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   2006篇
  免费   92篇
化学   1302篇
晶体学   3篇
力学   53篇
数学   405篇
物理学   335篇
  2023年   16篇
  2022年   20篇
  2021年   26篇
  2020年   30篇
  2019年   28篇
  2018年   33篇
  2017年   24篇
  2016年   81篇
  2015年   64篇
  2014年   75篇
  2013年   148篇
  2012年   141篇
  2011年   126篇
  2010年   95篇
  2009年   74篇
  2008年   95篇
  2007年   113篇
  2006年   110篇
  2005年   78篇
  2004年   71篇
  2003年   60篇
  2002年   72篇
  2001年   36篇
  2000年   31篇
  1999年   17篇
  1998年   22篇
  1997年   18篇
  1996年   18篇
  1995年   16篇
  1994年   16篇
  1993年   15篇
  1992年   20篇
  1991年   19篇
  1990年   21篇
  1989年   16篇
  1988年   12篇
  1987年   8篇
  1985年   12篇
  1984年   12篇
  1983年   18篇
  1982年   18篇
  1981年   15篇
  1980年   16篇
  1978年   7篇
  1977年   6篇
  1976年   10篇
  1974年   7篇
  1973年   6篇
  1955年   24篇
  1934年   11篇
排序方式: 共有2098条查询结果,搜索用时 0 毫秒
61.
62.
Quantum dots (QDs) have received considerable attention due to their unique optical and electrical properties. Although substantial research has focused on the potential applications and toxicological impacts of QDs, far less effort has been directed toward understanding their fate and transport in the environment. In this work, the effect of four coatings, polyethylene glycol functionalized polymer (PEGP), carboxyl derivatized polymer (COOHP), linoleic acid (LA), and polyacrylic acid-octylamine (PAA-OA), on the transport and retention of QDs in porous media were evaluated under environmentally relevant conditions. Aqueous QD suspensions (ca. 10 nM) were introduced into water-saturated columns packed with 40–50 mesh Ottawa sand at a pore-water velocity of 7.6 m/day. At an ionic strength (IS) of 3 mM and pH of 7, PEGP-coated QDs were completely retained within the column, while more than 60 % of COOHP-coated QDs were transported through a column run under identical conditions. When PAA-OA and LA were used as coatings, effluent QD recoveries increased to more than 65 and 89 % of the injected mass, respectively. Additionally, a decrease in pH from 9.5 to 5.0, or an increase of IS from 0 to 30 mM reduced the eluted mass of PAA-OA-coated QDs by more than 2 and 15 times, respectively. The relative mobility of coated QDs (LA > PAA-OA > COOHP > PEGP) was consistent with total interaction energy profiles between QDs and sand surfaces calculated based on Derjaguin–Landau–Verwey–Overbeek (DLVO) theory. At an IS of 3 mM (NaCl) and pH 7, a linear correlation was obtained between the fraction of eluted QDs and the magnitude of the primary interaction energy barrier. These findings demonstrate the strong dependence of QD transport on coating type and indicate that interaction energies based on DLVO theory can be used to predict the relative mobility of QDs in porous media.  相似文献   
63.
64.
A fully automated method for the determination of chromate is described. It is based on the selective reaction of Cr(VI) with diphenylcarbazide in acidic media to form a colored complex of Cr(III) with the oxidation product diphenylcarbazone. The reaction was performed within the syringe of an automatic burette containing a magnetic stirrer for homogenization of the sample and the required reagents. In-syringe stirring was made possible using a specially designed driving device placed around the syringe barrel to achieve a rotating magnetic field in the syringe, forcing the stirrer to spin. In a second step, the reaction mixture in the syringe was neutralized to allow in-syringe magnetic-stirring-assisted dispersive liquid–liquid microextraction of the complex into 125 μL of n-hexanol. After phase separation by droplet flotation over 30 s, the organic phase was propelled into a coupled spectrophotometric detection cell. The entire multistep procedure including in-system standard preparation was done within 270 s. The method was used for the analysis of natural waters, achieving average analyte recovery of 103 %, a limit of detection of 0.26 μg L-1, and a repeatability of less than 4 % relative standard deviation.  相似文献   
65.
