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   24672篇
  免费   1125篇
  国内免费   4711篇
化学   28167篇
晶体学   298篇
力学   52篇
综合类   231篇
数学   17篇
物理学   1743篇
  2024年   25篇
  2023年   242篇
  2022年   411篇
  2021年   730篇
  2020年   722篇
  2019年   753篇
  2018年   644篇
  2017年   794篇
  2016年   938篇
  2015年   877篇
  2014年   1029篇
  2013年   2259篇
  2012年   1776篇
  2011年   1386篇
  2010年   1215篇
  2009年   1443篇
  2008年   1527篇
  2007年   1684篇
  2006年   1584篇
  2005年   1474篇
  2004年   1345篇
  2003年   1071篇
  2002年   931篇
  2001年   685篇
  2000年   667篇
  1999年   552篇
  1998年   440篇
  1997年   470篇
  1996年   423篇
  1995年   388篇
  1994年   336篇
  1993年   290篇
  1992年   281篇
  1991年   206篇
  1990年   161篇
  1989年   174篇
  1988年   122篇
  1987年   87篇
  1986年   61篇
  1985年   50篇
  1984年   56篇
  1983年   29篇
  1982年   43篇
  1981年   28篇
  1980年   23篇
  1979年   20篇
  1978年   22篇
  1977年   5篇
  1973年   5篇
  1968年   4篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
21.
Juzo Oyamada 《Tetrahedron》2006,62(29):6918-6925
Synthesis of coumarins from phenols and propiolic acids was examined by using a Pt catalyst such as PtCl2/AgOTf, K2PtCl4/AgOTf, and K2PtCl4/AgOAc. Propiolic acid reacted even with less reactive phenols in trifluoroacetic acid to give coumarins and dihydrocoumarins. In the case of substituted propiolic acids, phenylpropiolic acid and 2-octynoic acid, the reactions proceeded selectively to afford coumarins in good to high yields.  相似文献   
22.
Proton conductivity of phosphoric acid derivative of fullerene   总被引:1,自引:0,他引:1  
The proton conductive property of methano [60] fullerene diphosphoric acid has been investigated under various humidity conditions at the temperature range between 15 and 45 °C. It shows proton conductivity as high as 10−2 S cm−1 at 25 °C under relative humidity of 95%. Thermal analyses including TG–DTA and thermal desorption mass spectroscopy (TDS) confirm that the compound is thermally stable up to 200 °C. Proton conduction of the compound depends very much on humidity or water content. The logarithmic conductivity at 25 °C is increased linearly with increasing relative humidity. The activation energy (Ea) estimated from the slope of log(σT) vs. 1/T is decreased from 1.08 to 0.52 eV, as the relative humidity is increased from 40% to 75%. The humidity dependence of conductivity is discussed in the light of the observed hydration isotherm.  相似文献   
23.
Intramolecular (2+2) photocycloaddition of β-stilbazoles tethered by silyl chains took place with high efficiency. Complexation with dicarboxylic acid or catechol further enhanced both the efficiency and stereoselectivity.  相似文献   
24.
Phosphonic acid analogues of acylcarnitine were prepared in an optically active form expecting CPT I inhibitory activities. The synthetic methodology was based on catalytic asymmetric dihydroxylation of β,γ-unsaturated phosphonates and subsequent regioselective amination via the cyclic sulfates.  相似文献   
25.
均苯三甲酸铕及铕镧配合物的合成及荧光性质   总被引:2,自引:0,他引:2       下载免费PDF全文
以均苯三甲酸为配体,水热条件下合成了均苯三甲酸铕及铕镧系列发光配合物LaxEu1-x(BTC)·nH2O(x=0,0.1,0.3,0.5,0.7,0.9),通过元素分析及化学滴定法测定了配合物的组成。用红外光谱对其进行了表征,确定了该系列配合物的组成为LaxEu1-x(BTC)·nH2O。研究了系列配合物的荧光性质,荧光光谱表明:该类配合物均能发出强的铕离子的特征荧光,并且镧元素的掺入能增强铕配合物的发光强度,但发射峰的位置基本上没有变化;其中5D07F15D07F2的跃迁发射较强,且均劈裂为两个峰(587,593nm)和(611,618nm),这是由于铕离子所处的配位环境引起的。  相似文献   
26.
