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   97240篇
  免费   3717篇
  国内免费   3285篇
化学   39706篇
晶体学   1119篇
力学   7500篇
综合类   240篇
数学   33917篇
物理学   21760篇
  2023年   333篇
  2022年   471篇
  2021年   693篇
  2020年   841篇
  2019年   928篇
  2018年   10995篇
  2017年   10865篇
  2016年   6986篇
  2015年   1894篇
  2014年   1582篇
  2013年   1904篇
  2012年   5655篇
  2011年   12326篇
  2010年   7044篇
  2009年   7315篇
  2008年   8075篇
  2007年   10009篇
  2006年   1412篇
  2005年   2262篇
  2004年   2263篇
  2003年   2598篇
  2002年   1764篇
  2001年   830篇
  2000年   672篇
  1999年   523篇
  1998年   460篇
  1997年   318篇
  1996年   369篇
  1995年   243篇
  1994年   192篇
  1993年   212篇
  1992年   148篇
  1991年   169篇
  1990年   120篇
  1989年   130篇
  1988年   95篇
  1987年   98篇
  1986年   86篇
  1985年   76篇
  1984年   60篇
  1983年   53篇
  1982年   49篇
  1981年   46篇
  1980年   53篇
  1979年   49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.
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   
992.
An easily prepared and highly efficient monodentate phosphoramidite ligand derived from BINOL, (S)-2,2'-O,O-(1,1'-binaphthyl)-dioxo-N,N-diethylphospholidine, was examined in the hydrogenation of both enamides and alpha-dehydroamino acid derivatives. The catalyst provided remarkably high enantioselectivities (up to 99.6% ee for enamides and >99.9% ee for alpha-dehydroamino acid derivatives).  相似文献   
993.
A series of novel 1,3,5-thiadiazine-2-thione derivatives bearing a hydrazide moiety were designed, synthesized and evaluated for their biological activities against phytopathogenic fungi. The antifungal bioassays indicated that the title compound 5b impressively displayed the obvious selectivity and specificity aganist Rhizoctonia solani (Rs) in vitro and in vivo. The above researches provide a significant reference for the further structural optimization of 1,3,5-thiadiazine-2-thione derivatives bearing a hydrazide moiety as potential fungicides.  相似文献   
994.
用XPS和XRD表征了Ba-K-Bi-O超导体熔盐电结晶的阳极和阴 极产物,用SEM分析了Ba-K-Bi-O单生长形态。结果表明,阳极产物是Ba-K-Bi-O超导体单晶,以台阶式方式生长。-K-B-  相似文献   
995.
 A GLP study can be performed at more than one site. This is called a multi-site study. Although, the study is performed at different sites, it is still one study and must completely comply with the GLP principles. The fact that different activities are conducted at different sites implies that the planning, the organization and the communication are crucial for the success of the study. This means that all the staff involved should know their responsibilities and should have the knowledge and skills to realize all the phases of the study according to the GLP principles. To achieve a well managed multi-site study, several strategies for setting up such a study can be followed. This paper focuses on the responsibilities, communication, and collaboration of the personnel, which are involved in a multi-site study. Several case studies are highlighted, and we concluded that the basic communication triangle in a single-site GLP study between test facility management, study director, and the quality assurance unit should be extended to the communication among test facility and test site management, study director, principle investigator(s), and the quality assurance units at the test sites. Introduction Received: 14 August 2002 Accepted: 26 November 2002  相似文献   
996.
In search for a cheaper anode catalyst for the oxidation of ethanol for development of direct alcohol fuel cells, Pd has been considered here as an interesting substitute for Pt in Pt Ru binary electrodeposite. The binary catalyst when co-deposited on nickel support has been found to increase the current density and decrease the anodic overvoltage significantly with respect to pure Pt, Pd and Ni. Its electrocatalytic capability is also comparable with that of the Pt-Ru binary electrocatalyst on Ni-support, when studied in 1 M EtOH containing 1 M NaOH solution. The effect of loading of Pd Ru electrocatalyst on Ni support has also been tested. The electrocatalytic activity of the electrodes for oxidation of ethanol has been explained by studies of cyclic voltammetry, chronopotentiometry, steady-state polarization, and conjugated scanning electron microscopy–energy dispersion X-ray spectroscopy. It has been found that electrode containing the higher amount of deposit are less affected by carbonaceous poisons.  相似文献   
997.
