全文获取类型
收费全文 | 17166篇 |
免费 | 493篇 |
国内免费 | 82篇 |
专业分类
化学 | 10215篇 |
晶体学 | 149篇 |
力学 | 692篇 |
数学 | 3076篇 |
物理学 | 3609篇 |
出版年
2022年 | 184篇 |
2021年 | 278篇 |
2020年 | 304篇 |
2019年 | 310篇 |
2018年 | 284篇 |
2017年 | 249篇 |
2016年 | 433篇 |
2015年 | 381篇 |
2014年 | 479篇 |
2013年 | 1028篇 |
2012年 | 904篇 |
2011年 | 1013篇 |
2010年 | 651篇 |
2009年 | 590篇 |
2008年 | 816篇 |
2007年 | 751篇 |
2006年 | 674篇 |
2005年 | 589篇 |
2004年 | 608篇 |
2003年 | 493篇 |
2002年 | 502篇 |
2001年 | 306篇 |
2000年 | 277篇 |
1999年 | 215篇 |
1998年 | 157篇 |
1997年 | 195篇 |
1996年 | 237篇 |
1995年 | 177篇 |
1994年 | 166篇 |
1993年 | 207篇 |
1992年 | 204篇 |
1991年 | 198篇 |
1990年 | 147篇 |
1989年 | 147篇 |
1988年 | 157篇 |
1987年 | 218篇 |
1986年 | 189篇 |
1985年 | 239篇 |
1984年 | 212篇 |
1983年 | 174篇 |
1982年 | 205篇 |
1981年 | 207篇 |
1980年 | 198篇 |
1979年 | 208篇 |
1978年 | 195篇 |
1977年 | 186篇 |
1976年 | 166篇 |
1975年 | 178篇 |
1974年 | 142篇 |
1973年 | 132篇 |
排序方式: 共有10000条查询结果,搜索用时 109 毫秒
141.
[reaction: see text] Since peroxidase-catalyzed dityrosine formation is inefficient for peptides, we have developed alternative conditions for intermolecular dityrosine formation using the Miyaura-Suzuki reaction. A one-pot reaction is effective for cross-linking short peptides, but longer peptides inhibit the Suzuki step, mandating a traditional two-step procedure using potassium acetate for the Miyaura reaction and potassium carbonate for the Suzuki coupling. These palladium-based methods are complementary to the well-established peroxidase-catalyzed oxidative phenolic coupling of full-length proteins. 相似文献
142.
143.
144.
When a two-phase column consisting of paraffin oil and silicon oil is placed in an otherwise air-filled, horizontal glass capillary, the column starts moving spontaneously. Silicon oil displaces paraffin oil, which in its turn displaces air at atmospheric conditions; a stable film of silicon oil is left at the receding silicon oil/air meniscus. The driving force for the motion is the difference in capillary pressure at the free interfaces. However, the column moves considerably more slowly than predicted by the driving forces; it appears that the forces resisting the motion at the moving liquid/liquid/solid line are much larger than one would expect on the basis of the interfacial tension and the viscosities of the two phase system. Some considerations are made on the relationship of the theory of Fowkes to our system. Also, a method for measuring low interfacial tensions between immiscible liquids is proposed. 相似文献
145.
