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   427篇
  免费   15篇
  国内免费   4篇
化学   298篇
晶体学   5篇
力学   9篇
数学   37篇
物理学   97篇
  2024年   2篇
  2023年   3篇
  2022年   20篇
  2021年   22篇
  2020年   22篇
  2019年   23篇
  2018年   18篇
  2017年   16篇
  2016年   16篇
  2015年   18篇
  2014年   25篇
  2013年   33篇
  2012年   24篇
  2011年   26篇
  2010年   21篇
  2009年   22篇
  2008年   20篇
  2007年   13篇
  2006年   12篇
  2005年   4篇
  2004年   9篇
  2003年   7篇
  2002年   10篇
  2001年   3篇
  2000年   8篇
  1998年   1篇
  1996年   3篇
  1993年   1篇
  1992年   1篇
  1991年   1篇
  1989年   1篇
  1988年   6篇
  1987年   2篇
  1985年   4篇
  1984年   2篇
  1983年   1篇
  1982年   1篇
  1981年   2篇
  1980年   1篇
  1979年   3篇
  1978年   2篇
  1976年   3篇
  1975年   2篇
  1974年   3篇
  1973年   1篇
  1972年   1篇
  1969年   1篇
  1968年   3篇
  1967年   2篇
  1957年   1篇
排序方式: 共有446条查询结果,搜索用时 31 毫秒
31.
A facile and simple protocol for the 1,3‐dipolar cycloaddition of organic azides with terminal alkynes catalyzed by doped nano‐sized Cu2O on melamine? formaldehyde resin (nano‐Cu2O? MFR) as a new and convenient heterogeneous catalyst is described. In this method, ‘click’ cycloaddition of various structurally diverse β‐azido alcohols and alkynes in the presence of nano‐Cu2O? MFR in H2O/THF 1 : 2 furnished the corresponding 1,4‐disubstituted 1H‐1,2,3‐triazole adducts 1a – 1o in good to excellent yields at room temperature (Scheme and Table 3). The nano‐Cu2O? MFR was characterized by scanning electron microscopy (SEM), X‐ray diffraction (XRD), inductively coupled plasma (ICP) analysis, and FT‐IR. The nano‐Cu2O? MFR could be easily recovered and recycled from the reaction mixture and reused for many consecutive trials without significant decrease in activity (Table 4). The in vitro antibacterial activities of all synthesized compounds were tested on several Gram‐positive and/or Gram‐negative bacteria (Table 5). The results demonstrate the promising antibacterial activity for some of the synthesized compounds.  相似文献   
32.
Imidazolium‐based ionic liquids that contain perrhenate anions are very efficient reaction media for the epoxidation of olefins with H2O2 as an oxidant, thus affording cyclooctene in almost quantitative yields. The mechanism of this reaction does not follow the usual pathway through peroxo complexes, as is the case with long‐known molecular transition‐metal catalysts. By using in situ Raman, FTIR, and NMR spectroscopy and DFT calculations, we have shown that the formation of hydrogen bonds between the oxidant and perrhenate activates the oxidant, thereby leading to the transfer of an oxygen atom onto the olefin demonstrating the special features of an ionic liquid as a reaction environment. The influence of the imidazolium cation and the oxidant (aqueous H2O2, urea hydrogen peroxide, and tert‐butyl hydrogen peroxide) on the efficiency of the epoxidation of cis‐cyclooctene were examined. Other olefinic substrates were also used in this study and they exhibited good yields of the corresponding epoxides. This report shows the potential of using simple complexes or salts for the activation of hydrogen peroxide, owing to the interactions between the solvent medium and the active complex.  相似文献   
33.
34.
