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   22692篇
  免费   3749篇
  国内免费   3723篇
化学   17113篇
晶体学   305篇
力学   1283篇
综合类   329篇
数学   2899篇
物理学   8235篇
  2024年   41篇
  2023年   272篇
  2022年   587篇
  2021年   612篇
  2020年   705篇
  2019年   790篇
  2018年   648篇
  2017年   647篇
  2016年   974篇
  2015年   1065篇
  2014年   1306篇
  2013年   1631篇
  2012年   1889篇
  2011年   2141篇
  2010年   1697篇
  2009年   1679篇
  2008年   1910篇
  2007年   1723篇
  2006年   1621篇
  2005年   1247篇
  2004年   1005篇
  2003年   877篇
  2002年   891篇
  2001年   724篇
  2000年   587篇
  1999年   473篇
  1998年   353篇
  1997年   282篇
  1996年   311篇
  1995年   258篇
  1994年   186篇
  1993年   171篇
  1992年   148篇
  1991年   135篇
  1990年   110篇
  1989年   91篇
  1988年   64篇
  1987年   65篇
  1986年   53篇
  1985年   43篇
  1984年   25篇
  1983年   36篇
  1982年   17篇
  1981年   12篇
  1980年   7篇
  1978年   5篇
  1977年   6篇
  1972年   5篇
  1970年   4篇
  1957年   4篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
1.
Wacker oxidation is an industry-adopted process to transform olefins into value-added epoxides and carbonyls. However, traditional Wacker oxidation involves the use of homogeneous palladium and copper catalysts for the olefin addition and reductive elimination. Here, we demonstrated an ultrahigh loading Cu single atom catalyst(14% Cu, mass fraction) for the palladium-free Wacker oxidation of 4-vinylanisole into the corresponding ketone with N-methylhydroxylamine hydrochloride as an additive under mild conditions. Mechanistic studies by 18O and deuterium isotope labelling revealed a hydrogen shift mechanism in this palladium-free process using N-methylhydroxylamine hydrochloride as the oxygen source. The reaction scope can be further extended to Kucherov oxidation. Our study paves the way to replace noble metal catalysts in the traditional homogeneous processes with single atom catalysts.  相似文献   
2.
JPC – Journal of Planar Chromatography – Modern TLC - A new high-performance thin-layer chromatographic (HPTLC) method has been developed for the simultaneous estimation of...  相似文献   
3.
This minireview describes the strategies for synthesis of fiuorinated surfactants potentially nonbioaccumulable.Various strategies have been focused on(Ⅰ) reducing the length of the perfluorocarbon chain,(Ⅱ) introducing hetero atoms into the fluorocarbon chain,(Ⅲ) introducing branch(herein and after branch means the fluoro-carbon chain section is not straight).In most cases,the surface tensions versus the surfactant concentrations have been assessed.These above strategies led to various highly fiuorinated(perfluorinated or not perfluorinated) surfactants whose chemical changes enabled to obtain novel alternatives to perfluorooctanoic acid(PFOA) and perfluorooctane sulphonate(PFOS).  相似文献   
4.
5.
Embedding endohdedral metallofullerenes (EMFs) into electron donor–acceptor systems is still a challenging task owing to their limited quantities and their still largely unexplored chemical properties. In this study, we have performed a 1,3‐dipolar cycloaddition reaction of a corrole‐based precursor with Sc3N@C80 to regioselectively form a [5,6]‐adduct ( 1 ). The successful attachment of the corrole moiety was confirmed by mass spectrometry. In the electronic ground state, absorption spectra suggest sizeable electronic communications between the electron acceptor and the electron donor. Moreover, the addition pattern occurring at a [5,6]‐bond junction is firmly proven by NMR spectroscopy and electrochemical investigations performed with 1 . In the electronically excited state, which is probed in photophysical assays with 1 , a fast electron‐transfer yields the radical ion pair state consisting of the one‐electron‐reduced Sc3N@C80 and of the one‐electron‐oxidized corrole upon its exclusive photoexcitation. As such, our results shed new light on the practical work utilizing EMFs as building blocks in photovoltaics.  相似文献   
6.
7.
8.
Journal of Radioanalytical and Nuclear Chemistry - In the present work the final products of coumarin radiation chemical transformation are investigated by chromatography. During radiolysis of...  相似文献   
9.
Dioscin (DIS), one of the most abundant bioactive steroidal saponins in Dioscorea sp., is used as a complementary medicine to treat coronary disease and angina pectoris in China. Although the pharmacological activities and pharmacokinetics of DIS have been well demonstrated, information regarding the final metabolic fates is very limited. This study investigated the in vivo metabolic profiles of DIS after oral administration by ultra‐performance liquid chromatography quadrupole time‐of‐flight mass spectrometry method. The structures of the metabolites were identified and tentatively characterized by means of comparing the molecular mass, retention time and fragmentation pattern of the analytes with those of the parent compound. A total of eight metabolites, including seven phase I and one phase II metabolites, were detected and tentatively identified for the first time. Oxidation, deglycosylation and glucuronidation were found to be the major metabolic processes of the compound in rats. In addition, a possible metabolic pathway on the biotransformation of DIS in vivo was proposed. This study provides valuable and new information on the metabolism of DIS, which will be helpful for further understanding its mechanism of action. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   
10.
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