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   531篇
  免费   49篇
  国内免费   158篇
化学   621篇
力学   7篇
综合类   5篇
数学   22篇
物理学   83篇
  2021年   1篇
  2019年   1篇
  2017年   5篇
  2016年   2篇
  2015年   2篇
  2014年   35篇
  2013年   58篇
  2012年   46篇
  2011年   10篇
  2010年   6篇
  2009年   8篇
  2008年   26篇
  2007年   25篇
  2006年   31篇
  2005年   30篇
  2004年   34篇
  2003年   37篇
  2002年   87篇
  2001年   198篇
  2000年   34篇
  1999年   22篇
  1998年   10篇
  1997年   11篇
  1996年   1篇
  1995年   5篇
  1994年   3篇
  1993年   1篇
  1992年   2篇
  1987年   1篇
  1986年   1篇
  1983年   1篇
  1982年   4篇
排序方式: 共有738条查询结果,搜索用时 15 毫秒
21.
The chiral diols ((,(,((,((-Tetraaryl-1,3-dioxolane-4,5-dimethanols) have been used for the formation of cyclic titanates and similar derivatives of Mg, Al and Zr. These complexes of oxophilic metal centers were employed in catalytic and stiochiometric enantioselective reactions such as enantioselective addition reactions of carbon-centered nucleophiles to aldehydes1, [2+2] cycloadditions2, and Diels-Alder reactions3. So far, the two hydrogen atoms of all this type of diols are in trans form…  相似文献   
22.
Our group have explored the reaction of allylsamarium bromide with a variety of substrates, such as N-(2-aminoalkyl)benzotriazoles1, imines2, nitriles3, diorgano diselenides4, disulfides5, isocyanates6 and nitroalkenes7. Here we wish to report the monoallylation of gem-diacetates with allylsamarium bromide. Gem-diacetates are stable in neutral and basic media, thus they are frequently used to protect aldehydes8. However, the presence of two leaving groups at the same carbon may make carbon …  相似文献   
23.
1 INTRODUCTIONAtrope alkaloids, which exist in eggplant plants, such as atrope and scopolamine, are used as a series of important drugs in medical science [1,2]. The typical character of atrope alkaloid is that these compounds contain the main skeleton of 8-azabicycle[3,2,1]octane , which results in the very complicated synthetic routine[3]. During our research for the reaction of 1,3,5,7-tetraphenyl-4- nitro-1,7-heptadione with low-valent titanium reagent, we easily synthesized the title …  相似文献   
24.
Goniothalamus cheliensis Hu (Annonaceace) is a small tree or shrub in Yunnan Province, southwest of China. Acetogenins, styryllactones and alkaloids1-3 from the genus were reported in the previous literature and many of them showed strong cytotoxic activities against a number of human cancer cell lines4. The titled plant has been the subject of our investigation due to the impressive cytotoxicity of its organic extract against mouse lymphocytic leukemia cells in preliminary pharmacological s…  相似文献   
25.
贾义明  王永成  赵佩佩  盛阳 《化学通报》2017,80(12):1128-1132
采用密度泛函理论中的B3LYP方法研究了气相中过渡金属La在二、四重态势能面上催化C2H4的反应机理。全参数优化了二、四重态势能面上各个驻点的几何构型,同时对过渡态进行了频率分析,使用内禀反应坐标(IRC)方法验证了过渡态的准确性,通过AIM理论和NBO分析方法对主要的驻点进行了键分析,并对2IM1、2IM3进行了态密度分析。结果表明:La与C2H4的反应存在两种可能的路径,反应在二重态势能面上进行且均为放热反应。键分析表明初始复合物中La与C2H4分子之间为共价作用。  相似文献   
26.
1 INTRODUCTIONItwaswellknown thatelementsofthesecondary and higherrow are in generaldifficulty to form multiplebondsin which apπ hybridized stateisinvolved〔1〕.Thus,simple compounds containing multiple phosphorus carbon bonds,such as methyl dynephosphine( HC≡P) 〔2 - 3〕 and methylenephosphine( H2 C=PH〔4〕,are notstableat room temperature.Three methods to stabilize compounds containing double ormultiple bond involving phosphorusatom in the pπ hybridized state are often used.The f…  相似文献   
27.
Selectively chemical cleavage of peptides and proteins is one of the most important reactions in both chemical and biochemical processes. Over the past decade, the interaction of palladium(II) complexes with methionine, cysteine and histidine-containing peptides and proteins and the hydrolytic cleavage of the corresponding amide bond by Pd(II) complexes have been extensively studied1-13. However, reports concerning the directly selective hydrolysis of peptides and proteins with other simple …  相似文献   
28.
Isodon enanderianus (Hand. -Mazz.) H. W. Li, has been used in folk medicine as anti-inflammatory and detoxified agent1. The Isodon genus is known to be rich in ent-kaurane diterpenoids, a series of new ent-kaurane diterpenoids have been isolated from the dried leaves of I. enanderianus2-4. In order to find more biologically active substances, we have carefully investigated the chemical constituents of I. enanderianus collected in Shiping county of Yunnan province, and as a result, enanderi…  相似文献   
29.
Reduction of C=N double bonds has been recognized as an important reaction both in organic chemistry and bio-chemistry1. Hantzsch 1,4-dihydropyridine (HEH, one of NADH model compounds) has been reported as a reductive reagent for imines2. However, application of dihydropyridines as practical reducing reagents in organic synthesis is limited because of their instability3. Like NADH models, 2-phenyl-N, N-dimethylbenzimidazoline (PDMBI) is an efficient electron and hydrogen donor (Eox = 0…  相似文献   
30.
The determination of molecular weights (Mw) of polysaccharides has served as an important process since the physical properties of the polysaccharides are closely related to their Mw and/or molecular weights distribution (MWD). For Mw and MWD determinations, high performance gel permeation chromatography (HPGPC) has gained wide acceptance as a preferred method due to its high sensitivity, speed and reproducibility. In chromatography, it is well known that the molecular weights are determ…  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