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   20331篇
  免费   3429篇
  国内免费   2381篇
化学   14227篇
晶体学   210篇
力学   1491篇
综合类   196篇
数学   2332篇
物理学   7685篇
  2024年   47篇
  2023年   385篇
  2022年   470篇
  2021年   685篇
  2020年   813篇
  2019年   783篇
  2018年   657篇
  2017年   559篇
  2016年   946篇
  2015年   967篇
  2014年   1124篇
  2013年   1488篇
  2012年   1761篇
  2011年   1966篇
  2010年   1255篇
  2009年   1195篇
  2008年   1226篇
  2007年   1131篇
  2006年   1122篇
  2005年   930篇
  2004年   831篇
  2003年   617篇
  2002年   573篇
  2001年   504篇
  2000年   458篇
  1999年   431篇
  1998年   380篇
  1997年   323篇
  1996年   335篇
  1995年   319篇
  1994年   299篇
  1993年   233篇
  1992年   247篇
  1991年   205篇
  1990年   180篇
  1989年   152篇
  1988年   91篇
  1987年   89篇
  1986年   74篇
  1985年   75篇
  1984年   42篇
  1983年   44篇
  1982年   37篇
  1981年   22篇
  1980年   15篇
  1979年   8篇
  1977年   5篇
  1975年   6篇
  1969年   4篇
  1957年   8篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
The Knoevenagel condensation of Meldrum's acid with aromatic aldehydes proceeded efficiently in a reusable ionic liquid, ethylammonium nitrate, at room temperature in the absence of any catalyst with high yields.  相似文献   
992.
A general and efficient synthetic method of 1,3-bis(phenylseleno)-2-propanol by reducing diphenyl diselenides with sodium borohydride in basic environment and then reacting with epichlorohydrin are described.  相似文献   
993.
Phosphonyl hydrazones react with DMF/POC13 to afford 3-phosphonyl pyrazoles. Phosphonyl methylene hydrazones react with DMF/POC13 to provide 4-phosphonyl pyrazoles. 5-Phosphonyl pyrazoles are obtained from the reaction of phosphonyl chlorovinylaldehydes with phenylhydrazine.  相似文献   
994.
Shipeng Tao  Qinquan Hu  Huan Li  Shan Ma 《合成通讯》2013,43(11):1354-1361
A direct, concise, synthetic method for the generation of [1,2,3]triazolo[5,1-a]isoquinoline derivatives, using a selective cascade cyclization of unsymmetrical substituted 1,2-bis(phenylethynyl)benzene derivatives with NaN3, has been developed. The reaction gave different substituted [1,2,3]triazolo[5,1-a]isoquinolines in moderate to good yields. It was found that the substituents on the alkynes were important for the selectivities of the cascade cyclization sequences.  相似文献   
995.
Calculations using density functional theory were performed to explore the mechanisms for atmospheric degradation of isopropyl methyl methylphosphonate (IMMP). The potential energy surface profiles for OH‐initiated reaction of IMMP were constructed, and all possible degradation channels were considered. Rate constants were further calculated using transition state theory. It was established from these calculations that H‐abstractions from alkyl groups have much lower energy barriers than substitutions of alkoxyl groups, and four possible H‐abstraction channels are competitive. Investigations into the secondary reactions under the presence of O2/NO were also performed. It is shown that O2 addition, reaction of peroxide radicals with NO to form RO radicals, and removal of ·RO are the major degradation pathways for alkyl radicals. Four selected products, CH3OP(O)(CH3)OC(O)CH3, CH3OP(O)(O)CH3, (CH3)2CHOP(O)(CH3)OH, and (CH3)2CHOP(O)(CH3)OCH?O, are predicted to be the major products in this study. © 2013 Wiley Periodicals, Inc.  相似文献   
996.
