全文获取类型
收费全文 | 20936篇 |
免费 | 3412篇 |
国内免费 | 2388篇 |
专业分类
化学 | 14476篇 |
晶体学 | 208篇 |
力学 | 1526篇 |
综合类 | 205篇 |
数学 | 2329篇 |
物理学 | 7992篇 |
出版年
2024年 | 69篇 |
2023年 | 401篇 |
2022年 | 708篇 |
2021年 | 777篇 |
2020年 | 830篇 |
2019年 | 797篇 |
2018年 | 679篇 |
2017年 | 586篇 |
2016年 | 968篇 |
2015年 | 1016篇 |
2014年 | 1159篇 |
2013年 | 1527篇 |
2012年 | 1788篇 |
2011年 | 1962篇 |
2010年 | 1248篇 |
2009年 | 1190篇 |
2008年 | 1218篇 |
2007年 | 1134篇 |
2006年 | 1120篇 |
2005年 | 931篇 |
2004年 | 835篇 |
2003年 | 613篇 |
2002年 | 572篇 |
2001年 | 505篇 |
2000年 | 455篇 |
1999年 | 431篇 |
1998年 | 380篇 |
1997年 | 323篇 |
1996年 | 335篇 |
1995年 | 319篇 |
1994年 | 299篇 |
1993年 | 232篇 |
1992年 | 247篇 |
1991年 | 205篇 |
1990年 | 180篇 |
1989年 | 152篇 |
1988年 | 91篇 |
1987年 | 89篇 |
1986年 | 75篇 |
1985年 | 75篇 |
1984年 | 42篇 |
1983年 | 44篇 |
1982年 | 37篇 |
1981年 | 22篇 |
1980年 | 15篇 |
1979年 | 8篇 |
1977年 | 5篇 |
1975年 | 6篇 |
1969年 | 4篇 |
1957年 | 8篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
191.
In this study, we developed an analytical method for the enantioseparation of ofloxacin, using capillary electrophoresis with fluorescence detection. The optimum background electrolyte was obtained to be 60 mM hydroxylpropyl‐β‐cyclodextrin (HP‐β‐CD) in 50 mM phosphate buffer at pH 2.30. Under these conditions, the (+) and (‐) ofloxacin were completely separated, with the detection limit of 10 nM when the sample was prepared in deionized water. The linear ranges of levofloxacin in deionized water and untreated urine were 10?7 to 5 × 10?3 M with R2 = 0.9989 and 5 × 10?6to 5 × 10?3 M with R2 = 0.9943, respectively. We also applied this method to investigate the purity of a commercial drug. The results revealed that the ratio between (+)‐ofloxacin and (‐)‐ofloxacin (levofloxacin) was 99.9:0.1, and there is about 93 mg levofloxacin per tablet (200 mg). The concentration of levofloxacin in patient's urine was founded to be 7.9 × 10?4M, and the ratio between the two optical isomers was 99.3:0.7. 相似文献
192.
Shen J Ye Y Hu J Shen H Le Z 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2001,57(3):551-559
Copper(II), zinc(II), cobalt(II) and cobalt(III) complexes of N-D-glucosamine beta-naphthaldehyde (C17H19O6N, NG) and glycine were synthesized. The four novel metal complexes, Cu(II)C19H28O11N2(CuGNG), Zn(II)C19H24O9N2 (ZnGNG), Co(II)C19H28O11N2(Co(II)GNG) and Co(III)C21H29O12N2(Co(III)GNG) were characterized by means of infrared (IR), electronic absorption spectroscopy and NMR etc. The surface-enhanced Raman spectra of the four complexes and their interaction with DNA were studied. By comparison of the surface-enhanced Raman spectra (SERS), the information of the four complexes' SER active sites and adsorption orientation were obtained. Combined with fluorescence spectra of Ethidium bromide (EthBr) DNA system, we concluded that none of the four complexes intercalate into DNA and that the presence of the glycine ligand lowered the anticancer activity of NG series complexes. 相似文献
193.
A hydrazide-derived bis(meta-phenylene)-32-crown-10 host showed a dimeric structure via quadruple N-H?O hydrogen bonds, but a polymeric structure via two N-H?O hydrogen bonds and two C-H?O hydrogen bonds at each knot in the presence of paraquat in the solid state, which led to a novel poly(taco complex) and ordering arrangement of the guest molecules indirectly. 相似文献
194.
