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   91923篇
  免费   2884篇
  国内免费   2231篇
化学   34930篇
晶体学   956篇
力学   7423篇
综合类   97篇
数学   33183篇
物理学   20449篇
  2023年   268篇
  2022年   329篇
  2021年   480篇
  2020年   637篇
  2019年   633篇
  2018年   10856篇
  2017年   10601篇
  2016年   6727篇
  2015年   1525篇
  2014年   1116篇
  2013年   1471篇
  2012年   5069篇
  2011年   11741篇
  2010年   6504篇
  2009年   6920篇
  2008年   7565篇
  2007年   9616篇
  2006年   1048篇
  2005年   2026篇
  2004年   2118篇
  2003年   2469篇
  2002年   1560篇
  2001年   634篇
  2000年   575篇
  1999年   452篇
  1998年   436篇
  1997年   363篇
  1996年   395篇
  1995年   280篇
  1994年   210篇
  1993年   201篇
  1992年   157篇
  1991年   164篇
  1990年   118篇
  1989年   113篇
  1988年   97篇
  1987年   87篇
  1986年   91篇
  1985年   80篇
  1984年   63篇
  1983年   52篇
  1982年   55篇
  1981年   54篇
  1980年   55篇
  1979年   46篇
  1914年   45篇
  1913年   40篇
  1912年   40篇
  1909年   41篇
  1908年   40篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Poly(vinyl chloride) supported tetraethylenepentamine (PVC-TEPA) has been found to be an efficient catalyst for the Knoevenagel condensation. A wide range of aromatic aldehydes easily undergo condensations with ethyl cyanoacetate and malononitrile in the commercial 95% ethanol in refluxing using PVC-TEPA as catalyst to afford the desired products of good purity in moderate to excellent yields. A recycling study confirmed that the catalyst could be reused, the yield of the desired condensation product were not reduced. The merits of this protocol are environmentally benign, simple operation, convenient work-up and good yields. Furthermore, the catalyst can easily be recovered and reused at five times with comparable yields.  相似文献   
992.
The stability of spontaneous thin layers and thin layers formed upon cathodical polarization of Ti in KOH solutions have been studied by potentiostatic and ellipsometric methods. At open circuit potential (OCP) the strongly adherent films, whose thickness depends on the concentration of the KOH solution, were formed. During the cathodic polarization the transformation of these films to weakly adsorbed precipitated layers on the electrode surface was observed. Comparing the theoretically computed curves with the experimental Ψ vs Δ loci measured ellipsometrically, the complex indices of refraction and the thickness of the generated films, from 3.6 to 60 nm in 1 M KOH and from 36 to 105 nm in 5 M KOH (adherent to the electrode surface), were determined. At OCP the rate of film growth increases with increasing the concentration of KOH solution. Cathodic polarizations change the chemical composition and retard the rate of film growth. Based on the ellipsometric and electrochemical data the chemical compositions of the formed films consisted of TiO2, Ti2O3, TiO2·H2O, Ti(OH)3 and TiOOH·nH2O.  相似文献   
993.
In this paper, the fuzzy symmetry of some prototypical linear molecules has been analyzed. The results show that some molecular orbitals (MOs) are less symmetrical but some others are more symmetrical than the molecular skeleton, which the MOs correspond to. The membership functions of space inversion for MOs are closely related to the chemical characteristics of the MOs. Sometimes, although the symmetry of a molecular skeleton is not obvious, however that of some MO is quite obvious. The membership functions of the fuzzy inversion symmetry depend on the choice of the position of the center of inversion. As compared to those of diatomic molecules and linear tri-atomic molecules, the linear polyatomic molecules in which a distinctive fuzzy symmetry of space translation may exist, and thus a significant effect on their properties can be expected.  相似文献   
994.
Microcapsules containing healing agents have been used to develop the self-healing polymeric composites. These microcapsules must possess special properties such as appropriate strength and stability in surrounding medium. A new series of microcapsules containing dicyclopentadiene (DCPD) with melamine–formaldehyde (MF) resin as shell material were synthesized by in situ polymerization technology. These microcapsules may satisfy the requirements for self-healing polymeric composites. The chemical structure of microcapsule was identified by using Fourier transform infrared (FTIR) spectrometer. The morphology of microcapsule was observed by using optical microscope (OM) and scanning electron microscope. Size distribution and mean diameter of microcapsules were determined with OM. The thermal properties of microcapsules were investigated by using thermogravimetric analysis and differential scanning calorimetry. Additionally, the self-healing efficiency was evaluated. The results indicate that the poly(melamine–formaldehyde) (PMF) microcapsules containing DCPD have been synthesized successfully, and their mean diameters fall in the range of 65.2∼202.0 μm when the adjusting agitation rate varies from 150 to 500 rpm. Increasing the surfactant concentration can decrease the diameters of microcapsules. The prepared microcapsules are thermally stable up to 69 °C. The PMF microcapsules containing DCPD can be applied to polymeric composites to fabricate the self-healing composites.  相似文献   
995.
