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   34308篇
  免费   5691篇
  国内免费   4129篇
化学   24309篇
晶体学   395篇
力学   1963篇
综合类   246篇
数学   4292篇
物理学   12923篇
  2024年   145篇
  2023年   723篇
  2022年   1162篇
  2021年   1236篇
  2020年   1390篇
  2019年   1367篇
  2018年   1195篇
  2017年   1148篇
  2016年   1658篇
  2015年   1652篇
  2014年   1968篇
  2013年   2619篇
  2012年   3042篇
  2011年   3217篇
  2010年   2221篇
  2009年   2066篇
  2008年   2221篇
  2007年   2030篇
  2006年   1736篇
  2005年   1522篇
  2004年   1251篇
  2003年   1034篇
  2002年   1071篇
  2001年   880篇
  2000年   755篇
  1999年   675篇
  1998年   551篇
  1997年   473篇
  1996年   513篇
  1995年   436篇
  1994年   383篇
  1993年   279篇
  1992年   276篇
  1991年   245篇
  1990年   206篇
  1989年   169篇
  1988年   94篇
  1987年   97篇
  1986年   113篇
  1985年   86篇
  1984年   61篇
  1983年   42篇
  1982年   21篇
  1981年   20篇
  1980年   10篇
  1979年   12篇
  1977年   6篇
  1976年   9篇
  1975年   8篇
  1957年   8篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
21.
A Nafion-modified glassy carbon electrode incorporated with tobramycin for the voltammetric stripping determination of Cu2+ has been explored. The electrode was fabricated by tobramycin containing Nafion on the glassy carbon electrode surface. The modified electrode exhibited a significantly increased sensitivity and selectivity for Cu2+ compared with a bare glassy carbon electrode and the Nafion modified electrode. Cu2+ was accumulated in HAc-NaAc buffer (pH 4.6) at a potential of -0.6 V (vs. SCE) for 300 s and then determined by differential pulse anodic stripping voltammetry. The effects of various parameters, such as the mass of Nafion, the concentration of tobramycin, the pH of the medium, the accumulation potential, the accumulation time and the scan rate, were investigated. Under the optimum conditions, a linear calibration graph was obtained in the concentration range of 1.0 x 10(-9) to 5.0 x 10(-7) mol l(-1) with a correlation coefficient of 0.9971. The relative standard deviations for eight successive determinations were 4.3 and 2.9% for 1.0 x 10(-8) and 2.0 x 10(-7) mol l(-1) Cu2+, respectively. The detection limit (three times signal to noise) was 5.0 x 10(-10) mol l(-1). A study of interfering substances was also performed, and the method was applied to the direct determination of copper in water samples, and also in analytical reagent-grade salts with satisfactory results.  相似文献   
22.
Non-dispersive atomic fluorescence spectrometry (NDAFS) coupled with vapor generation (VG) sample introduction was applied to the determination of the concentrations of hazardous heavy metals, such as arsenic, cadmium, lead and mercury, in seawater, soils and total airborne particulate matter (PM) collected around the Xiamen area in China. Almost 100% sample introduction efficiency was achieved by using thiourea and ascorbic acid for the pre-reduction of As(V) to As(III), K3Fe(CN)6 and tartaric acid for pre-oxidation of Pb(II) to Pb(IV), and masking the interferences arising from the co-existing transition metals to As, Cd, Hg and Pb during their vapor generation process. Moreover, a novel sample pretreatment device was developed to avoid the loss of mercury, lead, cadmium and arsenic during sample pretreatment. With such methods, the detection limit (DL) of arsenic, cadmium, lead and mercury was down to 0.08, 0.03, 0.05, 0.01 ng mL(-1) (3sigma), respectively. The relative standard deviations (RSD, n = 11) for arsenic, cadmium, lead and mercury at 10 ng mL(-1) were 0.9%, 1.6%, 1.3% and 2.0%, respectively. The concentrations of hazardous heavy metals in the environmental samples collected in Xiamen, China are in the range from 0.02 +/- 0.001 ng mL(-1) in seawater to 15.3 +/- 0.2 microg g(-1) in soils. Besides flame/GF-AAS and ICP-AES/MS, VG-NDAFS should be another choice for the determination of hazardous heavy metals in environmental samples.  相似文献   
23.
