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   332篇
  免费   25篇
  国内免费   62篇
化学   330篇
力学   5篇
综合类   1篇
数学   36篇
物理学   47篇
  2023年   2篇
  2022年   4篇
  2021年   5篇
  2020年   8篇
  2019年   11篇
  2018年   3篇
  2017年   6篇
  2016年   16篇
  2015年   10篇
  2014年   10篇
  2013年   16篇
  2012年   21篇
  2011年   31篇
  2010年   18篇
  2009年   23篇
  2008年   31篇
  2007年   25篇
  2006年   30篇
  2005年   25篇
  2004年   17篇
  2003年   9篇
  2002年   22篇
  2001年   22篇
  2000年   17篇
  1999年   15篇
  1998年   4篇
  1997年   2篇
  1996年   1篇
  1995年   3篇
  1994年   2篇
  1993年   3篇
  1992年   1篇
  1991年   1篇
  1990年   1篇
  1983年   1篇
  1980年   1篇
  1976年   1篇
  1974年   1篇
排序方式: 共有419条查询结果,搜索用时 15 毫秒
1.
A new asymmetric Salamo‐based ligand H2L was synthesized using 3‐tertbutyl‐salicylaldehyde and 6‐methoxy‐2‐[O‐(1‐ethyloxyamide)]‐oxime‐1‐phenol. By adjusting the ratio of the ligand H2L and Cu (II), Co (II), and Ni (II) ions, mononuclear, dinuclear, and trinuclear transition metal (II) complexes, [Cu(L)], [{Co(L)}2], and [{Ni(L)(CH3COO)(CH3CH2OH)}2Ni] with the ligand H2L possessing completely different coordination modes were obtained, respectively. The optical spectra of ligand H2L and its Cu (II), Co (II) and Ni (II) complexes were investigated. The Cu (II) complex is a mononuclear structure, and the Cu (II) atom is tetracoordinated to form a planar quadrilateral structure. The Co (II) complex is dinuclear, and the two Co (II) atoms are pentacoordinated and have coordination geometries of distorted triangular bipyramid. The Ni (II) complex is a trinuclear structure, and the terminal and central Ni (II) atoms are all hexacoordinated, forming distorted octahedral geometries. Furthermore, optical properties including UV–Vis, IR, and fluorescence of the Cu (II), Co (II), and Ni (II) complexes were investigated. Finally, the antibacterial activities of the Cu (II), Co (II), and Ni (II) complexes were explored. According to the experimental results, the inhibitory effect was found to be enhanced with increasing concentrations of the Cu (II), Co (II), and Ni (II) complexes.  相似文献   
2.
A two-dimensional model for the simulation of a binary dendritic growth with convection has been developed in order to investigate the effects of convection on dendritic morphologies. The model is based on a cellular automaton (CA) technique for the calculation of the evolution of solid/liquid (s/l) interface. The dynamics of the interface controlled by temperature, solute diffusion and Gibbs–Thomson effects, is coupled with the continuum model for energy, solute and momentum transfer with liquid convection. The solid fraction is calculated by a governing equation, instead of some approximate methods such as lever rule method [A. Jacot, M. Rappaz, Acta Mater. 50 (2002) 1909–1926.] or interface velocity method [L. Nastac, Acta Mater. 47 (1999) 4253; L. Beltran-Sanchez, D.M. Stefanescu, Mat. and Mat. Trans. A 26 (2003) 367.]. For the dendritic growth without convection, mesh independency of simulation results is achieved. The simulated steady-state tip velocity are compared with the predicted values of LGK theory [Lipton, M.E. Glicksmanm, W. Kurz, Metall. Trans. 18(A) (1987) 341.] as a function of melt undercooling, which shows good agreement. The growth of dendrite arms in a forced convection has been investigated. It was found that the dendritic growth in the upstream direction was amplified, due to larger solute gradient in the liquid ahead of the s/l interface caused by melt convection. In the isothermal environment, the calculated results under very fine mesh are in good agreement with the Oseen–Ivanstov solution for the concentration-driven growth in a forced flow.  相似文献   
3.
珊瑚属腔肠动物门 ( Clelenterata) ,海鸡冠目 ( Alcyonacea) ,是一种热带与亚热带海洋中广泛分布Scheme 1  Structure of cervicoside(1 )的低等海洋生物 .软珊瑚的次生代谢物中含有萜类和甾体类等各类生理活性物质[1~ 5] .我们在对鹿角短指软珊瑚的次生代谢产物研究中 ,分离到一个新三糖甙 ,命名为 Cervicoside( 1 ) ,结构见 Scheme 1 .该化合物具有较强的体外抗癌活性 .1 实验部分1 .1 样品 鹿角短指软珊瑚采自海南岛三亚海域 .样品储藏于中山大学化学与化学工程学院天然有机化学研究室 ,编号为 98- SY- 3.种属由中国科学院南海…  相似文献   
4.
