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   2036篇
  免费   122篇
  国内免费   53篇
化学   1511篇
晶体学   12篇
力学   94篇
综合类   2篇
数学   206篇
物理学   386篇
  2024年   3篇
  2023年   13篇
  2022年   44篇
  2021年   53篇
  2020年   70篇
  2019年   100篇
  2018年   105篇
  2017年   82篇
  2016年   154篇
  2015年   97篇
  2014年   143篇
  2013年   245篇
  2012年   174篇
  2011年   184篇
  2010年   131篇
  2009年   117篇
  2008年   144篇
  2007年   74篇
  2006年   69篇
  2005年   34篇
  2004年   52篇
  2003年   17篇
  2002年   19篇
  2001年   4篇
  2000年   5篇
  1999年   5篇
  1998年   4篇
  1996年   4篇
  1995年   5篇
  1994年   6篇
  1993年   3篇
  1992年   2篇
  1990年   6篇
  1989年   4篇
  1988年   3篇
  1986年   4篇
  1985年   5篇
  1984年   3篇
  1983年   3篇
  1981年   2篇
  1980年   3篇
  1979年   1篇
  1978年   2篇
  1977年   2篇
  1974年   1篇
  1970年   1篇
  1964年   1篇
  1941年   1篇
  1937年   2篇
  1927年   3篇
排序方式: 共有2211条查询结果,搜索用时 15 毫秒
101.
The chromone alkaloid dysoline (1), a new regioisomer of rohitukine (2) along with rohitukine and rohitukine-N-oxide (3) were isolated from the stem barks of Dysoxylum binectariferum. The structure of dysoline (1) was determined by extensive 2D-NMR studies and the absolute configuration was established by NOESY and CD spectra. Dysoline (1) consisted of a 5,7-dihydroxy-2-methylchromone nucleus substituted with a 2′-hydroxylated N-Me piperidine ring at the C-6 position. Dysoline differs from rohitukine by the position of the piperidine ring on the chromone nucleus. Dysoline displayed promising cytotoxicity in HT1080 fibrosarcoma cells with an IC50 of 0.21 μM, and also displayed significant inhibition of proinflammatory cytokines TNF-α and IL-6.  相似文献   
102.
In this work based on the modified scaled particle theory (SPT), the solubility of non-polar gases (He, Ar, N2, H2, O2, CO2 and CH4) in water has been studied over a wide range of temperatures. Calculations of Henry’s law constant by the SPT are related to the inherent physical properties and parameters of solvent and solute, all of which are considered temperature dependent. The temperature dependence of molar volume and hard sphere diameter of solvent and polarizability of solute have the most significant effects on the solubilities of gases in water. The average relative deviation is less than 3 %. Also, the effect of different mixing rules in the application of SPT to prediction of gas solubility has been studied.  相似文献   
103.
Ternary Ni–Mo–P thin films have been electrodeposited from citrate‐based electrolyte onto graphite substrates for application as anode catalysts for ethanol electrooxidation. The operating deposition parameters were optimized to produce Ni–Mo–P alloy films of outstanding catalytic activity. The phase structure of the deposits was evaluated employing X‐ray diffraction technique. Morphology and chemical composition of the deposited alloy films were studied using scanning electron microscopy and energy‐dispersive X‐ray analysis, respectively. The results demonstrated that the rate of Ni–Mo–P deposition increases with increasing the ammonium molybdate concentration in the plating electrolyte up to 10 g l?1. Also, the amount of Mo in the deposits increases with increasing the ammonium molybdate concentration up to 7.5 g l?1, and the maximum Mo content in the film was 9.1 at.%. The catalytic activity of Ni–Mo–P/C alloy films has been evaluated towards electrooxidation of ethanol in 1.0 M NaOH solution by using cyclic voltammetry and chronoamperometry. The catalytic performance of the prepared anodes as a function of the amount of Mo was studied. The results showed an increase in the oxidation peak current density of ethanol with increasing the Mo at.% in the deposited alloy films. Additionally, Ni–Mo–P/C electrodes displayed significantly improved catalytic activity and stability towards electrooxidation of ethanol compared with that of Ni–P/C electrode. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   
104.
Erbium-165 with 10.3 h physical half-life decays completely by electron capture to the ground state of stable isotope 165Ho and it is an ideal radio lanthanide for Auger electron therapy. Excitation function of 165Er via natEr(p,x)165Tm → 165Er, 166Er(p,2n)165Tm → 165Er, 165Ho(p,n)165Er and 165Ho(d,2n)165Er reactions were calculated using ALICE/ASH (Hybrid and GDH models) and EMPIRE 3.1 codes and then were compared with the reported measurement by experimental data and TENDL-2011. Physical yield and target thickness were evaluated with attention to excitation function, stopping power and SRIM code. 165Er was produced using the sedimentation technique through the natEr (p,x)165Tm → 165Er reaction. The deposited target was irradiated with 15 MeV proton beams at 20 μA current for 1 h. The 165Tm production yield was 26 MBq/μA h at the end of bombardment.  相似文献   
105.