New biodegradable/biocompatible ABC block copolymers, poly(ethylene oxide)‐b‐poly(glycidol)‐b‐poly(L ,L ‐lactide) (PEO‐PGly‐PLLA), were synthesized. First, PEO‐b‐poly(1‐ethoxyethylglycidol)‐b‐PLLA was synthesized by a successive anionic ring‐opening copolymerization of ethylene oxide, 1‐ethoxyethylglycidyl ether, and L ,L ‐lactide initiated with potassium 2‐methoxyethanolate. In the second step, the 1‐ethoxyethyl blocking groups of 1‐ethoxyethylglycidyl ether were removed at weakly acidic conditions leaving other blocks intact. The resulting copolymers were composed of hydrophilic and hydrophobic segments joined by short polyglycidol blocks with one hydroxyl group in each monomeric unit. These hydroxyl groups may be used for further copolymer transformations. The PEO‐PGly‐PLLA copolymers with a molecular weight of PLLA blocks below 5000 were water‐soluble. Above the critical micellar concentration (ranging from 0.05 to1.0 g/L, depending on the composition of copolymer), copolymers formed macromolecular micelles with a hydrophobic PLLA core and hydrophilic PEO shell. The diameters of the micelles were about 25 nm. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3750–3760, 2003  相似文献   
27.
1 INTRODUCTION The self-assembly of organic-inorganic hybrid ma- terials is an intriguing area, which is yielding new generations of supramolecular architectures[1, 2]. Coor- dination by transition metals with multifunctional ligands is one of the main design principles. As a rigid multi-dentate ligand, 5-aminoisophthalic acid (AIP) has received considerable attention owing to the variety of bridging abilities[3~8]. It can engage in three types of intermolecular interactions: (1) M-L b…  相似文献   
28.
车前子中多糖含量的测定   总被引:12,自引:1,他引:11  
采用蒽酮-硫酸法比色测定,用精制车前子多糖测得车前子多糖对葡萄糖的换算因子,对我国同属不同品种的车前子不同采集时间及炮制前后其多糖含量进行了比较研究。结果表明:此测定方法简便可行。供试液在8h内显色稳定,重现性较好,平均回收率为97.8%,RSD=1.41%(n=5)。江西吉安产大粒车前子生品多糖含量在9.15%~9.83%之间,炮制后其多糖含量在6.29%~6.81%之间;南昌新祺周车前GAP标准基地的大粒车前子生品多糖含量为7.85%~8.38%,炮制后其多糖含量为6.01%~6.64%;东北产的小粒车前子生品多糖含量为6.61%,炮制后其多糖含量为6.45%。  相似文献   
29.
A mild, decarboxylative, aldol-type addition of malonic acid hemithioesters to aldehydes has been shown to occur with up to 39% enantioselectivity when the reaction was carried out in the presence of catalytic amounts of a Cu(II) salt, an enantiopure, tartaric acid-derived bis-benzimidazole and an achiral base.  相似文献   
30.
A guest-host nanocomposite based on electroconducting polyaniline doped with 12-phosphotungstic acid and V2O5 as well as its bifunctional analog containing not more than 5 mass% nanosized platinum were obtained. A study was carried out on the structure of these nanocomposites, their redox characteristics, and electrocatalytic activity in the reduction of oxygen. These nanocomposites were found to display catalytic properties in the electrochemical reduction of oxygen, while the presence of even a slight amount of nanosized platinum in the bifunctional composite leads to a significant increase in its electrocatalytic activity. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 43, No. 5, pp. 307–314, September–October, 2007.  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