首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   64163篇
  免费   5311篇
  国内免费   9799篇
化学   56811篇
晶体学   1784篇
力学   968篇
综合类   360篇
数学   5758篇
物理学   13592篇
  2024年   106篇
  2023年   630篇
  2022年   1401篇
  2021年   1360篇
  2020年   1661篇
  2019年   2638篇
  2018年   1650篇
  2017年   2689篇
  2016年   2210篇
  2015年   2168篇
  2014年   2841篇
  2013年   5435篇
  2012年   3784篇
  2011年   4265篇
  2010年   3418篇
  2009年   3937篇
  2008年   4271篇
  2007年   4205篇
  2006年   3893篇
  2005年   3555篇
  2004年   3337篇
  2003年   2751篇
  2002年   2584篇
  2001年   2001篇
  2000年   1942篇
  1999年   1526篇
  1998年   1363篇
  1997年   1162篇
  1996年   964篇
  1995年   931篇
  1994年   781篇
  1993年   668篇
  1992年   580篇
  1991年   412篇
  1990年   286篇
  1989年   286篇
  1988年   230篇
  1987年   148篇
  1986年   143篇
  1985年   148篇
  1984年   124篇
  1983年   78篇
  1982年   105篇
  1981年   112篇
  1980年   94篇
  1979年   108篇
  1978年   70篇
  1977年   51篇
  1976年   38篇
  1973年   34篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
971.
A convenient and practical InCl3 catalyzed three-component reaction of 4-hydroxy coumarin/1,3 diones, aromatic aldehyde, and secondary amine for the synthesis of α-benzylamino coumarins and diketones in good yields has been reported.  相似文献   
972.
As a photocatalyst, mesoporous carbon nitride (mpg‐C3N4) shows higher photocatalytic activities in organic synthesis. Herein we report an mpg‐C3N4‐catalyzed oxidation of α‐hydroxy ketones to synthesize 1,2‐diketones using visible light. This transformation represents a green and highly efficient synthetic route to synthesize 1,2‐diketones for which catalytic approaches are scarce.  相似文献   
973.
A novel sensor for detection of trace gallium ion [Ga(III)] was created by stepwise modification of a gold electrode with β‐cyclodextrin (β‐CD)/multi‐walled carbon nanotubes (MWCNTs) and an ion imprinted polymer (IIP). The sensor surface morphology was characterized by scanning electron microscopy. The electrochemical performance of the imprinted sensor was investigated by cyclic voltammetry, differential pulse voltammetry and chronoamperometry. The sensor displayed excellent selectivity towards the target Ga(III) ion. Meanwhile, the introduced MWCNTs displayed noticeable catalytic activity, and β‐CD demonstrated significant enrichment capacity. A linear calibration curve was obtained covering the concentration range from 5.0×10?8 to 1.0×10?4 mol·L?1, with a detection limit of 7.6×10?9 mol·L?1. The proposed sensor was successfully applied to detect Ga(III) in real urine samples.  相似文献   
974.
α,β‐Unsaturated esters have been employed as substrates in iridium‐catalyzed asymmetric hydrogenation. Full conversions and good to excellent enantioselectivities (up to 99 % ee) were obtained for a broad range of substrates with both aromatic‐ and aliphatic substituents on the prochiral carbon. The hydrogenated products are highly useful as building blocks in the synthesis of a variety of natural products and pharmaceuticals.  相似文献   
975.
In a one‐pot process without isolation of intermediates, (but‐3‐en‐1‐yl)pyridine ( 13 ) is treated sequentially with dicyclohexylborane, trimethylaluminium, and ethyl carbonochloridate yielding ethyl 1,4‐dihydro‐4,4‐(tetramethylene)pyridine‐1‐carboxylate (=ethyl 8‐azaspiro[4.5]deca‐6,9‐diene‐8‐carboxylate; 2 ) in 46% yield based on starting alkenylpyridine 13 (Scheme 5).  相似文献   
976.
