全文获取类型
收费全文 | 4035篇 |
免费 | 207篇 |
国内免费 | 406篇 |
专业分类
化学 | 3059篇 |
晶体学 | 71篇 |
力学 | 33篇 |
综合类 | 26篇 |
数学 | 604篇 |
物理学 | 855篇 |
出版年
2024年 | 4篇 |
2023年 | 23篇 |
2022年 | 85篇 |
2021年 | 95篇 |
2020年 | 70篇 |
2019年 | 176篇 |
2018年 | 231篇 |
2017年 | 71篇 |
2016年 | 98篇 |
2015年 | 78篇 |
2014年 | 119篇 |
2013年 | 253篇 |
2012年 | 147篇 |
2011年 | 222篇 |
2010年 | 213篇 |
2009年 | 309篇 |
2008年 | 270篇 |
2007年 | 256篇 |
2006年 | 239篇 |
2005年 | 211篇 |
2004年 | 205篇 |
2003年 | 146篇 |
2002年 | 204篇 |
2001年 | 117篇 |
2000年 | 82篇 |
1999年 | 66篇 |
1998年 | 71篇 |
1997年 | 51篇 |
1996年 | 63篇 |
1995年 | 56篇 |
1994年 | 70篇 |
1993年 | 61篇 |
1992年 | 48篇 |
1991年 | 28篇 |
1990年 | 26篇 |
1989年 | 19篇 |
1988年 | 21篇 |
1987年 | 16篇 |
1986年 | 15篇 |
1985年 | 9篇 |
1984年 | 13篇 |
1983年 | 5篇 |
1982年 | 10篇 |
1981年 | 13篇 |
1980年 | 10篇 |
1979年 | 16篇 |
1978年 | 11篇 |
1977年 | 7篇 |
1976年 | 8篇 |
1975年 | 4篇 |
排序方式: 共有4648条查询结果,搜索用时 31 毫秒
221.
Tahya Bamine Edouard Boivin Christian Masquelier Laurence Croguennec Elodie Salager Dany Carlier 《Magnetic resonance in chemistry : MRC》2020,58(11):1109-1117
7Li, 31P, and 19F solid-state nuclear magnetic resonance (NMR) spectroscopy was used to investigate the local arrangement of oxygen and fluorine in LiVPO4F1-yOy materials, interesting as positive electrode materials for Li-ion batteries. From the evolution of the 1D spectra versus y, 2D 7Li radiofrequency-driven recoupling (RFDR) experiments combined, and a tentative signal assignment based on density functional theory (DFT) calculations, it appears that F and O are not randomly dispersed on the bridging X position between two X–VO4–X octahedra (X = O or F) but tend to segregate at a local scale. Using DFT calculations, we analyzed the impact of the different local environments on the local electronic structure. Depending on the nature of the VO4X2 environments, vanadium ions are either in the +III or in the +IV oxidation state and can exhibit different distributions of their unpaired electron(s) on the d orbitals. Based on those different local electronic structures and on the computed Fermi contact shifts, we discuss the impact on the spin transfer mechanism on adjacent nuclei and propose tentative signal assignments. The O/F clustering tendency is discussed in relation with the formation of short VIVO vanadyl bonds with a very specific electronic structure and possible cooperative effect along the chain. 相似文献
222.
A simple, sensitive and rapid ultra‐high‐performance liquid chromatography–electrospray ionization–tandem mass spectrometry method was developed and validated for the quantification of warfarin and 7‐hydroxy warfarin in Sprague Dawley (SD) rats. Animals were administered a single dose of warfarin sodium formulations (crystalline and amorphous) at 12 mg/kg via oral gavage and blood was drawn over a 96‐h time course. Sample process recoveries, matrix effect and analyte stability were determined. The linearity for warfarin and 7‐hydroxy warfarin was from 5 to 2000 ng/mL in blank SD rat plasma. Correlation coefficients (r2) for standard calibration curves were >.98 and analytes quantified within ±15% of target at all calibrator concentrations. The average percent accuracy and precision for intra‐ and inter‐day were 93.7%–113.8% and ≤12.1%, respectively, for warfarin and 7‐hydroxy warfarin, across the quality control standards (5, 10, 500, 1800 and 2000 ng/mL). Acceptable analytical recovery (>55%) was achieved with process efficiencies >41.5% and matrix effects <139.9% over the analytical range. Both analytes were stable in stock solution, autosampler, benchtop and three cycles of freeze–thaw with percent accuracy ≥90.2% and precision (percent relative standard deviation) ≤14%. The validated method was successfully applied to a pre‐clinical bioavailability study of crystalline and amorphous warfarin sodium formulations in SD rats. 相似文献
223.
224.
225.