Microwave irradiation (MWI) has accelerated the synthesis of S‐(2,3,4,6‐tetra‐O‐acetyl‐β‐D‐glucopyranosyl)thiouronium bromide (2a), whose reaction with 2,3,4,6‐tetra‐O‐acetyl‐α‐D‐glucopyranosyl bromide (1a) in the presence of Et3N afforded stereoselectively the acetylated β,β‐1‐thiotrehalose 4a. Similarly, the respective D‐galactopyranosyl 4b and 2‐acetylamino‐2‐deoxy‐D‐glucopyranosyl 4c analog as well as 4,4′‐di‐O‐(2,3,4,6‐tetra‐O‐acetyl‐β‐D‐galactopyranosyl) 4d and 4,4′‐di‐O‐(2,3,4,6‐tetra‐O‐acetyl‐α‐D‐glucopyranosyl) 4e derivatives of 2,2′,3,3′,6,6′‐hexa‐O‐acetyl β,β‐1‐thiotrehalose were prepared.  相似文献   
106.
Adsorption and recovery of uranium by nanoporous MCM-41 from aqueous solutions (synthetic solution and uranium conversion facility liquid waste) were investigated by use of a fixed-bed column (1.2 cm diameter and 3.0 cm height). Adsorption was carried out at flow rates 0.2 and 0.5 mL min?1, which correspond to retention times of 10 and 6 min. The maximum breakthrough capacity for uranium ions was achieved by use of nanoporous MCM-41 at the optimum pH of 3.6 and flow rate 0.2 mL min?1 (61.95 μg g?1). The Thomas and Yan models were applied to the experimental data, by use of linear regression, to determine the characteristics of the column for process design. The breakthrough curves calculated from the models were in good agreement with the experimental data. The elution behavior of uranium on nanoporous MCM-41 was studied with different eluents; the results showed that 0.1 M HCl is good eluent for uranium recovery. The regenerated column could be used in a multitude of adsorption–desorption cycles.  相似文献   
107.
Electroless Ni–P and Ni–P–TiCN composite coatings have been deposited successfully on Al substrates. Scanning electron microscopy (SEM) and energy dispersive X‐ray (EDX) techniques were applied to study the surface morphology and the chemical composition of the deposited films. Moreover, X‐ray diffraction (XRD) proved that Ni–P and Ni–P–TiCN deposits have amorphous structures. The properties of Ni–P–TiCN/Al composite films such as hardness, corrosion resistance and electrocatalytic activity were examined and compared with that of Ni–P/Al film. The results of hardness measurements reveal that the presence of TiCN particles with Ni–P matrix improves its hardness. Additionally, the performance against corrosion was examined using Tafel lines and electrochemical impedance spectroscopy techniques in both of 0.6 M NaCl and a mixture of 0.5 M H2SO4 with 2 ppm HF solutions. The results indicate that the incorporation of high dispersed TiCN particles into Ni–P matrix led to a positive shift of the corrosion potential and an increase in the corrosion resistance for all aluminum substrates after their coating with Ni–P–TiCN. In addition, Ni–P–TiCN/Al electrodes showed a higher electrochemical catalytic activity and stability toward methanol oxidation in 0.5 M NaOH solution compared with that of Ni–P/Al. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   
108.
A novel one-pot, five-component synthesis of 1-(alkylimino)-5,5-dicyano-3a-aryloctahydro-3-oxacyclobuta[cd]pentalene-1a,2,5a,5b(2H,3aH)-tetracarboxylates is described. A mixture of phenacyl bromide, malononitrile, isocyanide, and two equivalents of a dialkyl acetylenedicarboxylate undergoes a novel 1:1:1:2 addition reaction at ambient temperature in absolute ethanol to produce diastereoselectively the title compounds in good yields.  相似文献   
109.
110.
Mononuclear copper(II) complexes of 1,2,4-triazole-based Schiff base macrocyclic hydrazones, III and IV, have been reported. The prepared amorphous complexes have been characterized by spectroscopic methods, electron spray ionization mass spectrometry, and elemental analysis data. Electrochemical studies of the complexes in DMSO show only one quasi-reversible reduction wave at +0.43 V (ΔE = 70 mV) and +0.42 V (ΔE = 310 mV) for III and IV, respectively, which is assigned to the Cu(II) → Cu(I) reduction process. Temperature dependence of magnetic susceptibilities of III and IV has been measured within an interval of 2–290 K. The values of χM at 290 K are 1.72 × 10?3 cm3 mol?1 and 1.71 × 10?3 for III and IV, respectively, which increases continuously upon cooling to 2 K. EPR spectra of III and IV in frozen DMSO and DMF were also reported. The trend g|| > g⊥ > ge suggests the presence of an unpaired electron in the dx2?y2 orbital of the Cu(II) in both complexes. Furthermore, spectral and antimicrobial properties of the prepared complexes were also investigated.  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