195.
196.
Fan CA Hu XD Tu YQ Wang BM Song ZL 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(18):4301-4310
A novel and highly diastereoselective samarium-catalyzed tandem rearrangement/reduction of secondary alpha-hydroxy epoxides, which involves a C1 to C3 carbon migration rearrangement and a very interesting hetero-Tishchenko reduction of the intermediate aldehyde and the reductant aldehyde, has been reported. This reaction could be developed to provide a facile and stereoselective construction of 2-quarternary 1,3-diol units with an hydroxymethyl moiety attached to the diastereogenic quaternary carbon center. Detailed investigations have been carried out concerning the screening of the aldehydes as a reductant, the optimization of reaction conditions, and the substrate scope of this tandem reaction. A catalytic cycle for this reaction, the electronic and steric effects of the reductant aldehydes, and the mechanism for the acyl migration of 1,3-diol monoesters are proposed. 相似文献
197.
In this communication, we report the first simple and fast one-step method for synthesizing highly monodisperse micron-size PMMA particles in organic media through dispersion polymerization in the presence of PHSA (a polyhydroxyl-stearic-acid graft PMMA copolymer) as a stabilizer. There are two significant advantages of our method over earlier methods. First, by optimizing the composition of a solvent mixture of hexane and dodecane, we were able to increase the concentration of monomer up to 50-56% and obtain unusually large (up to 10 mum in diameter) PMMA particles. Second, by strictly controlling the nucleation time, we were able to make PMMA particles with a low polydispersity of around 1%, much lower than has ever before been achieved for such large particles. We also report an unusual apparent metastable state in the nucleation stage. 相似文献
198.
Wang Li Duan Liying Wang Enbo Xiao Dongrong Li Yangguang Lan Yang Xu Lin Hu Changwen 《Transition Metal Chemistry》2004,29(2):212-215
The novel complex, Co(H2O)5[Co(2,6-pydc)2] (1) has been prepared in aqueous solution and characterized by single-crystal X-ray diffraction, elemental analyses and i.r. spectra. X-ray structural analysis revealed that three novel compounds each possess both – stacking and hydrogen-bonding interaction three-dimensional (3-D) networks. 相似文献
199.
用TRP技术研究了以全硅MCM-41(Si-MCM-41)和HNO3交换的全硅MCM-41(H-MCM-41)为载体制备的Ni-Mo、Co-Mo和Ni-W加氢脱硫(HDS)催化剂的还原性能,并以0.8(wt)%二苯并噻吩(DBT)的十氢萘溶液为模型化合物,在高压固定床反应器上考察了上述催化剂的加氢脱硫(HDS)反应性能。结果表明,Si-MCM-41经稀HNO3交换后,所担载的Ni-Mo和Ni-W催化剂还原性能、HDS活性和加氢活性有显著变化,但对Co-Mo催化剂影响不大。这说明在Ni-Mo/H-MCM-41和Ni-W/H-MCM-41中可能存在氢溢流现象,DBT的HDS活性与载体表面酸性和氢溢流有关。 相似文献
200.
Huang S Xiao Z Wang F Zhou J Yuan G Zhang S Chen Z Thiel W von Ragué Schleyer P Zhang X Hu X Chen B Gan L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(18):5449-5456
[60]Fullerene mixed peroxides C60(O)(OOtBu)4 exhibit chemo- and regioselective reactions under mild conditions. The epoxy moiety is opened by ferric chloride to form vicinal hydroxy chloride C60Cl(OH)(OOtBu)4. BF3 is also effective in opening the epoxy moiety. The O-O bond of the fullerene mixed peroxide is cleaved by aluminum chloride to form both [5,6]- and [6,6]-fullerene hemiketals (oxohomo[60]fullerenes). A Hock-type rearrangement is proposed for the formation of the hemiketals, in which a fullerene C-C bond is cleaved. Lewis acids and/or visible light can initiate isomerization of the hemiketal isomers. Single-crystal X-ray analysis and theoretical calculations confirmed the results. 相似文献