New complexes of general empirical formula, [M(NS)2] · nCHCl3 (M = NiII, CuII, PdII or PtII; NS = anionic form of the thiophene-2-aldehyde Schiff bases of S-methyl- and S-benzyldithiocarbazate; n = 0, 1) have been synthesized and characterized by physico-chemical techniques. Magnetic and spectroscopic evidence support a square-planar structure for these complexes. The crystal structures of the [Ni(tasbz)2] and [Cu(tasbz)2] · CHCl3 complexes (tasbz = anionic form of the thiophene-2-aldehyde Schiff base of S-benzyldithiocarbazate) have been determined by X-ray diffraction. Both complexes have a trans-planar structure in which the two Schiff base ligands are coordinated to the metal(II) ion as uninegatively charged bidentate ligands via the thiolate sulfur and the azomethine nitrogen atoms. This revised version was published online in June 2006 with corrections to the Cover Date.  相似文献   
35.
The kinetics of Ru(III) catalyzed oxidation of triethylamine by molecular oxygen has been investigated in the pH range 1.5 to 2.5 at 35°C and I=0.1 M KCl. The reaction is first order with respect to substrate, catalyst and molecular oxygen concentrations. The rate of the reaction increases with the increase of pH from 1.5 to 2.5 and then there is a slight decrease in the rate above pH 2.5. Based on the kinetic data, a mechanism for the catalytic oxidation of triethylamine is proposed. The major products in the oxidation of triethylamine are the N-oxide, diethylamine and acetaldehyde.
, Ru(III), pH=1,5+2,5 35°C I=0,1M KCl. , . pH 1,5 2,5, pH 2,5. , . N-, .
  相似文献   
36.
The bimetallic, decanuclear Ni3Ga7-cluster of the formula [Ni3(GaTMP)3(μ2-GaTMP)3(μ3-GaTMP)] ( 1 , TMP=2,2,6,6-tetramethylpiperidinyl) reacts reversibly with dihydrogen under the formation of a series of (poly-)hydride clusters 2 . Low-temperature 2D NMR experiments at −80 °C show that 2 consist of a mixture of a di- ( 2Di ), tetra- ( 2Tetra ) and hexahydride species ( 2Hexa ). The structures of 2Di and 2Tetra are assessed by a combination of 2D NMR spectroscopy and DFT calculations. The cooperation of both metals is essential for the high hydrogen uptake of the cluster. Polyhydrides 2 are catalytically active in the semihydrogenation of 4-octyne to 4-octene with good selectivity. The example is the first of its kind and conceptually relates properties of molecular, atom-precise transition metal/main group metal clusters to the respective solid-state phase in catalysis.  相似文献   
37.
Journal of Radioanalytical and Nuclear Chemistry - Modified pomegranate peel was utilized as a sorbent for the biosorption of uranium(VI) from the aqueous solution. The biosorbent was characterized...  相似文献   
38.
Research on Chemical Intermediates - Optimization of sulfasalazine degradation using the heterogeneous Fenton-like process in batch mode was investigated by response surface methodology. The...  相似文献   
39.
High oxygen reduction (ORR) activity has been for many years considered as the key to many energy applications. Herein, by combining theory and experiment we prepare Pt nanoparticles with optimal size for the efficient ORR in proton‐exchange‐membrane fuel cells. Optimal nanoparticle sizes are predicted near 1, 2, and 3 nm by computational screening. To corroborate our computational results, we have addressed the challenge of approximately 1 nm sized Pt nanoparticle synthesis with a metal–organic framework (MOF) template approach. The electrocatalyst was characterized by HR‐TEM, XPS, and its ORR activity was measured using a rotating disk electrode setup. The observed mass activities (0.87±0.14 A mgPt?1) are close to the computational prediction (0.99 A mgPt?1). We report the highest to date mass activity among pure Pt catalysts for the ORR within similar size range. The specific and mass activities are twice as high as the Tanaka commercial Pt/C catalysis.  相似文献   
40.
Journal of Radioanalytical and Nuclear Chemistry - Receptor tyrosine kinase Ror1 is widely expressed during embryogenesis but it is absent within most mature tissues. However, expression of Ror1...  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