The microwave-mediated reaction of 4-aryl-4-oxobutanoic acids with benzylamines furnished 1-arylmethyl-3-[(E)-1-arylmethylidene]-5-phenyl-2,3-dihydro-1H-pyrrolones. This result is in contract to the earlier report on this reaction conducted under neat conditions. Structures for the products were assigned on the basis of spectral data and confirmed by independent synthesis. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 368–373, March, 2007.  相似文献   
998.
Wen XL  Jia YH  Liu ZL 《Talanta》1999,50(5):1027-1033
The electrochemistry of dopamine (3-hydroxytyramine) was studied by cyclic voltammetry at a glassy carbon electrode in the presence of cetyltrimethylammonium bromide (CTAB) and sodium dodecyl sulfate (SDS) micelles at different pH. The anodic peak potential (E(pa)) and peak current (I(pa)) were found to be remarkably dependent on the charge and the concentration of the surfactant. The E(pa) and I(pa) change abruptly around the critical micellar concentration (CMC) of the surfactants and reach a plateau above the CMC. The E(pa) at the plateau shifts to more positive values in the cationic CTAB micellar solution, e.g. from 180 mV vs SCE in aqueous solution at pH 6.8 to 410 mV in CTAB micelle, whilst it shifts to less positive values in the anionic SDS micellar solution, e.g. 150 mV at pH 6.8. Therefore, the overlapped anodic peaks of dopamine and ascorbic acid in the mixture of the two compounds in aqueous solutions can be separated in CTAB micelles since the micelle shifts the E(pa) of ascorbic acid to less positive values. The two peaks are separated by ca. 400 mV at pH 6.8 in CTAB micelle, hence dopamine can be determined in the presence of 100 times excess of ascorbic acid. In SDS micelle and in the presence of ascorbic acid, the I(pa) of dopamine is greatly enhanced due to the catalytic oxidation of the latter that enables quantitative determination of both compounds.  相似文献   
999.
风毛菊化学成分研究(Ⅰ)   总被引:6,自引:0,他引:6  
从风毛菊中分离得到16种化合物,经光谱方法鉴定为山奈素-3-O-(6"-O-巴豆酰)-β-D-葡萄糖甙(1)、槲皮素-3-O-(6"-O-巴豆酰)-β-D-葡萄糖甙(2)、丁香甙甲醚(3))、山奈素-3-O-β-D-葡萄糖甙、槲皮素-3-O-β-D-葡萄糖甙、丁香甙、α-香树脂醇棕榈酸酯、β-香树酯醇棕榈酸酯、羽扇豆醇棕榈酸酯、羽扇豆醇乙酸酯、羽扇豆醇、β-谷甾醇、棕榈酸、二十四烷酸、二十六烷酸、二十五烷烃,其中(1)、(2)和(3)为新化合物。  相似文献   
1000.
Two new isostructural tellurites, Pb(4)Te(6)M(10)O(41) (M = Nb(5+) or Ta(5+)), have been synthesized by standard solid-state techniques using PbO, Nb(2)O(5) (or Ta(2)O(5)), and TeO(2) as reagents. The structures of Pb(4)Te(6)Nb(10)O(41) and Pb(4)Te(6)Ta(10)O(41) were determined by single-crystal and powder X-ray diffraction. The materials exhibit a three-dimensional framework consisting of layers of corner-shared NbO(6) octahedra connected by TeO(3) and PbO(6) polyhedra. The Nb(5+), Te(4+), and Pb(2+) cations are in asymmetric coordination environments attributable to second-order Jahn-Teller effects. The Nb(5+) cations undergo an intraoctahedral distortion either toward a face or a corner, whereas the Te(4+) and Pb(2+) cations are in distorted environments attributable to their lone pair. In addition, the TeO(3) polyhedra strongly influence the direction of the Nb(5+) intraoctahedral distortion. Infrared and Raman spectroscopy, thermogravimetric analysis, and dielectric measurements are also presented. Crystal data: Pb(4)Te(6)Nb(10)O(41), monoclinic, space group C2/m (No. 12), with a = 23.412(3) A, b = 20.114(3) A, c = 7.5008(10) A, beta = 99.630(4) degrees, V = 3482.4(8) A(3), and Z = 4; Pb(4)Te(6)Ta(10)O(41), monoclinic, space group C2/m (No. 12), with a = 23.340(8) A, b = 20.068(5) A, c = 7.472(2) A, beta = 99.27(3) degrees, V = 3453.8(2) A(3), and Z = 4.  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