Alternate adsorption of positively charged colloid-Au nanoparticles (nano-Au⊕) and negatively charged hemoglobin (Hb) on L-cysteine (L-cys) modified gold electrode resulted in the assembly of {Hb/nano-Au⊕}n layer-by-layer films/L-cys modified gold electrode. The nano-Au⊕ was characterized by transmission electron micrograph (TEM) and microelectrophoresis. The modified electrode interface morphology was characterized by electrochemical impedance spectroscopy (EIS), atomic force mi- croscopy (AFM), cyclic voltammograms (CV) and chronoamperometry. Direct electron transfer between hemoglobin and gold electrodes was studied, and the apparent Michaelis-Menten constant ( km app) of the modified electrode was evaluated to be 0.10 mmol·L?1. Moreover, the higher activity of proteins in the nano-Au⊕ films could be retained compared with the electropolymerization membrane, since the pro- teins in nano-Au⊕ films retained their near-native structure. Direct electron transfer between hemoglo- bin and electrode and electrochemically catalyzed reduction of hydrogen peroxide on a modified elec- trode was studied, and the linear range was from 2.1×10-8 to 1.2 ×10?3 mol·L-1 (r = 0.994) with a detection limit of 1.1×10-8 mol·L-1 H2O2.  相似文献   
5.
A novel potentiometric immunosensor for detection of Japanese B encephalitis vaccine was developed by immobilizing antiserum of Japanese B encephalitis on nano-Au/polymerized o-phenylenediamine (o-PDA) film on the platinum (Pt) electrode. The performance and factors influencing the performance of the resulting immunosensor were studied. The immunosensor showed a specific response to Japanese B encephalitis vaccine in the range 1.1 × 10−8 to 2.0 × 10−6 lgpfu/ml (plaque forming unit) with a detection limit of 6 × 10−9 lgpfu/ml. The correlation coefficient is 0.9986. The incubation time, incubation temperature, pH, reproducibility and stability of the immunosensor were also studied. The present work supplied a promising test method for biological products.  相似文献   
6.
水杨醛肟铜络合物中性载体高选择性水杨酸根电极的研究   总被引:2,自引:0,他引:2  
采用合成的Schiff碱金属络合物水杨醛肟铜(Ⅱ)、锌(Ⅱ)、镍(Ⅱ)为中性载体制备阴离子选择性电极。结果表明水杨醛肟铜(Ⅱ)对水杨酸根(Sal-)具有高选择性及优良的电位响应性能,电极呈现反Hofmeister选择性行为,其选择性次序为Sal->ClO4->SCN->I->NO2->NO3->Br->Cl->OAc->SO42-。采用交流阻抗技术和紫外可见光谱技术研究了电极的响应机理。该电极具有响应快、重现性好、检出限低和制备简单等优点。将电极用于药品及人体尿液分析,结果令人满意。  相似文献   
7.
A Novel Dihydroflavone from the Roots of Uvaria Macrophylla   总被引:1,自引:0,他引:1  
A new dihydroflavone (1), named macrophyllol A, was isolated from the roots of Uvaria macrophylla. Its structure was elucidated on the basis of spectroscopic evidence.  相似文献   
8.
The immobilization of anti-IgG on Au-colloid modified gold electrodes has been investigated. A cleaned gold electrode was first immersed in a mercaptoethylamine (AET) solution, and then gold nanoparticles were chemisorbed onto the thiol groups of the mercaptoethylamine. Finally, anti-IgG was adsorbed onto the surface of the gold nanoparticles. Potentiometric immunosensor, cyclic voltammetry, and electrochemical impedance techniques were used to investigate the immobilization of anti-IgG on Au colloids. In the impedance spectroscopic study, an obvious difference of the electron transfer resistance between the Au-colloid modified electrode and the bare gold electrode was observed. The cyclic voltammogram tends to be more irreversible with increased anti-IgG concentration. Using the potentiometric immunosensor, the proposed technique is based on that the specific agglutination of antibody-coated gold nanoparticles, averaging 16 nm in diameter, in the presence of the corresponding antigen causes a potential change that is monitored by a potentiometry. It is found that the developed immunoagglutination assay system is sensitive to the concentration of IgG antigen as low as 12 ng mL(-1). Experimental results showed that the developed technique is in satisfactory agreement with the ELISA method, and that gold nanoparticles can be used as a biocompatible matrix for antibody or antigen immobilization.  相似文献   
9.
Ruo  Jun  SUN  Hui  Jiang 《中国化学快报》2003,14(3):243-244
Phosphonium or arsonium salt 1 can undergo the tandem reaction of deprotonation -oxidation-Wittig reaction with alcohol 2 in the presence of sodium hydroxide and manganese dioxide,which affords a general simplified method for the stereoselective synthesis of (E)- α-β-unsaturated esters 3.  相似文献   
10.
Cunninghmia lanceolata Hook. is a traditional Chinese medicine used for thetreatment of hernia, arthritis and strangury. its chemical constituents have beenexamined]' 2' 3' '. In a previous paper we reported a bislabdane-type diterpenoidlanceolatic acid from the roots of the plant 5. Further chemical studies on this plantled to the isolation of another new bislabdane-type diterpenoid, named lanceolatin(I ).Compound I was obtained as white amorphous powder. mp 232-234 'C, [a]."-24 (c 0. 10, C…  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