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   1172篇
  免费   87篇
  国内免费   25篇
化学   983篇
晶体学   8篇
力学   23篇
数学   92篇
物理学   178篇
  2023年   12篇
  2022年   29篇
  2021年   47篇
  2020年   79篇
  2019年   77篇
  2018年   112篇
  2017年   80篇
  2016年   83篇
  2015年   58篇
  2014年   93篇
  2013年   123篇
  2012年   99篇
  2011年   83篇
  2010年   57篇
  2009年   49篇
  2008年   59篇
  2007年   47篇
  2006年   21篇
  2005年   22篇
  2004年   13篇
  2003年   17篇
  2002年   5篇
  2001年   5篇
  2000年   1篇
  1999年   3篇
  1998年   2篇
  1997年   3篇
  1996年   1篇
  1995年   1篇
  1994年   1篇
  1990年   1篇
  1976年   1篇
排序方式: 共有1284条查询结果,搜索用时 750 毫秒
1.
In this work, a vanillin complex is immobilized onto MCM-41 and characterized by FT-IR, X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, thermogravimetric analysis, and BET techniques. This supported Schiff base complex was found to be an efficient and recoverable catalyst for the chemoselective oxidation of sulfides into sulfoxides and thiols into their corresponding disulfides (using hydrogen peroxide as a green oxidant) and also a suitable catalyst for the preparation of 2,3-dihydroquinazolin-4(1H)-one derivatives in water at 90°C. Using this protocol, we show that a variety of disulfides, sulfoxides, and 2,3-dihydroquinazolin-4(1H)-one derivatives can be synthesized in green conditions. The catalyst can be recovered and recycled for further reactions without appreciable loss of catalytic performance.  相似文献   
2.
The black-body radiation is considered in a theory with noncommutative electromagnetic fields; that is noncommutativity is introduced in field space, rather than in real space. A direct implication of the result on cosmic microwave background map is argued.  相似文献   
3.
The palladium(II) chloride/triethylsilane system has been successfully applied for the selective hydrogenation of the carbon-carbon double bond of α,β-unsaturated ketones to yield the corresponding saturated carbonyl compounds. The reaction takes place under mild conditions and affords high yields.  相似文献   
4.
A novel PVC-based membrane sensor based on vanadyl salophen (VNSP) for determination of trace amounts of monohydrogenphosphate (MHP) ions is introduced. The electrode revealed Nernstian response towards monohydrogenphosphate over the wide concentration range from 1.0×10−1 to 1.0×10−6 M at the pH of 8.2. The effect of solvent mediator, cationic additives and amount of ion-carrier on the behavior of the sensor was investigated. The sensor shows a short response time (<20 s) in the whole concentration ranges. The selectivity of the electrode is very high, and it can be used for detection of trace amounts of monohydrogenphosphate in the presence of large amounts of other anions. The detection limit of the electrode was 5.0×10−7 M (48 ng/ml) and it could be used for 14 weeks without any measurable changes in the slope. The potentiometric selectivity coefficients data revealed negligible interference from 16 common anions. It was successfully applied for the direct determination of monohydrogenphosphate in fertilizer samples and, as an indicator electrode, in potentiometric titration of HPO42− ion with barium nitrate.  相似文献   
5.
A variety of aromatic amines are oxidized to their corresponding quinones in excellent yields by supported iodic acid under microwave irradiation and solvent free conditions.  相似文献   
6.
Hindered internal rotation about the C‐N single bonds joining the thiuram disulfide was studied by 1H NMR complete line‐shaped analysis in different dimethyl sulfoxide‐chloroform (DMSO‐CDCl3) mixtures. From the temperature dependence of methyls proton spectra, activation parameters (Ea, ΔH, ΔS, and ΔG) were obtained. The Arrhenius plots showed a distinct isokinetic temperature at about 35 °C at which the exchange rate is more or less independent of the solvent composition. The resulting ΔH against TΔS plot showed a firmly good linear correlation, indicating the existence of an enthalpy‐entropy composition in an exchange process.  相似文献   
7.
The configuration of asphaltenes on the water-oil interface was evaluated from a combination of molar mass, interfacial tension, drop size distribution, and gravimetric measurements of model emulsions consisting of asphaltenes, toluene, heptane, and water. Molar mass measurements were required because asphaltenes self-associate and the level of self-association varies with asphaltene concentration, the resin content, solvent type, and temperature. Plots of interfacial tension versus the log of asphaltene molar concentration were employed to determine the average interfacial area of asphaltene molecules on the interface. The moles of asphaltenes per area of emulsion interface were determined from the molar mass data as well as drop size distributions and gravimetric measurements of the model emulsions. The results indicate that asphaltenes form monolayers on the interface even at concentrations as high as 40 kg/m(3). As well, large aggregates with molar masses exceeding approximately 10,000 g/mol did not appear to adsorb at the interface. The area occupied by the asphaltenes on the interface was constant indicating that self-associated asphaltenes simply extend further into the continuous phase than nonassociated asphaltenes. The thickness of the monolayer ranged from 2 to 9 nm.  相似文献   
8.
Tribromoisocyanuric acid (TBCA) and Oxone®‐MX systems were used as effective oxidizing agents for the oxidation of thiols to their corresponding disulfides under mild conditions at room temperature with good to excellent yields.  相似文献   
9.
Protonation of the highly reactive 1:1 intermediates produced in the reaction between alkyl(aryl) isocyanides and dibenzoylacetylene by isatin, leads to vinylnitrilium cations, which undergo carbon-centered Michael-type addition with the conjugate base of the NH-acid to produce highly functionalized 1-(3-furyl)-1H-indole-2,3-diones. A dynamic NMR effect is observed in the 1H NMR spectra of these compounds as a result of restricted rotation around the single bond linking the indole moiety and the furan system. The free-energy of activation (ΔG #) for this process is 69–71 ± 2 kJ mol−1.  相似文献   
10.
Hydroxylamine was found to be a mild reagent for conversion of arylboronic acids and their pinacolyl boronate esters into phenols. This procedure works on most arylboronic acids at room temperature, yielding phenols in moderate to good yields, and efficiently on arylboronates also yielding phenols in good yields.  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