Nanoparticles of nitrogen-modified TiO2 (N-doped TiO2) calcined at 300°C and 350°C, have been prepared with and without water rinsing. Samples were characterized by x-ray diffractrometry (XRD) and optical spectroscopy. The electron paramagnetic resonance (EPR) spectra from centers involving oxygen vacancies were recorded for all samples. These could be attributed to paramagnetic surface centers of the hole type, for example to paramagnetic oxygen radicals O?, O2 ? etc. The concentration of these centers increased after water rising and it further increased for samples annealed at higher temperature. Additionally, for samples calcined at 300°C, and calcined at 350°C and rinsed, the EPR spectra evidenced the presence of magnetic clusters of Ti3+ ions. The photocatalytic activity of samples was studied towards phenol decomposition under unltraviolet-visible (UV-Vis) irradiation. It was found that, in comparison to the starting materials, the rinsed materials showed increased photocatalytic activity towards phenol oxidation. The light absorption (UV-Vis/DRS) as well as surface Fourier transform infrared/diffuse reflectance spectroscopy (FTIR/DR) studies confirmed a significantly enhanced light absorption and the presence of nitrogen groups on the photocatalysts surfaces, respectively. A significant increase of concentration of paramagnetic centers connected with oxygen vacancies after water rising has had an essential influence on increasing their photocatalytic activity.   相似文献   
66.
A multiconfiguration time‐dependent Hartree method oriented toward calculations of a non‐Born‐Oppenheimer nature has been applied to the calculation of the dynamical properties of a confined H atom. The calculation is fully six‐dimensional and does not take into account constraints arising from linear or angular momentum conservation. The orbital evolution is monitored and the energy level spectrum of the system, as well as the dependence of the results on the decomposition of the Hamiltonian and on the correlation between radial degrees of freedom, is determined. © 2012 Wiley Periodicals, Inc.  相似文献   
67.
New procedures for the preparation of drugs and drug intermediates (isosorbide-5-nitrate, diltiazem) and intermediates of potential drugs using isopropenyl acetate are described.  相似文献   
68.
α-Hydroxy carboxylate ligands like gluconate or polyaminocarboxylate ligands such as ethylenediaminetetraacetate (EDTA) are frequently used in decontamination procedures at nuclear power plants. The presence of these organic substances among nuclear wastes could enhance the solubility of actinides by forming soluble complexes. Thermodynamic data on the stability of gluconate and EDTA with actinides are essential to predict their increase in mobility, especially in high pH systems characteristic of cement environments of a nuclear waste repository. In this work, the solubility of thorium oxyhydroxide in the presence of gluconate and EDTA has been studied. The results highlight the key role of these organics in increasing the solubility of thorium at pHc = 12. The presence of calcium at concentrations below 10?2 mol·dm?3 (characteristic of cement porewaters corresponding to cement compositions at the second degradation stage) does not seem to affect significantly the thorium solubility under the studied conditions.  相似文献   
69.
A method for determination of 61 organic pollutants (polycyclic aromatic hydrocarbons and organochlorine, organophosphorous and organonitrogen pesticides) is proposed. It is based on solid phase extraction (SPE) and subsequent analysis of the extract by liquid and gas chromatography coupled to tandem mass spectrometry. Method validation yielded to the following values: limits of quantification, from 0.005 to 0.020?µg?L?1; trueness, 95% to 113% and reproducibility (as percent relative standard deviation), 2% to 15%. Additionally, the method performed well in various proficiency tests.  相似文献   
70.
As a consequence of the depleting of fossil reserves and environmental issues, today, plant oils and fatty acids derived therefrom have a respectable status within the polymer chemistry community. However, maximizing the benefits of these renewable feedstocks requires the utilization of sustainable and efficient chemical transformations. The emergence of click chemistry concept and especially the renaissance of thiol‐ene addition reaction have had an impact on the way to make plant oil‐derived polymers. This highlight discusses the applicability and success of thiol‐ene addition and other click reactions in the transformation of oleochemicals into monomers and polymers. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013  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