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   35025篇
  免费   3058篇
  国内免费   2986篇
化学   25414篇
晶体学   504篇
力学   1203篇
综合类   161篇
数学   5157篇
物理学   8630篇
  2023年   337篇
  2022年   586篇
  2021年   824篇
  2020年   867篇
  2019年   940篇
  2018年   828篇
  2017年   847篇
  2016年   1488篇
  2015年   1406篇
  2014年   1573篇
  2013年   2825篇
  2012年   2800篇
  2011年   2936篇
  2010年   1961篇
  2009年   2085篇
  2008年   2334篇
  2007年   2140篇
  2006年   1815篇
  2005年   1706篇
  2004年   1794篇
  2003年   1315篇
  2002年   1204篇
  2001年   699篇
  2000年   628篇
  1999年   454篇
  1998年   372篇
  1997年   326篇
  1996年   331篇
  1995年   304篇
  1994年   217篇
  1993年   229篇
  1992年   195篇
  1991年   176篇
  1990年   157篇
  1989年   147篇
  1988年   163篇
  1987年   117篇
  1986年   134篇
  1985年   206篇
  1984年   202篇
  1983年   146篇
  1982年   136篇
  1981年   129篇
  1980年   127篇
  1979年   102篇
  1978年   86篇
  1977年   76篇
  1976年   78篇
  1975年   63篇
  1974年   64篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
11.
The aim of this work was to determine the parameters that have decisive roles in microwave-assisted reactions and to develop a model, using computational chemistry, to predict a priori the type of reactions that can be improved under microwaves. For this purpose, a computational study was carried out on a variety of reactions, which have been reported to be improved under microwave irradiation. This comprises six types of reactions. The outcomes obtained in this study indicate that the most influential parameters are activation energy, enthalpy, and the polarity of all the species that participate. In addition to this, in most cases, slower reacting systems observe a much greater improvement under microwave irradiation. Furthermore, for these reactions, the presence of a polar component in the reaction (solvent, reagent, susceptor, etc.) is necessary for strong coupling with the electromagnetic radiation. We also quantified that an activation energy of 20–30 kcal mol−1 and a polarity (μ) between 7–20 D of the species involved in the process is required to obtain significant improvements under microwave irradiation.  相似文献   
12.
Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis.  相似文献   
13.
14.
15.
We conducted measurements of black carbon(BC) aerosol in Jiaxing,China during autumn from September 26 to November 30,2013.We investigated temporal and diurnal variations of BC,and its correlations with meteorological parameters and other major pollutants.Results showed that hourly mass concentrations of BC ranged from 0.2 to 22.0 μg/m3,with an average of 5.1 μg/m3.The diurnai variation of BC exhibited a bimodal distribution,with peaks at 07:00 and 18:00.The morning peak was larger than the evening peak.The mass percentages of BC in PM2.5 and PM10 were 7.1%and 4.8%,respectively.The absorption coefficient of BC was calculated to be 44.4 Mm-1,which accounted for 11.1%of the total aerosol extinction.BC was mainly emitted from local sources in southwestern Jiaxing where BC concentrations were generally greater than 11 μg/m3 during the measurement period.Correlation analysis indicated that the main sources of BC were motor vehicle exhaust,and domestic and industrial combustion.  相似文献   
16.
17.
Journal of Thermal Analysis and Calorimetry - The aim of this work is to synthesize and characterize a new structured silver–clay dried, calcined or sintered at different temperatures...  相似文献   
18.
19.
20.
以4-羟基吲哚为原料,经吲哚环4位乙酰基化、3位亲电取代、酰胺化和还原加氢等反应合成目标化合物7.通过核磁共振氢谱及碳谱对化合物进行结构表征,并对目标化合物进行体外抗氧化生物活性测试.初步生物活性测试结果表明,化合物7a,7b,7c和7d对DPPH·均有很强的清除作用(清除率为85.25%~90.73%),7e,7f,7g,7h作用较差;目标化合物与Vc相比,对·OH的清除作用稍差,最高清除率25.66%(Vc的最高清除率为34.67),但各化合物整体水平相当;在清除O-2·能力上化合物7a,7d,7g,7h最大清除率(分别为19.34,35.35,27.93和31.74)均强于同等浓度的Vc(17.58).  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