Alexander A. Bredikhin Zemfira A. Bredikhina Alexey V. Kurenkov Dmitry B. Krivolapov 《Tetrahedron: Asymmetry》2017,28(3):442-446
Racemic 3-(4-indolyloxy)-1,2-propanediol 2 has been effectively resolved into (S)- and (R)-enantiomers by a preferential crystallization procedure. Non-racemic (S)-2 was converted into (S)-4-(2,3-epoxypropoxy)-1H-indole (S)-4 via a Mitsunobu reaction and then into (S)-pindolol (S)-1. The crystalline (S)-1 was studied by single crystal X-ray diffraction. A large number of symmetry independent molecules (Z′ = 6) led to a weakening of the system of strong intermolecular hydrogen bonds, which combined with a loose packing (PI = 64.6%), may be the cause of the abnormally low melting point of (S)-1 as compared with rac-1. 相似文献
226.
TiO2 nanoparticles with unique crystalline-core/disordered-shell structures were synthesized in a one step process by employing 4-methoxycalix[7]arene nanoreactors. The nanoparticles were anchored on the surface of quartz beads as a monolayer and showed high visible-light driven photocatalytic activity, excellent long term durability and anti-poisoning property. Photocatalytic performance of the TiO2 nanoparticles was tested in a packed bed and complete decolorization of methyl orange was achieved under ultraviolet light or visible light. The decolorization process followed first-order kinetics and showed different behaviors for ultraviolet and visible radiation, while the overall rates of degradation were the same. 相似文献
227.
Dhananjai Pandey V. S. Tiwari A. K. Singh V. K. Wadhawan M. S. Somayazulu 《Phase Transitions》2013,86(2-3):165-202
Crystal structures and structural inhomogeneities observed in YBa2Cu3O7-y are reviewed. It is brought out that a proper understanding of the nature of the structural inhomogeneities is essential for exploiting the technological potential of this material. The need for an adequate characterization of specimens used for experiments is emphasized. Practical implications of the ferroelastic nature of the material are discussed. 相似文献
228.
Synthesis,characterization, density functional theory,X‐ray study,thermal stability,and biological and MOE relevance of metal complexes of griseofulvin
下载免费PDF全文
![点击此处可从《应用有机金属化学》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Metal(II) and metal(III) coordination compounds of griseofulvin (GFV) drug were synthesized. The structure of the ligand was determined on the basis of elemental analyses, infrared and 1H NMR spectroscopies and thermal studies. GFV behaved as a neutral tridentate chelating agent and coordinated to metal ions through three oxygen atoms: two methoxy groups and oxygen atom of furan ring. Metal complexes were characterized by means of elemental analyses and molar conductance, spectral (infrared, electron spin resonance) and thermal studies. All the complexes showed molar conductance behaviour corresponding to an electrolytic nature. All the complexes showed octahedral geometry, except [Zn(GFV)Cl]Cl that showed tetrahedral geometry. Density functional theory (DFT) calculations were employed to understand and estimate the contribution of each interaction in the formation of the assembly using several theoretical models. The computed parameters from DFT calculations for structure optimizations and vibrational frequencies were in good agreement with the experimental data. Newly synthesized metal complexes in addition to GFV were examined against opportunistic pathogens. The biological applications of complexes were studied with two Gram‐positive bacteria (Bacillus subtilis and Staphylococcus aureus) and two Gram‐negative bacteria (Escherichia coli and Neisseria gonorrhoeae) as well as their antifungal activity against Candida albicans. Results suggested that metal complexes were more biologically sensitive than free ligand. The complexes showed a moderate inhibition of MCF7 breast cancer cell line growth. Molecular docking studies further helped in understanding the mode of action of the compounds through their various interactions with the crystal structures of: human serum albumin (PDB: 5FUO), Staphylococcus aureus nucleoside (PDB: 3Q8U), human acetylcholinesterase (PDB: 1B41) and the human DNA–Topo I complex (PDB: 1SC7). 相似文献
229.
230.
Bo-Hwa Choi Goutam Chakraborty Kwanghee Baek Ho Sup Yoon 《Experimental & molecular medicine》2013,45(10):e47
Here, we report that B-cell lymphoma 2 (Bcl-2) is a novel target molecule of aspirin in breast cancer cells. Aspirin influenced the formation of a complex by Bcl-2 and FKBP38 and induced the nuclear translocation of Bcl-2 and its phosphorylation. These events inhibited cancer cell proliferation and subsequently enhanced MCF-7 breast cancer cell apoptosis. Bcl-2 knockdown using small interfering RNA (siRNA) delayed apoptotic cell death, which correlated with increased proliferation following aspirin exposure. In contrast, Bcl-2 overexpression enhanced the onset of aspirin-induced apoptosis, which was also associated with a significant increase in Bcl-2 phosphorylation in the nucleus. Therefore, this study may provide novel insight into the molecular mechanism of aspirin, particularly its anticancer effects in Bcl-2- and estrogen receptor-positive breast cancer cells. 相似文献