, derivatization and chromatographic conditions were optimized. The six derivatives
were eluted in 20 min with good reproducibility. The relative standard derviations (n=6) at an analytical concentration of
2×10−6 M are <5%. Detection limits (signal-to-noise ratio=3) for the six derivatives are 23–68 fmol. 相似文献
85.
Syntheses and Crystal Structures of [Pd9As8(PPh2)8] and [Pd9Sb6(PPh3)8] [PdCl2(PPh3)2] reacts with As(SiMe3)3 to give the new cluster [Pd9As8(PPh3)8] ( 4 ). 4 has been characterized by X-ray crystal structure analysis. It is a molecule in which four [Pd2(PPh3)2]-units are bridged by As2-units. A further Pd atom is located in the centre of the cluster. 4 crystallizes in the space group C2/c with four formula units per unit cell. The lattice constants at 200 K are: a = 3 970.6(3), b = 1 648.90(16), c = 3 266.30(20) pm, β = 131,44(4)°. The reaction of [PdCl2(PPh3)2] with Sb(SiMe3)3 yields [Pd9Sb6(PPh3)8] ( 5 ). 5 consists of a body centred cubic Pd9-cluster. All of the cube faces are capped by μ4-Sb-ligands. 5 crystallizes in the space group Pn3 with two formula units per unit cell. The lattice constants at 200 K are: a = b = c = 1 995.4(2) pm. 相似文献
86.
87.
We have prepared SrFe2/3B″1/3O3 (B″=Mo, U, Te, and W) double perovskites in polycrystalline form by ceramic methods. Phases with B″=U, Te and W have been studied by X-ray powder diffraction and the results have been compared with neutron diffraction data available for B″=Mo. At room temperature, the stoichiometric samples crystallize in the tetragonal crystal system (space group I4/m, Z=4). Cell parameters when B″=U, Te and W are a=5.6936(1) Å, c=8.0637(1)Å; a=5.5776(1) Å, c=7.9144(3) Å and a=5.5707(3) Å, c=7.9081(5) Å, respectively.The Mössbauer spectra at room temperature for all compounds show hyperfine parameters belonging to two Fe3+ sites located at lattice positions with different degrees of distortion. This is in agreement with diffraction data that indicate that the series of compounds display different degrees of Fe-site disorder, which increases in the following sequence: Mo<U<Te<W. 相似文献
88.
麝香草的新单萜配糖物的分离与合成 总被引:1,自引:0,他引:1
从麝香草(Thymus vulgaris L)的甲醇萃取物中分离出三个单萜配糖物. 用核磁共振光谱确定了它们的结构为对伞花-9-基-β-D-葡糖苷(1), 5-β-D-葡糖苷百里氢醌(2)和2-β-D-葡糖苷百里氢醌(3). 其中1是新化合物, 用以对伞花-9-醇为原料的对映体选择性合成方法确定了化合物1的8位的立体化学为R型. 相似文献
89.
Condensation of 1-alkyl-, 1-allyl-, and 1-benzyl-1,2,3,9a-tetrahydro-9H-imidazo[1,2-a]indol-2-ones with benzaldehydes in acetic acid and subsequent treatment of the reaction mixture with potassium hydroxide afforded 1-substituted 9a-(2-phenylethenyl)-1,2,3,9a-tetrahydro-9H-imidazo[1,2-a]indol-2-one derivatives. 1-Methyl- and 1-ethyl-9a-[2-(4-dimethylaminophenyl)ethenyl]-1,2,3,9a-tetrahydro-9H-imidazo[1,2-a]indol-2-ones were synthesized by alkylation of 9a-[2-(4-dimethylaminophenyl)ethenyl]-1,2,3,9a-tetrahydro-9H-imidazo[1,2-a]indol-2-one with methyl- and ethyl iodides in DMF in the presence of a strong base. 相似文献
90.
C.N.R. Rao D.D. Sarma P.R. Sarode E.V. Sampathkumaran L.C. Gupta R. Vijayaraghavan 《Chemical physics letters》1980,76(3):413-415
The valence state of Yb in some of its intermetallics, YbNi2Ge2, YbCu2Si2 and YbPd2Si2 has been investigated by LIII(Yb) absorption edges and X-ray pnotoelectron spectra in the 4f and 4d regions. These studies establish the presence of mixed valence in all three systems and illustrate the utility of 4f and 4d spectra in the study of mixed valence in Yb compounds. 相似文献