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   1609篇
  免费   240篇
  国内免费   399篇
化学   2152篇
晶体学   2篇
力学   6篇
综合类   9篇
物理学   79篇
  2023年   24篇
  2022年   29篇
  2021年   157篇
  2020年   132篇
  2019年   109篇
  2018年   68篇
  2017年   65篇
  2016年   90篇
  2015年   93篇
  2014年   100篇
  2013年   156篇
  2012年   88篇
  2011年   79篇
  2010年   81篇
  2009年   89篇
  2008年   70篇
  2007年   85篇
  2006年   81篇
  2005年   64篇
  2004年   68篇
  2003年   79篇
  2002年   62篇
  2001年   47篇
  2000年   51篇
  1999年   35篇
  1998年   33篇
  1997年   41篇
  1996年   29篇
  1995年   50篇
  1994年   27篇
  1993年   24篇
  1992年   15篇
  1991年   10篇
  1990年   9篇
  1989年   4篇
  1988年   2篇
  1984年   1篇
  1981年   1篇
排序方式: 共有2248条查询结果,搜索用时 234 毫秒
71.
A mild and green electro-oxidative protocol to construct aromatic esters from methylarenes and alcohols is herein reported. Importantly, the reaction is free of metals, chemical oxidants, bases, acids, and operates at room temperature. Moreover, the design of the electrolyte was found critical for the oxidation state and structure of the coupling products, a rarely documented effect. This electro-oxidative coupling process also displays exceptional tolerance of many fragile easily oxidized functional groups such as hydroxy, aldehyde, olefin, alkyne, as well as neighboring benzylic positions. The enantiomeric enrichment of some chiral alcohols is moreover preserved during this electro-oxidative coupling reaction, making it overall a promising synthetic tool.  相似文献   
72.
73.
Two tandem oxidative two‐component reactions (O‐2CRs) and Ugi‐type three‐component reactions (OU‐3CRs) of aromatic hydrocarbons of petroleum naphtha have been investigated for the synthesis of 2‐phenyl‐1H ‐benzo [d ]imidazole, 2‐aryl‐4‐quinazolinone and 3,4‐dihydroquinoxalin‐2‐amine derivatives using six new biopolymer‐supported ferrite nanocatalysts: CoFe2O4@wool‐SO3H, MnFe2O4@wool‐SO3H, ZnFe2O4@wool‐SO3H, MnCoFe2O4@wool‐SO3H, ZnCoFe2O4@wool‐SO3H and CrCoFeO4@wool‐SO3H. The best results are obtained with the CrCoFeO4@wool‐SO3H catalyst. All of the catalysts were characterized using flame atomic absorption spectrometry, X‐ray diffraction, thermogravimetric analysis, scanning electron microscopy and energy‐dispersive spectroscopy. To the best of our knowledge, this approach can be considered as the first example of O‐2CRs and OU‐3CRs of aromatic hydrocarbons of petroleum naphtha with ferrite nanocatalysts, which would be very useful from a practical point of view. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   
74.
Cu(II) immobilized on Fe3O4–diethylenetriamine was designed as a new, inexpensive and efficient heterogeneous catalyst for the synthesis of 2,3‐dihydroquinazolin‐4(1H )‐ones and the oxidative coupling of thiols. The structure of the nanomagnetic catalyst was comprehensively characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, vibrating sample magnetometry, thermogravimetric analysis, X‐ray diffraction and atomic absorption spectroscopy. Simple preparation of the catalyst from commercially available materials, high catalytic activity, simple operation, high yields, use of green solvents, easy magnetic separation and reusability of the catalyst with unaltered activity make our protocol a green and feasible synthetic strategy.  相似文献   
75.
实验探究NaOH、Na2CO3、NaHCO3这三种常见的碱基物质在模拟燃煤烟气中的实际表现,发现三种碱基物质均具有一定的脱氯性能,NaOH、Na2CO3、NaHCO3的脱氯性能依次下降,以脱氯效率70%为目标,使用三种碱基物质Na/Cl比分别需要达到5.8、7.1、8.7。高浓度SO2的存在对烟气脱氯有竞争作用,随着SO2浓度的提高,脱氯效率线性下降,不同碱基物质下,SO2浓度对脱氯效率的影响规律基本一致,SO2浓度每增加100 mg/m3,脱氯效率下降约1.4%。由于三种碱基物质达到相同脱氯效率时的Na/Cl比不同,综合考虑成本和溶解性,NaOH最具工业应用价值。  相似文献   
76.
金属氧化物对十氯联苯的降解研究   总被引:1,自引:0,他引:1  
分别以市售的Fe2O3、MgO和CaO为催化剂,对十氯联苯(CB209)进行了催化降解研究.结果表明,MgO对CB209的降解具有较高的活性.在反应温度为300℃,反应时间为60 min时,MgO对CB209的降解效率达到98.9%.进一步研究表明,MgO催化降解CB209的动力学符合准一级动力学反应.通过GC-MS和GC-ECD,并结合衍生化实验,检测到九氯联苯、五氯苯和四氯苯、五氯苯酚、四氯苯酚和三氯苯酚等降解产物,进而推测出MgO催化降解CB209的过程中存在相互竞争的反应路径:氧化反应、碳碳桥键断裂和加氢脱氯.  相似文献   
77.
An Rh‐catalyzed selective C?H bond activation of diaryl‐substituted anilides is described. In an attempt to achieve C?H activation of C‐aryl rings, we unexpectedly obtained an N‐aryl ring product under non‐coordinating anion conditions, whereas the C‐aryl ring product was obtained in the absence of a non‐coordinating anion. This methodology has proved to be an excellent means of tuning and adjusting selective C?H bond activation of C‐aryl and N‐aryl rings. The approach has been rationalized by mechanistic studies and theoretical calculations. In addition, it has been found and verified that the catalytic activity of the rhodium catalyst is obviously improved by non‐coordinating anions, which provides an efficient strategy for obtaining a highly chemoselective catalyst. Mechanistic experiments also unequivocally ruled out the possibility of a so‐called “silver effect” in this transformation involving silver.  相似文献   
78.
Acetaminophen (N-acetyl-p-aminophenol, APAP) overdosage can produce fatal centrilobular hepatic necrosis in humans. The present study attempted to investigate the protective effect of an anthocyanin-rich extract from bilberries and blackcurrants (AE) against APAP-induced acute hepatic damage in rats. Treatment with AE normalised blood activities of glutamate oxaloacetate and glutamate pyruvate transaminase and prevented APAP-induced plasmatic and tissutal alterations in biomarkers of oxidative stress, probably due to various bioproperties of the components of the extract.  相似文献   
79.
80.
采用非水溶剂溶胶-凝胶法制备了具有四方晶体相结构的纳米LaOX(X=Cl,Br).X射线粉末衍射和扫描电子显微镜结果表明,纳米LaOX样品的形貌规整、粒径均匀(平均粒径约为47nm).在甲烷氧化偶联(OCM)反应中,纳米LaOX显示出比常规尺度LaOX更高的催化活性和C2选择性,且纳米LaOX具有良好的稳定性.此外,常...  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