全文获取类型
收费全文 | 37277篇 |
免费 | 5495篇 |
国内免费 | 3652篇 |
专业分类
化学 | 25772篇 |
晶体学 | 358篇 |
力学 | 2227篇 |
综合类 | 241篇 |
数学 | 4280篇 |
物理学 | 13546篇 |
出版年
2024年 | 111篇 |
2023年 | 759篇 |
2022年 | 1224篇 |
2021年 | 1401篇 |
2020年 | 1443篇 |
2019年 | 1329篇 |
2018年 | 1150篇 |
2017年 | 1067篇 |
2016年 | 1611篇 |
2015年 | 1633篇 |
2014年 | 2004篇 |
2013年 | 2579篇 |
2012年 | 3254篇 |
2011年 | 3210篇 |
2010年 | 2180篇 |
2009年 | 2051篇 |
2008年 | 2203篇 |
2007年 | 1961篇 |
2006年 | 1843篇 |
2005年 | 1539篇 |
2004年 | 1301篇 |
2003年 | 984篇 |
2002年 | 894篇 |
2001年 | 738篇 |
2000年 | 691篇 |
1999年 | 829篇 |
1998年 | 693篇 |
1997年 | 635篇 |
1996年 | 705篇 |
1995年 | 601篇 |
1994年 | 550篇 |
1993年 | 470篇 |
1992年 | 449篇 |
1991年 | 364篇 |
1990年 | 324篇 |
1989年 | 236篇 |
1988年 | 216篇 |
1987年 | 198篇 |
1986年 | 141篇 |
1985年 | 156篇 |
1984年 | 135篇 |
1983年 | 116篇 |
1982年 | 80篇 |
1981年 | 59篇 |
1980年 | 49篇 |
1979年 | 33篇 |
1978年 | 26篇 |
1976年 | 27篇 |
1975年 | 31篇 |
1974年 | 23篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
91.
Wu X Ding S Ding Q Gray NS Schultz PG 《Journal of the American Chemical Society》2002,124(49):14520-14521
Purmorphamine, which is a 2,6,9-trisubstituted purine compound, was discovered through cell-based high-throughput screening from a heterocycle combinatorial library. It differentiates multipotent mesenchymal progenitor cells into an osteoblast lineage. It will serve as a unique chemical tool to study the molecular mechanisms of osteogenesis of stem cells and bone development. 相似文献
92.
Preparative separation of methyl gallate in leaves extract of Acer truncatum Bunge was conducted using high-speed counter-current chromatography (HSCCC) with a solvent system composed of ethyl acetate-ethanol-water at volume ratios of 5:1:5 (v/v/v). In a single operation, 57.5 mg of methyl gallate was obtained from 120 mg of the extract. HPLC analyses of the counter-current chromatography (CCC) fraction revealed that the methyl gallate was having over 97% purity. Its structure was identified by 1H NMR and 13C NMR. 相似文献
93.
Three new pavine N-oxide alkaloids, (-)-isocaryachine-N-oxide B, (+)-caryachine-N-oxide, (-)-caryachine-N-oxide, and a new isoquinoline alkaloid, 6,7-methylenedioxy-N-methylisoquinoline together with 11 known alkaloids were isolated and characterized from the stem bark of Cryptocarya chinensis. The structures of the isolated compounds were determined by spectral methods. The stereochemistry of pavine-N-oxide alkaloids is also discussed. 相似文献
94.
We have prepared a series of chiral dendrons (1-4) in which chiral subunits are placed in individual generational shells at varying distances from the focal point. The optical activity of these chiral dendritic structures is successfully modeled using structurally similar low-molecular weight model compounds. In dendrons 1a and 1b a chiral subunit is directly adjacent to the focal point, whereas in dendrons 2, 3, and 4a,b the chiral subunits are incorporated in the interior of the dendron. A marked difference in optical activity between the former 1a and 1b) and latter (2, 3, 4a,b) dendrons is mirrored in the optical activities of model compounds 12a, 12b, 19a, and 19b. These model compounds directly mimic the surrounding constitution of the chiral subunits in the dendrons. This successful analysis of the chiroptical data using low-molecular weight model compounds suggests that these dendrons do not possess conformational order in solution. 相似文献
95.
