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   14692篇
  免费   2207篇
  国内免费   3330篇
化学   12378篇
晶体学   307篇
力学   609篇
综合类   230篇
数学   1490篇
物理学   5215篇
  2024年   48篇
  2023年   231篇
  2022年   495篇
  2021年   536篇
  2020年   552篇
  2019年   578篇
  2018年   478篇
  2017年   541篇
  2016年   665篇
  2015年   778篇
  2014年   966篇
  2013年   1268篇
  2012年   1311篇
  2011年   1408篇
  2010年   1098篇
  2009年   1044篇
  2008年   1200篇
  2007年   1097篇
  2006年   953篇
  2005年   819篇
  2004年   673篇
  2003年   535篇
  2002年   503篇
  2001年   463篇
  2000年   374篇
  1999年   298篇
  1998年   208篇
  1997年   145篇
  1996年   139篇
  1995年   126篇
  1994年   127篇
  1993年   98篇
  1992年   79篇
  1991年   74篇
  1990年   71篇
  1989年   30篇
  1988年   41篇
  1987年   23篇
  1986年   32篇
  1985年   26篇
  1984年   20篇
  1983年   20篇
  1982年   10篇
  1981年   10篇
  1980年   5篇
  1979年   8篇
  1978年   3篇
  1976年   4篇
  1973年   3篇
  1957年   2篇
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
101.
李英奇  杨斌盛 《中国化学》2004,22(10):1153-1157
The rates at which aluminum was removed from the N- and C-terminal monoaluminum ovotransferrins by pyrophosphate were evaluated by UV difference spectra in 0.01 mol/L Hepes, pH=7.4 and at 37℃. Pesudo first-order rate constants as a function of pyrophosphate concentration were measured. The results indicate that the pathways of aluminum removal are different. For the N-terminal binding site, aluminum removal follows simple saturation kinetics, while the removal of aluminum from the C-terminal binding site reverts to the combination of saturation and first-order kinetics. The saturation component is consistent with a rate-limiting conformational change in the protein as has been reported. We propose that the first-order kinetics mechanism is attributed to a pre-equilibrium process. The rate constants of saturation kinetics are accelerated from both terminals with the addition of 0.1 mol/L chloride to the monoaluminum ovotransferrin solutions, whereas the rates of the first-order kinetics are decreased for the C-terminal binding site. The effect of chloride ionic strength causes a continuing increase on kobs for the N- and C-terminal binding sites. Moreover, the kinetics behavior of the N-terminal is more easily affected by chloride than that of the C-terminal. In the experiment presumably the N-terminal site is apparently kinetically more labile than the C-terminal site.  相似文献   
102.
A novel diterpene derivative, 5-methyl-5-(4,8,12-trimethyl-tridecyl)-dihydro-furan-2-one (1) and a new chromone, 5-hydroxy-7-methoxy-3-methyl-chromen-4-one (2), along with a known compound, phytol (3) have been isolated from the aerial parts of Hypericum perforatum. Their structures were established on the basis of spectroscopic analysis and by comparison with published values.  相似文献   
103.
The aqueous dispersion of polyurethaneurea-acrylate (PUA) including small amount of fluorinated block copolymers containing carboxyl groups (PATF), which can be dissolved in water, was used to make films and the surface properties of these films were examined. The experimental data show that the modified PUA film exhibits a hydrophobic surface property, although the original surface of PUA film is hydrophilic. The surface composition of the modified PUA film was measured by ATR and XPS. The results indicate that there is a concentration gradient of the fluorine groups along the lines of thickness of the modified film and towards the outmost surface layer, resulting from the migration of fluorinated blocks to the air side surface of the modified PUA film during the film formation process. However, the PUA film can not be modified effectively by adding the sodium salt of PATF, since the urethane groups in the system are easy to occupy on the surface of the film.  相似文献   
104.
