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   1751篇
  免费   86篇
  国内免费   389篇
化学   2053篇
晶体学   16篇
力学   5篇
综合类   13篇
物理学   139篇
  2024年   1篇
  2023年   18篇
  2022年   33篇
  2021年   40篇
  2020年   38篇
  2019年   46篇
  2018年   44篇
  2017年   69篇
  2016年   87篇
  2015年   74篇
  2014年   85篇
  2013年   184篇
  2012年   111篇
  2011年   129篇
  2010年   108篇
  2009年   127篇
  2008年   130篇
  2007年   129篇
  2006年   85篇
  2005年   126篇
  2004年   88篇
  2003年   63篇
  2002年   55篇
  2001年   33篇
  2000年   41篇
  1999年   40篇
  1998年   30篇
  1997年   29篇
  1996年   21篇
  1995年   31篇
  1994年   29篇
  1993年   13篇
  1992年   19篇
  1991年   16篇
  1990年   8篇
  1989年   14篇
  1988年   7篇
  1987年   6篇
  1986年   4篇
  1985年   3篇
  1984年   1篇
  1983年   3篇
  1982年   2篇
  1980年   1篇
  1979年   2篇
  1978年   1篇
  1976年   1篇
  1974年   1篇
排序方式: 共有2226条查询结果,搜索用时 15 毫秒
11.
溶剂热还原合成Cr2O3纳米管(英)   总被引:2,自引:0,他引:2  
Cr2O3 nanotubes with diameters of 80 nm and lengths of 550 nm were synthesized in a solvothermal reduction system at 180 ℃. The acetyl acetone (AcAc) and ethylene glycol (EG) were used as the chelate agent and the reductant respectively in the system. An intermediate compound-Cr(Ⅲ)(C5H7O2)3 was formed to force Cr2O3to crystallize along one direction.  相似文献   
12.
In order to study the influence of the adsorption of fulvic compounds on voltammetric signals and to understand better the adsorption of these compounds on hydrophobic natural water interfaces, adsorption studies of macromolecules such as poly(ethylene glycol) (HO(CH2CH2O)n) with molecular weight of 8000 were done on the mercury/water interface by a.c. voltammetry at the potential of zero charge. The maximum surface concentration, adsorption equilibrium constant and adsorption rate constant have been determined from the global adsorption mechanism, controlled by two determining steps: diffusion and kinetics of adsorption at the interface.  相似文献   
13.
用磺酸酯法制备单端氨基聚乙二醇引发剂,引发谷氨酸苄酯羧酸酐开环聚合,生成可生物降解的两亲嵌段共聚物聚乙二醇﹣聚谷氨酸苄酯(PEG-PBLG),用IR,NMR和GPC表征了共聚物。用超微透析法制备PEG-PBLG聚合物纳米粒,荧光芘探针法测定纳米粒的临界聚集浓度(cac)。紫外分光光度计考察纳米粒对疏水性药物的增溶作用,PEG-PBLG可作为亚微粒药物输送系统的载体。  相似文献   
14.
螯合型二甘醇钛酸酯的合成及其催化性能研究   总被引:3,自引:0,他引:3  
苏瑞兰  莫欣 《合成化学》1995,3(3):267-270
报导了两种新的螯合型二甘醇钛酸酯的合成方法,进行了IR和UV鉴定,并作为酯化反应催化剂催化合成了邻苯二甲酸二辛酯。研究了酯化反应转化率与反应时间、反应温度及催化剂用量的关系,探讨了催化剂结构与催化性能的关系。  相似文献   
15.