A series of new dispiropyrrolidine derivatives were synthesized via the three‐component 1,3‐dipolar cycloaddition reaction of azomethine ylides generated in situ by the decarboxylative condensation of acenaphthenequinone and sarcosine or l ‐thioproline with 5‐benzylidene‐1,3‐dimethylpyrimidine‐2,4,6‐trione. The structures of the products were identified by IR, 1H‐NMR, and HRMS spectra.  相似文献   
997.
We have prepared core-shell magnetic molecularly imprinted polymer nanoparticles for recognition and extraction of tributyl tin (TBT). The use of particles strongly improves the imprinting effect and leads to fast adsorption kinetics and high adsorption capacities. The functional monomer acrylamide was grafted to the surface of Fe3O4 nanospheres in two steps, and MIP layers were then formed on the surface by creating a MIP layer on the surface consisting of poly(ethyleneglycol dimethacrylate) with a TBT template. The particles were characterized in terms of morphological, magnetic, adsorption, and recognition properties. We then have developed a method for the extraction of TBT from spiked mussel (Mytilidae), and its determination by liquid chromatography-tandem mass spectrometry. The method has a limit of detection of 1.0 ng?g?1 (n?=?5) of TBT, with a linear response between 5.0 and 1,000 ng?g?1. The proposed method was successfully applied to the determination of trace TBT in marine food samples with recoveries in the range of 78.3–95.6 %.
Figure
The preparation procedures of core-shell magnetic molecularly imprinted polymer nanoparticles for recognition and extraction of tributyl tin (TBT) in seafood  相似文献   
998.
We are reviewing the state of electrochemical sensing of H2O2 based on the use of metal nanoparticles. The article is divided into subsections on sensors based on nanoparticles made from Ag, Pt, Pd, Cu, bimetallic nanoparticles and other metals. Some sensors display high sensitivity, fast response, and good stability. The review is subdivided into sections on sensors based on heme proteins and on nonenzymatic sensors. We also discussed the challenges of nanoscaled sensors and their future aspects.
Figure
Sensing mechanism of (A) mediator-based enzyme biosensor, (B) mediator-less enzyme biosensor and (C) nonenzymatic sensors with metal nanoparticles for the electrocatalytic reduction toward H2O2  相似文献   
999.
DNAzyme based electrochemical sensors for trace uranium   总被引:1,自引:0,他引:1  
We have developed a uranyl-specific DNAzyme that was immobilized on the surface of a gold electrode to give a highly sensitive and selective biosensor for uranyl ion. The typical DNAzyme system consisted of the RNA (rA) as the substrate (ADNA), and the other strand is the enzyme (TDNA) with a ferrocene (Fc). The presence of uranyl ion induces the cleavage of the DNA substrate strand at the rA position to form two fragments. The Fc unit thereby is released from the surface of the electrode, and this results in a decreased peak current. This electrochemical biosensor has a dynamic range from 2 nM to 14 nM of uranyl ion, with a detection limit at 1 nM. It exhibits high sensitivity and excellent selectivity over other metal ions, and thus represents a promising technique for simple, fast, on-site, and real-time electrochemical sensing of UO2(II) ion. It also serves as a guide in choosing different methods for designing electrochemical sensors for other metal ions.
Figure
We have developed a uranyl-specific DNAzyme that was immobilized on the surface of a gold electrode to give a highly sensitive and selective biosensor for uranyl ion. The typical DNAzyme system consisted of the RNA as the substrate and the other strand is the enzyme with a ferrocene (Fc). This electrochemical biosensor exhibits high sensitivity and excellent selectivity, and represents a promising technique for simple, fast, on-site, and real-time electrochemical sensing of UO2(II) ion.  相似文献   
1000.
Optically active 1, 2-Diphenylethylendiamine(9) is obtained by asymmetric oxidative coupling reaction of d-camphor ketimine anion (4). Among various oxidating agents, TiCl(Oipr)3 is better than l2, Br2, CuCl2, FeCl3 and BrCH2CH2Br.  相似文献   
[首页] « 上一页 [95] [96] [97] [98] [99] 100 下一页 » 末  页»
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