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   1446篇
  免费   31篇
  国内免费   9篇
化学   832篇
晶体学   6篇
力学   99篇
数学   249篇
物理学   300篇
  2023年   12篇
  2022年   36篇
  2021年   36篇
  2020年   27篇
  2019年   36篇
  2018年   35篇
  2017年   33篇
  2016年   57篇
  2015年   40篇
  2014年   51篇
  2013年   88篇
  2012年   92篇
  2011年   119篇
  2010年   86篇
  2009年   71篇
  2008年   103篇
  2007年   83篇
  2006年   82篇
  2005年   77篇
  2004年   55篇
  2003年   42篇
  2002年   43篇
  2001年   18篇
  2000年   18篇
  1999年   13篇
  1998年   14篇
  1997年   12篇
  1996年   15篇
  1995年   4篇
  1994年   8篇
  1993年   7篇
  1992年   9篇
  1991年   6篇
  1990年   10篇
  1989年   4篇
  1988年   2篇
  1987年   2篇
  1986年   2篇
  1985年   5篇
  1984年   2篇
  1983年   3篇
  1982年   5篇
  1981年   2篇
  1979年   4篇
  1978年   3篇
  1977年   2篇
  1976年   3篇
  1975年   3篇
  1973年   3篇
  1965年   1篇
排序方式: 共有1486条查询结果,搜索用时 15 毫秒
31.
An electrochemically stable monolayer of tris(2,2'-bipyridyl)ruthenium(II) was obtained for the first time. It was based on the electrostatic attachment of Ru(bpy)(3)(2+) to the benzene sulfonic acid monolayer film, which was covalently bound onto glassy carbon electrode by the electrochemical reduction of diazobenzene sulfonic acid. The surface-confined Ru(bpy)(3)(2+) underwent reversible surface process, and reacted with the coreactant, tripropylamine, to produce electrochemiluminescence. In view of the stability of the electrode, the results strongly suggested that light was emitted from the surface-confined Ru(bpy)(3)(2+), not from the detached Ru(bpy)(3)(2+). The Ru(bpy)(3)(2+) modified electrode was used to the determination of tripropylamine. It showed good linearity in the concentration range from 5 muM to 1 mM with a detection limit of 1 muM (S/N=4). The good stability of the Ru(bpy)(3)(2+) modified electrode also showed that the benzene sulfonic acid monolayer film prepared can be served as an excellent support to construct multilayers.  相似文献   
32.
The reaction of the dimer complex [{Ru(CO)3Cl2}2] with the ligands 4,6-dichloroquinoline-5,8-dione and 6-methoxybenzo[g]quinoline-5,10-dione in ethanol solution led to the neutral mononuclear complexes of general formula [Ru(CO)2Cl22-quinolinedione-N,O)]. The complexes were characterized by elemental analysis, IR and RMN spectroscopy, and the molecular structure of [Ru(CO)2Cl2(6-methoxybenzo[g]quinoline-5,10-dione)] was determined by single-crystal X-ray diffraction. The redox chemistry of ligands and complexes was investigated by cyclic voltammetry, and their potential antitumor activity was also evaluated.  相似文献   
33.
34.
The acid-catalysed esterification of myristic acid with isopropanol was studied by using near-infrared spectroscopy (NIR) in combination with soft-modeling curve resolution (MCR) methodology with a view to establishing the effect of experimental variables on the reaction kinetics. The reaction was conducted at temperatures above the boiling point of the alcohol, with continuous addition of an isopropanol/water mixture to the reactor. Spectral and concentration profiles were determined by applying soft-modeling curve resolution methodology to a column-wise augmented data matrix containing the spectra for the pure components. MCR profiles were compared with reference values and found to depart from then by less than 3% as %RSE for concentrations and to exhibit correlation above 0.999 for spectra.The reaction kinetics as estimated from the concentration profiles was found to be pseudo-first-order. Also, the pseudo-first-order rate constant was found to depend on the flow-rate of the isopropanol/water mixture and its water content; although the constant decreased with increase in the proportion of water, a content of ca. 15% could be used without important retarding effects on the kinetics. The proposed NIR-MCR method allows the rate constant and the influence of the initial water content to be determined with a view to minimizing consumption of the raw materials and optimizing the experimental conditions.  相似文献   
35.
In this work both the electrochemical behavior and the analysis of the hypnotic pyrazolopyrimidine derivative zaleplon were studied. Zaleplon in ethanol-0.1M Britton Robinson buffer solution (30-70) showed 2 irreversible, well-defined cathodic responses in the pH range of 2-12 using differential pulse polarography (DPP), tast polarography, and cyclic voltammetry. From chronocoulometric studies, it was possible to conclude that one electron was transferred in each reduction peak or wave. For analytical purposes, the DPP technique working at pH 4.5 for peak I was selected, which exhibited adequate repeatability, reproducibility, and selectivity. The recovery was 99.97 +/- 1.52%, and the detection and quantitation limits were 5.13 x 10(-7)M and 1.11 x 10(-6)M, respectively. The DPP method was applied successfully to the individual assay of capsules in order to verify the content uniformity of zaleplon. Treatment of the sample is not required because the excipients do not interfere, the method is not time consuming, and it is less expensive than column liquid chromatography.  相似文献   
36.

Films of titanate nanosheets (approx. 1.8-nm layer thickness and 200-nm size) having a lamellar structure can form electrolyte-filled semi-permeable channels containing tetrabutylammonium cations. By evaporation of a colloidal solution, persistent deposits are readily formed with approx. 10-μm thickness on a 6-μm-thick poly(ethylene-terephthalate) (PET) substrate with a 20-μm diameter microhole. When immersed in aqueous solution, the titanate nanosheets exhibit a p.z.c. of − 37 mV, consistent with the formation of a cation conducting (semi-permeable) deposit. With a sufficiently low ionic strength in the aqueous electrolyte, ionic current rectification is observed (cationic diode behaviour). Currents can be dissected into (i) electrolyte cation transport, (ii) electrolyte anion transport and (iii) water heterolysis causing additional proton transport. For all types of electrolyte cations, a water heterolysis mechanism is observed. For Ca2+ and Mg2+ions, water heterolysis causes ion current blocking, presumably due to localised hydroxide-induced precipitation processes. Aqueous NBu4+ is shown to ‘invert’ the diode effect (from cationic to anionic diode). Potential for applications in desalination and/or ion sensing are discussed.

  相似文献   
37.
We discuss various possible scenarios where 2q, where stands for the density parameter andq for the deceleration parameter. We further estimate the corrections necessary when a variable cosmological constant is considered in the theory.  相似文献   
38.
39.
40.
Three new cadmium-based coordination polymers, denoted [Cd(hfipbb)(4,4’-bipy)] ( CdPF-1 ), [Cd(hfipbb)(2,2’-bipy)] ( CdPF-2 ), and [Cd(hfipbb)(1,10-phen)] ( CdPF-3 ), have been hydrothermally synthesized by using the well-known V-shaped organic linker 4,4’-(hexafluoroisopropylidene)bis(benzoic acid) (H2hfipbb), together with different nitrogenated auxiliary linkers. Considering the d10 configuration of the transition metal selected, the luminescent properties for these CdPF-n materials were explored, finding that materials CdPF-2 and CdPF-3 act as excellent sensors in the detection of explosive nitro aromatic compounds. The photoluminescence properties of CdPF-2 and CdPF-3 revealed that significant and sensitive fluorescence quenching was observed toward NP (nitrophenol) for CdPF-2 and PA (picric acid) for CdPF-3 in MeOH suspensions.  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