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   478篇
  免费   13篇
  国内免费   4篇
化学   298篇
晶体学   11篇
力学   7篇
数学   47篇
物理学   132篇
  2024年   4篇
  2023年   3篇
  2022年   13篇
  2021年   6篇
  2020年   8篇
  2019年   20篇
  2018年   12篇
  2017年   16篇
  2016年   13篇
  2015年   12篇
  2014年   11篇
  2013年   33篇
  2012年   37篇
  2011年   29篇
  2010年   18篇
  2009年   17篇
  2008年   18篇
  2007年   16篇
  2006年   23篇
  2005年   18篇
  2004年   9篇
  2003年   8篇
  2002年   7篇
  2001年   10篇
  2000年   7篇
  1999年   4篇
  1998年   5篇
  1997年   3篇
  1996年   4篇
  1995年   3篇
  1994年   3篇
  1993年   5篇
  1992年   7篇
  1991年   3篇
  1990年   4篇
  1989年   6篇
  1988年   6篇
  1987年   4篇
  1986年   3篇
  1985年   5篇
  1983年   7篇
  1981年   5篇
  1980年   5篇
  1979年   7篇
  1978年   6篇
  1976年   7篇
  1975年   3篇
  1974年   3篇
  1973年   7篇
  1962年   2篇
排序方式: 共有495条查询结果,搜索用时 15 毫秒
131.
Raju Dey  Brindaban C. Ranu 《Tetrahedron》2010,66(13):2301-2305
Palladium(II) chloride supported on 4 Å molecular sieves efficiently catalyzes the Suzuki coupling reactions of chlorobenzenes in presence of tetrabutylammonium bromide without any ligand. The useful intermediates for the synthesis of bioactive compounds such as irbesartan, and losartan have been prepared in one step following this reaction. The preparation of this catalyst is very simple. The FE-SEM image shows a cube shape ordered structure. The catalyst does not exhibit any nanoparticles as indicated by TEM. EDS and XPS demonstrate anchoring of Pd on molecular sieves in +2 oxidation state. This heterogeneous catalyst is stable, non-air sensitive and recyclable.  相似文献   
132.
The use of 1-menthyl ester of 1,3-dithiane-2-carboxylic acid as a chiral auxilary for the conversion of acetophenone, propiophenone and butyrophenone to the corresponding optically active tertiary alcohols 2-phenylhexan-2-ol, 3-phenylheptan-3-ol and 4-phenyloctan-4-ol, has been demonstrated.  相似文献   
133.
134.
Reaction of sodium 2-formylbenzenesulphonate (1) with thionyl chloride or phosphorous pentachloride gives a mixture of pseudo (2) and normal (3) sulphonyl chlorides. Whereas ammonium 2-carboxybenzenesulphonate (6) gives only the normal sulphonyl chloride (7) on reaction with thionyl chloride, a mixture of normal (7) and pseudo (8) isomers are formed on reaction with phosphorous pentachloride. Sodium 2-benzoylbenzenesulphonate (15), on the other hand, gives the corresponding normal sulphonyl chloride (16) on reaction with both of the reagents mentioned above. Based on these observations it is concluded that γ-keto sulphonic acids are amenable to the influence of γ-carbonyl group as in the case of γ-keto carboxylic acids but to a lesser extent.  相似文献   
135.
A reaction of nitric acid with bromophenols and iodophenols results in substitution of the halogen with a nitro group. The study indicates moderate reactivity for bromophenols and iodophenols, while chlorophenols were found to be sluggish in this reaction.  相似文献   
136.
The kinetics of polymerization of acrylonitrile(AN) initiated by manganese(III) acetate in the presence of glycerol was investigated in the temperature range of 30–40°C. The effect of varying the concentrations of glycerol, sulfuric acid, acetic acid, metal ion, and monomer on the rate was studied. A suitable reaction scheme and rate expression have been proposed. Termination was mutual and was caused by the combination of two growing polymer radicals.  相似文献   
137.
138.
Dissipative supramolecular assemblies are hallmarks of living systems, contributing to their complex, dynamic structures and emerging functions. Living cells can spatiotemporally control diverse biochemical reactions in membrane compartments and condensates, regulating metabolite levels, signal transduction or remodeling of the cytoskeleton. Herein, we constructed membranous compartments using self-assembly of lipid-like amphiphiles (lipidoid) in aqueous medium. The new double-tailed lipidoid features Cu(II) coordinated with a tetravalent chelator that dictates the binding of two amphiphilic ligands in cis-orientation. Hydrophobic interactions between the lipidoids coupled with intermolecular hydrogen bonding led to a well-defined bilayer vesicle structure. Oil-soluble SNAr reaction is efficiently upregulated in the hydrophobic cavity, acting as a catalytic crucible. The modular system allows easy incorporation of exposed primary amine groups, which augments the catalysis of retro aldol and C−N bond formation reactions. Moreover, a higher-affinity chelator enables consumption of the Cu(II) template leveraging the differential thermodynamic stability, which allows a controllable lifetime of the vesicular assemblies. Concomitant temporal upregulation of the catalytic reactions could be tuned by the metal ion concentration. This work offers new possibilities for metal ion-mediated dynamic supramolecular systems, opening up a massive repertoire of functionally active dynamic “life-like” materials.  相似文献   
139.
Supercapacitors (SCs) are potentially trustworthy energy storage devices, therefore getting huge attention from researchers. However, due to limited capacitance and low energy density, there is still scope for improvement. The race to develop novel methods for enhancing their electrochemical characteristics is still going strong, where the goal of improving their energy density to match that of batteries by increasing their specific capacitance and raising their working voltage while maintaining high power capability and cutting the cost of production. In this light, this paper offers a succinct summary of current developments and fresh insights into the construction of SCs with high energy density which might help new researchers in the field of supercapacitor research. From electrolytes, electrodes, and device modification perspectives, novel applicable methodologies were emphasized and explored. When compared to conventional SCs, the special combination of electrode material/composites and electrolytes along with their fabrication design considerably enhances the electrochemical performance and energy density of the SCs. Emphasis is placed on the dynamic and mechanical variables connected to SCs′ energy storage process. To point the way toward a positive future for the design of high-energy SCs, the potential and difficulties are finally highlighted. Further, we explore a few important topics for enhancing the energy densities of supercapacitors, as well as some links between major impacting factors. The review also covers the obstacles and prospects in this fascinating subject. This gives a fundamental understanding of supercapacitors as well as a crucial design principle for the next generation of improved supercapacitors being developed for commercial and consumer use.  相似文献   
140.
A new strategy to access α-functionalized alicyclic amines via their corresponding imine-BF3 complexes is reported. Isolable imine-BF3 complexes, readily prepared via dehydrohalogenation of N-bromoamines in a base-promoted/18-crown-6 catalyzed process followed by addition of boron trifluoride etherate, undergo reactions with a wide range of organometallic nucleophiles to afford α-functionalized azacycles. Organozinc and organomagnesium nucleophiles add at ambient temperatures, obviating the need for cryogenic conditions. In situ preparation of imine-BF3 complexes provides access to α-functionalized morpholines and piperazines directly from their parent amines in a single operation. α-Functionalized morpholines can be elaborated further, for instance by installing a second substituent in the α′-position.  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