Introduction Humanserumalbumin(HSA)isawell known transportproteinforavarietyofmoleculesandions[1].Thebindingofadrugtoserumalbuminhasimportant pharmacokineticconsequencesbecauseitinfluences distribution,excretionandpharmacologicaleffectsof thedruginthebody…  相似文献   
105.
采用阳极氧化法在镍钛合金(NiTi)纤维上原位生长了双金属氧化物纳米孔(NiTiONPs)涂层,通过扫描电镜(SEM)和能谱(EDS)考察了电解质组成和电压对形貌的影响。将NiTiONPs涂层的NiTi纤维与高效液相色谱-紫外检测器联用,研究了4种典型芳香分析物的萃取性能。结果表明,富含TiO2的NiTiONPs涂层对多环芳烃(PAHs)具有良好的萃取效率,尤其对苯并[a]芘的萃取选择性优于市售聚二甲基硅氧烷纤维和聚丙烯酸酯纤维。在优化条件下,PAHs的线性范围为0.05~200μg/L,相关系数均大于0.999,检出限为0.012~0.134μg/L。对单支纤维日内和日间分析的相对标准偏差(RSDs)分别为4.0%~5.5%和6.0%~6.8%,使用分批组装的5支纤维分析的RSDs为6.4%~7.6%。实际水样分析的加标回收率为84.5%~111.5%。所制备NiTi纤维至少可重复使用250次以上,重现性好。  相似文献   
106.
A zinc phosphate coating process on 7075-T6 aluminum alloy has been significantly improved through a combined approach of titanium colloid pretreatment, pH level adjustment, fluoride additive and ZnO/H3PO4 ratio adjustment. In particular, optimum phosphate coatings were formed in coating baths with a ZnO/H3PO4 ratio of 0.205 and 0.256. Coating morphology studied by SEM reveals that the adjustment in the coating procedure produces an improved crystalline coating layer with high coverage and small grain size. For coatings formed in a bath with a ratio of 0.205, the coverage of the crystalline patches on top of the amorphous coating base is almost complete. The chemical composition of the coating layers has been characterized by XPS and SIMS. The crystalline and amorphous coating phases formed in the bath with a ratio of 0.205 were found to have compositions given schematically as Znx(PO4) and ZnxAly(PO4), respectively. In contrast, neither coating phase formed in the bath with a ratio of 0.256 shows the presence of Al.  相似文献   
107.
Density functional theory (DFT) and Monte Carlo (MC) simulation with free energy perturbation (FEP) techniques have been used to study the tautomeric proton transfer reaction of 2-amino-2-oxazoline, 2-amino-2-thiazoline, and 2-amino-2-imidazoline in the gas phase and in water. Two reaction pathways were considered: the direct and water-assisted transfers. The optimized structures and thermodynamic properties of stationary points for the title reaction system in the gas phase were calculated at the B3LYP/6-311+G(d, p) level of theory. The potential energy profiles along the minimum energy path in the gas phase and in water were obtained. The study of the solvent effect of water on the proton transfer of 2-amino-2-oxozoline, 2-amino-2-thiazoline, and 2-amino-2-imidazoline indicates that water as a solvent is favorable for the water-assisted process and slows down the rate of the direct transfer pathway.  相似文献   
108.
二芳基乙烯;超声条件下芳基格氏试剂与4-烷基苯乙酮的反应  相似文献   
109.
Formation of SnO2 Nanoparticles on External Surface of NaY Zeolite   总被引:1,自引:0,他引:1  
Tin dioxide nanoparticles of 5 nm in size were prepared on NaY zeolite external surface by impregnation of SnCl2 solution and subsequent calcination at 623 K. A SnO2-NaY based chemical sensor for detecting H2 was demonstrated.  相似文献   
110.
二-(二苯基膦)甲烷(dppm)是一种易与金属形成多核络合物的有机膦配体。我们用dppm作为配体合成了一系列银的多核络合物,并对其结构进行了研究。本文报导了其中一个双核化合物[Ag_2(dppm)_2(Py)_2(μ-Cl)]ClO_4的合成及晶体结构、分子结构的测定。  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