Thiourea compounds are excellent agents of bioactive substance. A number of biological activities are associated with substituted thiourea derivatives. A survey of literature reveals that some work has been reported on benzoylthiourea, which has found plenty of applications as a facile and simple ligand in determination of trances of the transition metal and as an available starting material in preparation of a wide variety of metal complexes. In recent years,N-benzoyl-N'-(2-hydroxyethyl)-thiourea has attracted considerable attention as selective reagents for the liquid-liquid extraction and preconcentration of platinum group metals and its antifungle activity.As a part of our works in studying coordination behaviours of N-benzoyl-N'-(2-hydroxyethyl)-thiourea and its bioactivity, in view of these observations and in continuation of our previous works on it, the present work was reported on the crystal structure of N-benzoyl-N'-( 2-hydroxyethyl)-thiourea.The crystals structure in the monoclinic system and space group of P21/c of N-benzoyl-N'-(2-hydroxyethyl)- thiourea (C10H12N2O2S) was determined from single-crystal X-ray diffraction analysis, a = 17.083 (3) A, b = 4.5490 (10) A, c = 14.279 (3)A, a = 90.00°, a = 102.44(3)°, a = 90.00 °, Ⅴ = 1083.6 (4)A3, Z = 4, Dc = 1.375 Mg/m3, i (Mo Ka)= 0.280 mm-1, F(000) =472. The final R and u R are 0.0399 and 0.0881 for 783 observed reflections [Ⅰ>26(Ⅰ)].Fig. 1 shows the molecular crystal structure of N-benzoyl-N'-(2-hydroxyethyl)thiourea indicating that the carbonyl and thiocarbonyl moieties are pointing in approximate opposite directions. The six atoms in the ring structure hydrogen bonded are almost in one plane. The N(2)-H proton pendant arm extends to the carbonyl oxygen atom, forms hydrogen bond between them.The existence of hydrogen bond in benzoyl-thiourea molecular six-membered ring structure has significant implications on coordination properties, suggest the possibility of intramolecular hydrogen bond controlled coordination behaviors of these potentially bidentate ligands. In the coordination compound reported by Bourne et al.,cis-bis(N-benzoyl-N'-propylthiourea)dichloroplatinum(Ⅱ), the two ligand molecules bind to Pt(Ⅱ)via the sulfur atoms only, the carbonyl oxygen atom being locked into hydrogen bond similar to that in the free ligands.  相似文献   
24.
Metabolites of A Novel Antibiotic Bitespiramycin in Rat Urine and Bile   总被引:3,自引:0,他引:3  
A sensitive analytical method to identify active metabolites of bitespiramycin in rat urine and bile was developed by liquid chromatography-electrospray ionization tandem mass spectrometry(LC/ESI-MS^n).Bitespiramycin and its major active metabolites in rat urine and bile were isolated and identified as M1 serial(spiramycin Ⅰ,Ⅱ,Ⅲ),M2 serial(platenomycin A1,josamycin and leucomycin A1) and M3 serial(deisovalerylplatenomycin A1,deisovaleryljosamycin,deisovalerylleucomycin A1).  相似文献   
25.
Baker‘s yeast mediated reduction of optically active diketone is described. The two keto groups are efficiently differentiated and the ee value of the recovered material is considerably raised. It affords highly optically active key intermediates efficiently for the synthesis of natural polyhydroxylated agarofuran products.  相似文献   
26.
The relation of the isoelectric point (IEP) and the point of zero net charge (PZNC) of the hydrotalcite-like compounds was discussed. It was found that the IEP does not equal to the PZNC and the IEP is higher than the PZNC. The structural positive charges existing in the HTlc,which cause the difference between the IEP and the PZNC. The effects of the structural positive charges of the HTlc on its IEP and PZNC are the same as the specific adsorption of metal cations.  相似文献   
27.
The crystal structures of two potential tumor imaging agents and therapeutic agents -copper(Ⅱ) complexes with salicylidene-tyrosinato Schiff base and nitrogen-donor chelating Lewis base, [Cu(sal-tyr)(bipy)] 1 and [Cu(sal-tyr)(phen)]2CH3OH 2 are presented. Our work is helpful to get deep understanding of novel 64Cu tumor imaging agents and therapeutic agents.  相似文献   
28.
关于具有给定Sylow子群正规化子的有限群Ⅱ   总被引:1,自引:0,他引:1  
郭文彬 《数学学报》1996,39(4):509-513
本文在有限可解群中解决了:任意m-秩≤2的子群闭的局部群系具有性质:“如果群G的非单位Sylow子群的正规化子属于,则群G也属于的一个充分必要条件.  相似文献   
29.
横向放大率法确定复合光学系统的基点   总被引:2,自引:0,他引:2  
曹国荣 《物理实验》2002,22(3):13-14,20
介绍了应用测量横向放大率确定两薄透镜组成的复合光学系统基点的方法。由于采用线阵光电耦合器件(CCD)测量物经光学系统成像的横向放大率,提高了测量精度。  相似文献   
30.
本文通过对大量的黄酮类化合物13C NMR图谱的分析和研究,总结了不同类型的黄酮类化合物的13C NMR图谱特征及化学位移规律.对影响黄酮类化合物结构骨架上不同位置碳原子化学位移的因素进行了分析,建立了用于黄酮类天然产物13C NMR图谱智能解析的知识库.  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