R. Meij D.J. Stufkens K. Vrieze W. Van Gerresheim C.H. Stam 《Journal of organometallic chemistry》1979,164(3):353-370
Each of the compounds [MCl(Pr3)2(ArylNSO)] (M = RhI, IrI; R = i-Pr, Cy: Aryl = C6H5, 4-MeC6H4, 4-ClC6H4, 2,4,6-Me3C6H2 appears to exist as two isomers both in the solid state and in solution. The molecular and single crystal structure of one of the isomers of [RhCl(P-i-Pr)3)2(4-Me6H4NSO)] shows that the N-sulfinylaniline ligand is in the cis-configuration and coordinated to the rhodium atom via the sulfur-atom. The ligand lies in a plane which includes the rhodium atom and is in agreement with the Rh-S distance of 2.10 Å. IR results of the compounds (solid and solutions), 21P NMR data and 15N NMR of a 15N labelled compound, which yielded a 103Rh15N coupling constant of 15.5 Hz, show that in the second isomer the N-sulfinylaniline ligand is probably bonded to the metal atom via the π-NS bond.The ratio of the metal-π-NS bonded isomer and the metal-S bonded isomer decreases in the order Aryl = 4-ClC6H4 > C6H5 > 4-MeC6H4; R = i-Pr > Cy and M = Rh > Ir. The interconversion of the two isomers is intramolecular and becomes observable on the 31P NMR time scale at about 40° C for M = Rh.In the case of [Ir(P-i-Pr3)2(4-MeC6H4NSO)], cyclometallation of the sul- finylaniline is observed via the ortho-carbon atom, whereas cyclometallation via P-i-Pr3 is observed when the ortho-positions are blocked by methyl groups, e.g. when L = 2,4,6-Me3C6H2NSO. 相似文献
146.
147.
Oxychelerythrine, benzo[c]phenanthridine alkaloid, was synthesized from easily available starting toluamide 5 and benzonitrile 6 using toluamide-benzonitrile cycloaddition reaction in 6 steps. 相似文献
148.
Martinho M Banse F Bartoli JF Mattioli TA Battioni P Horner O Bourcier S Girerd JJ 《Inorganic chemistry》2005,44(25):9592-9596
The green complex S=1 [(TPEN)FeO]2+ [TPEN=N,N,N',N'-tetrakis(2-pyridylmethyl)ethane-1,2-diamine] has been obtained by treating the [(TPEN)Fe]2+ precursor with meta-chloroperoxybenzoic acid (m-CPBA). This high-valent complex belongs to the emerging family of synthetic models of Fe(IV)=O intermediates invoked during the catalytic cycle of biological systems. This complex exhibits spectroscopic characteristics that are similar to those of other models reported recently with a similar amine/pyridine environment. Thanks to its relative stability, vibrational data in solution have been obtained by Fourier transform infrared. A comparison of the Fe=O and Fe=(18)O wavenumbers reveals that the Fe-oxo vibration is not a pure one. The ability of the green complex to oxidize small organic molecules has been studied. Mixtures of oxygenated products derived from two- or four-electron oxidations are obtained. The reactivity of this [FeO]2+ complex is then not straightforward, and different mechanisms may be involved. 相似文献
149.
Investigations on Metal Catalysts. XXII. Chemisorption of Hydrogen on Pt? Ru and η-Al2O3 Supported Pt? Ru Catalysts Measurements of the H2 chemisorption by volumetric method were carried out on several series of Pt? Ru and η-Al2O3 supported Pt? Ru catalysts. Addition of Ru to Pt and vice versa effects a remarkable influence on the sorption behaviour of the starting samples. For mixtures of carrier-free catalysts and η-Al2O3 as well as Pt? Ru/η-Al2O3 catalysts a hydrogen-spillover effect was found. 相似文献
150.
Omar El Tall Nicole Jaffrezic‐Renault Monique Sigaud Olivier Vittori 《Electroanalysis》2007,19(11):1152-1159
Boron‐doped Diamond (BDD) electrode has become one of the important tools for heavy metal detection. By studying some analytical parameters of DPASV method, like deposition time and potential in different electrolyte concentrations (acetate buffer), the conditions for detecting very low metal ion levels (Zn, Cd, Pb, and Cu) could be chosen. Diluted electrolyte (0.01 M buffer) was one of the factors favoring low detection and quantification limits, but its quantification range is short in comparison to more concentrated media. For ?1.7 V deposition potential, the detection of single metal at ppb levels was reached in 60 s deposition time. Understanding different metal‐metal interactions shows the limits to the simultaneous determination of heavy metals at BDD. Quantification was possible for the simultaneous determination of Zn, Cd and Pb despite the overlapping of Zn and Cd peaks. The performance of the BDD was compared with that of another C‐based solid electrode: the glassy carbon electrode (without mercury plating). A lower base line current, wider potential range, higher sensitivity (3 to 5 times higher than GC) and longevity of the material were noticed for the BDD. 相似文献