The novel compound, 3-(E)-ferrocenyl-vinyl-N-hexylcarbazole (FVHC) was first synthesized and fully characterized by elemental analysis, IR, 1H-NMR, single-crystal X-ray diffraction, ultraviolet (UV) absorption, cyclic voltammograms (CV) and optical limiting (OL) measurements. The result of single crystal X-ray diffraction for the compound reveals that the ferrocenyl and carbazole groups are approximately coplanar, and bridged by double-bond with E configuration, showing that there is a well-delocalized π-electron system in the molecule. The electrochemical investigation indicated that the electron in the FVHC may partially be delocalized over the π-conjugated system and CT process in functionalized carbazole systems. Besides, the compound exhibited strong UV absorption and large optical limiting effect, indicating promising potential applications as useful OL materials.  相似文献   
996.
It is of a great challenge to develop semiconductor photocatalysts with potential possibilities to simultaneously enhance photocatalytic efficiency and inhibit generation of toxic intermediates.In this study,we developed a facile method to induce the La doping and cationic vacancie(V(Zn))on ZnO for the highly efficient complete NO oxidation.The photocatalytic NO removal efficiency increases from 36.2%to 53,6%.Most importantly,a significant suppressed NO2 production also has been realized.According to the DFT calculations,ESR spectra and in situ FTIR spectra,the introduction of La^3+induce the redistribution of charge carriers in La-ZnO,which promote the production of·O2^- and lead to the formation of V(Zn)for the formation of·OH,contributing to the complete oxidation of NO to nitrate.Besides,the conversion pathway of photocatalytic NO oxidation has been elaborated,This work paves a new way to simultaneously realize the photocatalytic pollutants removal and the inhibition of toxic intermediates generation for efficient and safe air purification.  相似文献   
997.
化学镀法制备银壳聚苯乙烯微球   总被引:6,自引:0,他引:6  
采用一种新的化学镀法合成银壳包覆聚苯乙烯微球, 通过三乙醇胺和银离子络合来减小反应的氧化还原电位差, 降低银在改性聚苯乙烯微球表面的沉积速率. 采用TEM、XRD、UV 等测试手段对样品进行了分析和表征, 并考察了不同反应条件对实验结果的影响.实验表明, 该方法可在改性聚苯乙烯微球上包覆均匀的银层.  相似文献   
998.
Carbon nanotube array-based biosensor   总被引:8,自引:0,他引:8  
Aligned multi-wall carbon nanotubes (MWNT) grown on platinum substrate are used for the development of an amperometric biosensor. The opening and functionalization by oxidation of the nanotube array allows for the efficient immobilization of the model enzyme, glucose oxidase. The carboxylated open-ends of nanotubes are used for the immobilization of the enzymes, while the platinum substrate provides the direct transduction platform for signal monitoring. It is also shown that carbon nanotubes can play a dual role, both as immobilization matrices and as mediators, allowing for the development of a third generation of biosensor systems, with good overall analytical characteristics.  相似文献   
999.
Pyrolytic process has a promising potential for the environmentally friendly upgrading of lignocellulosic and plastic waste. Thermogravimetry and pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS) were used to get information about the reactive decomposition of PCL in binary mixtures with microcrystalline cellulose (MC) or sisal fibres (SF). Preliminary thermogravimetric investigation showed that biomass is thermally degraded at lower temperatures than PCL and this process has a predominant influence on the thermal behaviour of the mixtures. Discrepancies between the experimental and predicted TG/DTG profiles were considered as a measurement of the extent of interactions occurring on co-pyrolysis. It was found that reactivity of PCL was slightly increased in PCL-SF binary mixtures. Evolution of acidic products from cellulose and hemicelluloses decomposition may promote PCL degradation in binary mixtures with SF. It seems that the co-pyrolysis process could have potential for the environmentally friendly transformation of biocomposites.  相似文献   
1000.
Two novel alkaloids, 4,5‐dihydroxy‐1‐methyl‐3‐oxo‐2‐(trichloromethyl)‐3H‐indolium chloride ( 1 ) and 4‐(2‐methoxyethyl)‐N,N‐dimethylbenzenamine ( 2 ), were isolated from the EtOH extract of the roots of Zanthoxylum nitidum. Their structures were identified on the basis of spectroscopic and mass‐spectrometric analyses.  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