Two protocols for functionalization of glass supports with hexaethylene glycol (HEG)-linked oligonucleotides were developed. The first method (standard amidite protocol) made use of the 2-cyanoethyl-phosphoramidite derivative of 4,4′-dimethoxytrityl-protected HEG. This was first coupled to the support by standard solid-phase phosphoramidite chemistry followed by extension with a thymidylic acid icosanucleotide. Stepwise addition of the linker phosphoramidite graduated at 1% (relative to the total sites available) perstep at 50°C resulted in an optimal yield of immobilized oligonucleotides at a density of 2.24 × 1010 strands/mm2. This observed loading maximum lies well below the theoretical maximum loading owing to nonspecific adsorption of HEG on the glass and subsequent blocking of reactive sites. Surface loadings as high as 3.73 × 1010/mm2 and of excellent sequence quality were achieved with a reverse amidite protocol. The support was first modified into a 2-cyanoethyl-N,N-diisopropylphosphoramidite analog followed by coupling with 4,4′-dimethoxytrityl-protected HEG. This protocol is conveniently available when using a conventional DNA synthesizer. The reverse amidite protocol allowed for control of the surface loading at values suitable for subsequent analytical applications that make use of immobilized oligonucleotides as probes for selective hybridization of sample nucleic acids of unknown sequence and concentration.  相似文献   
16.
相转移催化合成对甲氧基肉桂酸-2-乙基己酯的研究   总被引:5,自引:1,他引:5  
对甲氧基肉桂酸 2 乙基己酯是一种有效的UVB防晒剂[1 ,2 ] ,一般采用Claisen Schmidt缩合反应制得[3] ,但由于催化剂KOH处于水相 ,对反应物不能充分起到催化作用导致产率较低[4] 。我们利用乙二醇 (PEG)为相转移催化剂合成立体专一的反式对甲氧基肉桂酸 2 乙基己酯 ,产率提高到 72 .5 %。合成路线如下 :1 实验部分1 .1 仪器与试剂BIO RAPFT45 0红外光谱仪 ,用液膜法测试 ;Brurer AM 30 0超导核磁共振仪 (溶剂DC Cl3) ;MAT/44S ,GC MS型色质联用谱仪 ;试剂均为分析纯 ,上海化学试剂…  相似文献   
17.
The first deaminative homologation of amines (-CH2NH2) to esters (-CH2CH2COOEt) in one-pot is reported. The reaction proceeds through, formation of an aldehyde from an amine in the presence of Pd/C as catalyst followed by Wittig reaction and catalytic hydrogenation using poly(ethylene glycol) as the solvent in one-pot.  相似文献   
18.
The first part of the paper deals with a critical discussion of the methodical basis of essential work of fracture (EWF) concept with respect to the specimen geometry (especially the notch depth) and application to polymers. In the second part, an in situ testing device, which combines a tensile testing machine with an optical strain-field measuring system, has successfully demonstrated possibility of characterization of fracture behaviour of polystyrene-polybutadiene block copolymers and block copolymer/homopolymer blends as examples of nanostructured polymer materials. It has been shown that knowledge of the time evolution of the strain field close to the crack tips leads to a simple verification of the basic precondition for the applicability of the EWF concept, the precondition “plastic zone coalescence-before-stable crack propagation”.  相似文献   
19.
The acid-catalyzed models on reaction mechanisms of pinacol rearrangement of propylene glycol conversion to propanal and propanone have been investigated using the density functional method at 298.15 K. Thermodynamic quantities of activation steps of four water-addition models were obtained. The number of added water interacting with the transition states of three concerted pathways has obviously affected the product ratio. The relative energetic profiles of the conversion reactions of all solvation models have been comparatively displayed. Estimation of the percent ratio of product composition computed from activation free energies of each acid-catalyzed reaction model was carried out. The percent ratios of propanal and propanone were decreased as the number of added water increased.  相似文献   
20.
相转移催化合成增塑剂BBP和水杨醛的研究   总被引:5,自引:0,他引:5  
相转移催化合成增塑剂BBP和水杨醛的研究郭锡坤,高文华,曾东宇(汕头大学化学系,汕头515063)关键词相转移催化,季铵盐,聚乙二醇,邻苯二甲酸丁苄酯,水杨醛,增塑剂邻苯二甲酸丁苄酯(增塑剂BBP)是一种优良的增塑剂.邻羟基苯甲醛(水杨醛)不仅是重要...  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