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   528篇
  免费   28篇
化学   344篇
晶体学   1篇
力学   22篇
数学   66篇
物理学   123篇
  2023年   5篇
  2022年   13篇
  2021年   14篇
  2020年   21篇
  2019年   8篇
  2018年   19篇
  2017年   11篇
  2016年   20篇
  2015年   27篇
  2014年   28篇
  2013年   27篇
  2012年   52篇
  2011年   47篇
  2010年   24篇
  2009年   19篇
  2008年   30篇
  2007年   33篇
  2006年   29篇
  2005年   25篇
  2004年   15篇
  2003年   19篇
  2002年   11篇
  2001年   1篇
  2000年   2篇
  1999年   1篇
  1998年   2篇
  1997年   1篇
  1996年   3篇
  1995年   3篇
  1994年   3篇
  1992年   3篇
  1991年   2篇
  1990年   1篇
  1989年   4篇
  1988年   1篇
  1987年   2篇
  1986年   1篇
  1984年   4篇
  1983年   1篇
  1982年   3篇
  1981年   3篇
  1980年   5篇
  1979年   2篇
  1978年   1篇
  1977年   1篇
  1976年   3篇
  1973年   2篇
  1972年   1篇
  1970年   1篇
  1905年   2篇
排序方式: 共有556条查询结果,搜索用时 15 毫秒
1.
Let (S,0) be a rational complex surface singularity with reduced fundamental cycle, also known as a minimal singularity. Using a fundamental result of M. Spivakovsky, we explain how to describe the equisingularity type of the discriminant curve for a generic projection of (S,0) onto (C2,0) from the resolution of (S,0). To cite this article: R. Bondil, C. R. Acad. Sci. Paris, Ser. I 337 (2003).  相似文献   
2.
3.
Using [Cp(Me)5Rh(bipy)C1]C1 (1) as redox catalyst for the continous NADH regeneration it was possible to perform an electrochemically driven enzymatic reduction of pyruvate to D-lactate catalyzed by D-LDH at a rate of 5 turnovers per hour. This is by a factor of 20 faster than the best results obtained until now. Current yields of 50 to 70 % may be obtained.  相似文献   
4.
5.
The kinetics of propene polymerization in heptane slurry at 1–4 bars was studied with a catalytic system that consisted of a solid catalyst prepared by adsorption of TiCI4 on pure porous MgCl2 (by dehydrating MgCl2, 6 H2O with thionyl chloride) and a cocatalytic, heptanic solution of ethylbenzoate (BE) and triethylaluminium (TEA). At a temperature approaching 60°C/polymerization began immediately after the introduction of the monomer. The polymerization rate decreased continuously during the reaction. The loss in activity, however, was not due to a diffusional effect (e.g., blocking of the catalyst by the growing polymer). Studies of the ageing of the catalytic system showed a deactivation of the catalytic system itself as a function of the time of contact between the catalyst and the cocatalyst. The product of the thermal decomposition of the complex 1:2 formed by the reaction of BE with TEA was not associated with the deactivation process or stereospecific control, which depend on the BE/AI ratio and the presence of the complex.  相似文献   
6.
Under Friedel-Crafts conditions, meso-tetraarylporphyrins give porphyrin spiro dimers in good yield. This reaction involves acylation, acid-catalyzed cyclization, and dimerization. A stable dimer possessing three additional six-membered rings could be isolated and its structure determined. By modifying the substrate and reagents, intermediates could be isolated and characterized. The reactivity of the substrates, the side-reactions, and the concentration requirements to form the dimers, all explain why this reaction remained apparently unexplored in the widely used meso-tetraarylporphyrin series. [reaction: see text]  相似文献   
7.
A new heptapode heptakis-6-(5-methylene-thioureido-5′-methyl-2,2′-bipyridyl)-β-cyclodextrin was prepared and its complexation properties towards metal cations were investigated. Substituting the urea functions by the corresponding thioureas promoted the inversion of the metal coordination selectivity. Preliminary results showed the heptapode unable to complex lanthanides but authorise selective complexation of ‘soft’ and ‘borderline’ metal cations.  相似文献   
8.
We report on the combination of nanodroplet sample preparation, ultra-low-flow nanoLC, high-field asymmetric ion mobility spectrometry (FAIMS), and the latest-generation Orbitrap Eclipse Tribrid mass spectrometer for greatly improved single-cell proteome profiling. FAIMS effectively filtered out singly charged ions for more effective MS analysis of multiply charged peptides, resulting in an average of 1056 protein groups identified from single HeLa cells without MS1-level feature matching. This is 2.3 times more identifications than without FAIMS and a far greater level of proteome coverage for single mammalian cells than has been previously reported for a label-free study. Differential analysis of single microdissected motor neurons and interneurons from human spinal tissue indicated a similar level of proteome coverage, and the two subpopulations of cells were readily differentiated based on single-cell label-free quantification.

The combination of nanodroplet sample preparation, ultra-low-flow nanoLC, high-field asymmetric ion mobility spectrometry (FAIMS) and latest-generation mass spectrometry instrumentation provides dramatically improved single-cell proteome profiling.  相似文献   
9.
A new tripodal α-cyclodextrin having three ureido-bipyridyl tethers symmetrically distributed on its upper rim was prepared in one step by the polymer supported ‘phosphine imide’ reaction in a medium yield. As expected, the highly selective complexation properties towards ‘hard’ and ‘soft’ cations were maintained with regards to the URFT-Cd (upper rim fully tethered) family previously investigated. Its EuIII and TbIII lanthanide complex fluorescence behaviour clearly indicates that a limited number of tethers allow a better bis-heterocyclic antenna self-organisation around the cation leading to enhanced fluorescence properties.  相似文献   
10.
A new series of channel-type molecules presenting the features of potential transmembrane structures is described. They result from the grafting of amphiphilic side chains on a β-cyclodextrin derivative 3 that constitutes the organizing core. They belong to the ‘bouquet’ family (B). Compounds bearing poly(oxyethylene) side chains, B 16 and 17 , and their polymethylene analogues B 18 and 19 , were synthesized. The properties investigated emphasize the suitability of such molecules to be incorporated into lipid bilayer membranes.  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