Apffel A Yin H Hancock WS McManigill D Frenz J Wu SL 《Journal of chromatography. A》1999,832(1-2):149-163
A system is described which allows operation of a range of capillary based liquid phase separations including capillary electrophoresis, isocratic and gradient capillary electrochromatography, isocratic and gradient capillary liquid chromatography and electrically assisted gradient capillary liquid chromatography. The system was coupled to electrospray ionization mass spectrometry in the electrically assisted capillary liquid chromatography mode to investigate the effect of applied voltage on the selectivity in peptide mapping separations. Analyses were performed on tryptic digests of recombinant human growth hormone and tissue plasminogen activator. The results show a small but useful effect on selectivity that can be used to fine tune specific separations. 相似文献
96.
DFT study on the geometric, electronic structure and Raman spectra of 5,15-diphenylporphine 总被引:1,自引:0,他引:1
Zhang YH Li ZY Wu Y Zhu YZ Zheng JY 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,62(1-3):83-91
The ground state geometric, electronic structure and Raman spectra of 5,15-diphenylporphine (H(2)DPP) have been studied using B3LYP/6-31G(d) method and compared with that of well-studied free base porphine (H(2)P) and meso-tetraphenylporphine (H(2)TPP). Calculation shows that 5,15-substitution causes remarkable in-plane distortion, whereas the resulting out-of-plane distortion is negligible. The calculated electronic structure of H(2)DPP is consistent with the absorption spectra compared with H(2)P and H(2)TPP. The calculated vibrational frequencies of H(2)DPP scaled with a single factor of 0.971 agree well with experimental data (the rms error is 8.0 cm(-1)). The assignment of experimental Raman bands of H(2)DPP was discussed on the basis of theoretical calculation and the comparison with that of H(2)P and H(2)TPP. The splitting of some vibrational modes involving the motion of C(m) atom, such as nu(1), nu(8), and nu(10), was observed and was attributed to the diversification of the environment around C(m) atoms. As the shift of absorption peaks, the shift of some structure-sensitive Raman bands of H(2)DPP form that of H(2)TPP and H(2)P was attributed to the in-plane nuclear reorganization (IPNR) induced by phenyl-substitution, though the contribution of nonplanarity mechanism could not be excluded completely. 相似文献
97.
LIU Si-Min WU Xiao-Jun YAO Jun-Hua WU Cheng-Tai 《有机化学》2003,23(Z1):261-262
Non-covalent attractive forces are commonly employed in biological systems to drive the assembly of highly orga nized supramolecular entities from relatively simple subunits. 相似文献
98.
The development of an efficient solid sorbent personal sampler with increased convenience for sample collection in workplaces is described. Several solid sorbents were coated with tryptamine, and sampling tubes were prepared with the coated sorbents. These tubes were evaluated for the collection of phenyl isocyanate vapour generated in a commercial test atmosphere generation system that permits the simultaneous collection of up to 12 uniformly loaded samples. Tryptamine-coated XAD-2 resin was shown to be the most efficient solid sorbent for the collection of airborne phenyl isocyanate. The optimum amount of tryptamine needed for coating XAD-2 resin was investigated. 相似文献
99.
Protection of carbonyls as acetals or ketals using Brønsted acidic ionic liquid [Hmim]BF4 as catalyst as well as solvent was investigated. Satisfactory results were obtained for the protection of carbonyls as cycloacetals or ketals with diols. The product can be separated conveniently from the reaction system, and the ionic liquid can be reused after removal of water. 相似文献
100.
Hulin Li Boyan Zhang Lin Ma Liliu Wu James Q. Chambers 《Transition Metal Chemistry》1995,20(6):552-556
Summary The spectrochemical, electrochemical and electrocatalytic properties of Co[15]aneN4 ([15]aneN4 = 1,4,8,12-tetraazacyclopentadecane) have been investigated. The results show that, in aqueous solution, this compound mainly exists as three species whose axial coordination positions are occupied by water and/or hydroxy ligands; it is marginal whether other substrates such as Cl– and NO
inf3
sup–
interact with the central ion in acid-base solutions. The approximate Pourbaix diagram of CoIII/II[15]ane N4 was determined. There is an electrochemically-induced isomerization between two trans conformational isomers of the Co[15]aneN4 complexes in acid and netural solutions. The Co[15]aneN4 complex has electrocatalytic properties for reduction of nitrate and nitrite only in strong alkaline solution. 相似文献