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   72374篇
  免费   13529篇
  国内免费   4289篇
化学   66889篇
晶体学   1337篇
力学   3638篇
综合类   134篇
数学   6558篇
物理学   11636篇
  2024年   28篇
  2023年   143篇
  2022年   393篇
  2021年   562篇
  2020年   897篇
  2019年   2651篇
  2018年   2567篇
  2017年   3082篇
  2016年   3490篇
  2015年   5701篇
  2014年   5573篇
  2013年   7740篇
  2012年   6240篇
  2011年   6017篇
  2010年   4958篇
  2009年   4888篇
  2008年   5149篇
  2007年   4612篇
  2006年   4289篇
  2005年   3983篇
  2004年   3352篇
  2003年   2968篇
  2002年   3570篇
  2001年   1982篇
  2000年   1794篇
  1999年   933篇
  1998年   384篇
  1997年   340篇
  1996年   303篇
  1995年   241篇
  1994年   208篇
  1993年   181篇
  1992年   183篇
  1991年   132篇
  1990年   110篇
  1989年   73篇
  1988年   76篇
  1987年   65篇
  1986年   42篇
  1985年   50篇
  1984年   41篇
  1983年   20篇
  1982年   38篇
  1981年   28篇
  1980年   16篇
  1979年   46篇
  1978年   28篇
  1977年   5篇
  1976年   4篇
  1974年   4篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
971.
A room temperature ionic liquid N‐butylpyridinium hexafluorophosphate (BPPF6) was used as a binder to make an ionic liquid modified carbon paste electrode (IL‐CPE), which showed good characteristics such as simple preparation procedure, fast electrochemical response and good conductivity. The electrochemical oxidation of ascorbic acid (AA) on the new IL‐CPE was carefully studied. The oxidation peak potential of AA on the IL‐CPE appeared at 109 mV (vs. SCE), which was about 338 mV decrease of the overpotential compared to that obtained on the traditional carbon paste electrode (CPE) and the oxidation peak current was increased for about four times. The electrochemical parameters of AA on the IL‐CPE were calculated with the charge transfer coefficient (α) and the electrode reaction rate constant (ks) as 0.87 and 0.800 s?1, respectively. Based on the relationship of the oxidation peak current and the concentration of AA a sensitive analytical method was established with cyclic voltammetry. The linear range for AA determination was in the range from 1.0×10?5 to 3.0×10?3 mol/L with the linear regression equation as Ip (μA)=?2.52–0.064C (μmol/L) (n=13, γ=0.9942) and the detection limit was calculated as 8.0×10?6 mol/L (3σ). The proposed method was free of the interferences of coexisting substances such as dopamine (DA) and amino acids etc., and successfully applied to the vitamin C tablets determination.  相似文献   
972.
The configurational properties of a series of cyclohexylidene imines are discussed on the basis of their 1H, 13C and 15N NMR spectral data.  相似文献   
973.
The use of a zinc substrate as an electrode and the modification of its surface by means of a thin film of platinum-doped nickel hexacyanoferrate (Pt-NiHCF) were developed. The modification conditions of the zinc surface including the electroless deposition of metallic nickel on the electrode surface from NiCl2 solution, chemical derivatization of the deposited nickel to the NiHCF film in 0.5 M K3[Fe(CN)6] solution, and electrochemical penetration of metallic platinum into the modified film are described. The modified zinc electrodes prepared under optimum conditions show a well-defined redox couple due to the [NiIIFeIII/II(CN)6]1–/2– system. The effects of pH, the alkali metal cation, and the anion of the supporting electrolyte on the electrochemical characteristics of the modified electrode were studied in detail. The diffusion coefficients of hydrated alkali metal cations in the film (D), the transfer coefficient (), and the transfer rate constant for the electron (ks) were calculated in the presence of some alkali metal cations. The electrocatalytic activity of the modified electrode for methanol oxidation was demonstrated. The stability of the modified electrode under various experimental conditions was investigated.  相似文献   
974.
The reactivity of a Cr‐Te multilayer film consisting of 326 Cr/Te double‐layers with about 88(3) at% Te was investigated with in‐situ X‐ray diffraction. The occurrence of a superstructure reflection caused by the multilayer system is observed. During the annealing procedure between 80 and 90 °C the layer‐by‐layer arrangement is destroyed and elemental Te crystallizes. After 6 h isothermal annealing at 140 °C CrTe3 starts to crystallize. The amount and the crystal size of CrTe3 increase with raising temperature and Te is consumed during the growth process. At 220 °C the formation of crystalline Cr2Te3 is observed and between 220 and 260 °C CrTe3 is completely decomposed into Cr2Te3. The two Cr tellurides grow as highly textured materials. The size of CrTe3 crystals is significantly larger than that of Cr2Te3. For a co‐deposited Cr‐Te film with composition 77(3) at% Te the tri‐telluride and elemental Te crystallize simultaneously. The texture of CrTe3 is less pronounced and different reflections of the tri‐telluride occur besides the (h00)‐reflections. Up to 160 °C a pronounced increase of the crystallite size is observed and the crystals are significantly larger than those obtained with the multifilm sample. At 130 °C the crystallization kinetics seem to be controlled by nucleation.  相似文献   
975.