Two types of metal-loaded visible-light-driven photocatalysts,Mo-BiVO4and Ag-BiVO4,were synthesized by wet impregnation method.Material poperties were characterized by UV-vis diffuse reflectance spectroscopy,X-ray diffraction,field emission scanning electron microscopy,X-ray photoelectron spectroscopy and low temperature nitrogen adsorption-desorption.Photocatalytic activity of the obtained materials was investigated through degrading methylene blue(MB) solution under visible-light irradiation.The results reveal that both metal loaded-BiVO4catalysts have monoclinic scheelite structure.Mo and Ag exist as oxides on the surface of the particles.The changes of absorption in visible-light region,band gap(E g) and specific surface area(A BET) caused by loading Ag are more obvious than those caused by loading Mo.But the isoelectric point of Ag-BiVO4decreases less than that of Mo-BiVO4does.Both catalysts show higher photocatalytic activity than pure BiVO4,resulting in the significantly improved efficiency of degradation of MB.And the degradation efficiency of these two metal-loaded BiVO4photocatalysts is similar to each other.However,mechanisms of such enhancement are different.The decrease of isoelectric point helps Mo-BiVO4improve the degradation efficiency.As for Ag-BiVO4,the augmentation of absorption in visible-light region as well as the abatement of E g plays more important roles.  相似文献   
977.
Solvothermal reaction of aromatic terphenyl-2,5,2',5'-tetracarboxylic acid (H 4 qptc) ligand and the transitional metal cation of Mn II in the presence of 3-(2-pyridyl)pyrazole (pp) affords one new coordination polymer, [Mn(qptc)0.5(pp)2]n·n(H2O) (1). The structure has been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR, TGA, and magnetism. The carboxyl groups of qptc 4-exhibit a μ1-η1 :η 0 coordination mode, and the qptc4- acts as a H-shaped ligand linking the Mn Ⅱ centers together to form a 2D polymeric [Mn(qptc) 0.5 ] n layer. The crystal of 1 crystallizes in orthorhombic, space group Pbca with a=9.3119(12), b=20.848(3), c=26.134(3) , V=5073.4(11) 3 , Z=8, C27H19MnN6O5 , Mr=562.42, Dc=1.473 g/cm3 , F(000)=2304 and μ(MoKα)=0.571 mm-1 . The final R=0.0468 and wR=0.1196 for 4429 observed reflections with I > 2σ(I) and R=0.0797 and wR=0.1383 for all data.  相似文献   
978.
LI Rui  TANG Yong-Jian  ZHANG Hong 《结构化学》2012,31(11):1634-1640
The binding energies, geometric structures and electronic properties of molybdenum trioxide (MoO3) molecule encapsulated inside (8,0), (9,0), (10,0) and (14,0) single-walled carbon nanotubes (SWNTs) have been investigated using density functional theory (DFT) method. Due to curvature effect, the calculated binding energy values are different, the variation of which indicated that the stability of MoO3 /SWNT systems increases with increasing the radius of SWNTs. At the same time, owing to the presence of MoO3 molecule, the band gap of MoO3 /SWNTs systems decreases. The analysis of density of states (DOS) reveals hybridization between C-2p and Mo-4d and between C-2p and O-2p orbitals near the Fermi level, which results in electron transfer from SWNTs to MoO3 molecule. The present computations suggest that electronic properties of SWNTs can be modified by doping MoO3 molecule.  相似文献   
979.
This procedure works efficiently for high selective mono nitration of phenol and substituted phenol to corresponding nitro compounds in moderate to high yield using poly(4-vinylpyridinium nitrate) and silica sulfuric acid in dichloromethane at room temperature.  相似文献   
980.
Abstract

Viscosities of the systems, 1-propanol + aniline, 1-propanol+N-methylaniline and 1-propanol+N,N-dimethylaniline have been measured in the temperature range 294.15 to 323.15K for the whole range of composition. The viscosities have been plotted against mole fraction of anilines. The viscosity-composition curves show minima, though not well-defined, in highly rich, moderately rich and moderately poor regions of 1-propanol respectively for 1-propanol + aniline, 1-propanol + N-methylaniline and 1-propanol +N,N-dimethylaniline systems. The excess viscosities have been found to be negative for all the systems throughout the whole composition and plotted against mole fraction of anilines. The thermodynamic activation parameters, such as, enthalpies, entropies and free energies and their excess values have been evaluated. The excess free energies have been found to be negative for all the systems and over the whole range of composition. The excess free energies have been plotted against the mole fraction of anilines. The viscosities, excess viscosities and excess free energies have been explained by assuming that the associated compounds, aniline, N-methylaniline and 1-propanol, are dissociated into smaller units in the solution systems by the rupture of H-bonds.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号