Although a number of computational studies have examined the relative stability of icosahedral and decahedral gold clusters from 1 to 3 nm in size, few studies have focussed on the variety of face-centered cubic (fcc) nanoparticles in this size regime. In most cases small fcc gold particles are assumed to adopt the truncated octahedral shape, but in light of the fact that the shape and structure of gold nanoparticles is known to vary, the relative stability of fcc polyhedra may change with size. Presented here are results of first-principles calculations investigating the preferred shape of gold particles less than 3 nm in size. Our results indicate that the equilibrium shape of fcc gold nanoparticles less than 1 nm is the cuboctahedron, but this shape rapidly becomes energetically unstable with respect to the truncated octahedron, octahedron and truncated cube shapes as the size increases.  相似文献   
976.
双电层相互重叠时蒙脱胶体表面阴离子的负吸附   总被引:2,自引:0,他引:2  
本文用Ag-AgCl电极判断平衡,测定双电层处于不同重叠程度下肢体表面阴离子的负吸附量Γ.结果表明,胶体表面双电层相互重叠程度可由两胶体表面间的中点电位φd与外Helmhotz面处的电位φd之比表征;阴离子负吸附随双电层重叠程度和电解质浓度的增加而显著减小.  相似文献   
977.
多嵌段聚醚氨酯脲为基质的新型高分子固态离子导体   总被引:2,自引:0,他引:2  
本文合成了一系列聚乙二醇型多嵌段聚醚氨酯脲,而且用这类聚醚氨酯甩与高氯酸锂制得了一种新型的高分子固态离子导体复合物。在室温和50℃之间,其电导率比聚环氧乙烷为基质的固体电解质的高一到二个数量级,它还具有优良的综合性能。因此,对于室温薄膜蓄电池来说,这种新型的固体电解质是一类良好的候选材料。  相似文献   
978.
Beta2-microglobulin (beta2-m) is a small amyloidogenic protein normally present on the surface of most nucleated cells and responsible for dialysis-related amyloidosis, which represents a severe complication of long-term hemodialysis. A therapeutic approach for this amyloidosis could be based on the stabilization of beta2-m through the binding to a small molecule, and consequent inhibition of protein misfolding and amyloid fibril formation. A few compounds have been described to weakly bind beta2-m, including the drug suramin. The lack of a binding site for nonpolypeptidic ligands on the beta2-m structure makes it difficult for both the identification of functional groups responsible for the binding and the search of hits to be optimized. The characterization of the binding properties of suramin for beta2-m by using three different techniques (surface plasmon resonance, affinity CE (ACE), ultrafiltration) is here described and the results obtained are compared. The common features of the chemical structures of the compounds known to bind the protein led us to select 200 sulfonated/suramin-like molecules from a wider chemical library on the basis of similarity rules, so as to possibly single out some interesting hits and to gain more information on the functional groups involved in the binding. The development of screening methods to test the compounds by using ultrafiltration and ACE is described.  相似文献   
979.
医用聚氯乙烯膜的等离子体表面改性   总被引:4,自引:0,他引:4  
用两种不同气氛的辉光放电等离子体工艺对医用软质聚氯乙烯(PVC)膜进行了表面改性研究。结果表明,聚合性气氛的等离子体改性效果明显优于非聚合性气氛。平整致密的聚合膜对PVC增塑剂——邻苯二甲酸二辛酯的迁移和扩散起了阻挡作用,也使膜表面亲水性和表面张力极性成份增大,液固相界面张力减小,生物相容性得以改善。  相似文献   
980.
Bismuth-modified glassy carbon electrodes have been investigated for their suitability in sonoelectroanalysis. The stability of the bismuth film to the application of ultrasound was assessed via voltammetric and atomic force microscopy (AFM) studies which revealed little ablation at powers up to an intensity of 130 W cm–2 delivered from a 25-kHz sonic horn. Furthermore, bismuth-film-modified glassy carbon electrodes were evaluated for the sonoelectroanalytical quantification of zinc and cadmium. Detection limits of 2×10–7 M and 6×10–9 M respectively were found after a 60-s deposition time via an acoustically assisted deposition protocol.  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