全文获取类型
收费全文 | 510篇 |
免费 | 13篇 |
国内免费 | 8篇 |
专业分类
化学 | 360篇 |
晶体学 | 1篇 |
力学 | 26篇 |
数学 | 59篇 |
物理学 | 85篇 |
出版年
2022年 | 7篇 |
2021年 | 16篇 |
2020年 | 25篇 |
2019年 | 20篇 |
2018年 | 21篇 |
2017年 | 20篇 |
2016年 | 30篇 |
2015年 | 21篇 |
2014年 | 32篇 |
2013年 | 93篇 |
2012年 | 33篇 |
2011年 | 36篇 |
2010年 | 26篇 |
2009年 | 22篇 |
2008年 | 37篇 |
2007年 | 19篇 |
2006年 | 12篇 |
2005年 | 15篇 |
2004年 | 12篇 |
2003年 | 9篇 |
2002年 | 6篇 |
2001年 | 3篇 |
2000年 | 2篇 |
1999年 | 1篇 |
1997年 | 1篇 |
1996年 | 2篇 |
1992年 | 2篇 |
1989年 | 1篇 |
1986年 | 3篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1977年 | 1篇 |
排序方式: 共有531条查询结果,搜索用时 15 毫秒
1.
Aluminium dodecyl sulfate trihydrate [Al(DS)3].3H2O is easily prepared and can be used as a Lewis acid surfactant catalyst in water to conduct the highly efficient Michael addition of indoles and pyrrole to alpha,beta-unsaturated electron-deficient compounds at room temperature. 相似文献
2.
[11C]Carbon monoxide at low concentrations, aryl halides and amines were used in the palladium-mediated synthesis of twenty 11C-amides. In the study several approaches to improve the radiochemical yield were explored. Eight of the selected amides were prepared by in situ activation of the amines using lithium bis(trimethylsilyl)amide and the radiochemical yields of these reactions were improved compared to utilising a previous reported method. In the synthesis of 1-[carbonyl-11C]benzoyl-3-methyl-1H-indole (11) from 3-methyl-1H-indole (25), the corresponding organotin-amine was prepared prior to the acylation reaction. In a typical experiment, N-(4-hydroxyphenyl)[carbonyl-11C]acetamide (5) was prepared in 15% radiochemical yield using 4-aminophenol (20) but the yield increased to 63% when the amine was activated by lithium bis(trimethylsilyl)amide. 相似文献
3.
Banks CE Kruusma J Hyde ME Salimi A Compton RG 《Analytical and bioanalytical chemistry》2004,379(2):277-282
Bismuth-modified glassy carbon electrodes have been investigated for their suitability in sonoelectroanalysis. The stability of the bismuth film to the application of ultrasound was assessed via voltammetric and atomic force microscopy (AFM) studies which revealed little ablation at powers up to an intensity of 130 W cm–2 delivered from a 25-kHz sonic horn. Furthermore, bismuth-film-modified glassy carbon electrodes were evaluated for the sonoelectroanalytical quantification of zinc and cadmium. Detection limits of 2×10–7 M and 6×10–9 M respectively were found after a 60-s deposition time via an acoustically assisted deposition protocol. 相似文献
4.
A highly sensitive and fast responding sensor for the determination of thiosulfate, sulfite, sulfide and dithionite is described. It consists of a chemically modified carbon ceramic composite electrode (CCE) containing [Ru(bpy)(tpy)Cl]PF6 complex that was constructed by the sol-gel technique. A reversible redox couple of Ru(II)/Ru(III) was observed as a solute in acetonitrile solution and as a component of carbon based conducting composite electrode. Electrochemical behavior and stability of modified CCE were investigated by cyclic voltametry, the apparent electron transfer rate constant (kappa(S)) and transfer coefficient (a) were determined by cyclic voltametry which were about 28 s(-1) and 0.43 respectively. Electrocatalytic oxidation of S(2-), SO3(2-), S2O4(2-) and S2O3(2-) were effective at the modified electrode at significantly reduced overpotentials and in the pH range 1-11. Optimum pH values for amperometric detection of thiosulfate, dithionite, sulfide and sulfite are 7, 9, 2 and 2. Under the optimized conditions the calibration curves are linear in the concentration ranges 1-500, 3-80, 2-90 and 1-100 microM for S2O3(2-), SO3(2-), S2- and S2O4(2-) determination. The detection limit (signal to noise is 3) and sensitivity are 0.5 and 12, 2.8 and 6, 1.6 and 8, and 0.65 microM and 80 nA microM(-1) for thiosulfate, sulfite, sulfide and dithionite detection. The modified carbon ceramic electrode doped with Ru-complex shows good reproducibility, a short response time (t < 2 s), remarkable long term stability (> 6 month) and especially good surface renewability by simple mechanical polishing (RSD for eight successive polishing is 2%). The advantages of this sulfur compound amperometric detector based on ruthenium doped CCE are high sensitivity, inherent stability at a broader pH range, excellent catalytic activity, less expense and simplicity of preparation in comparison with recently published papers. This sensor can be used as a chromatographic detector for analysis of sulfur derivatives. 相似文献
5.
The carbon ceramic electrode prepared with sol-gel technique is modified by a thin film of chlorogenic acid (CGA). By immersing the carbon ceramic electrode in aqueous solution of chlorogenic acid at less than 2 s a thin film of chlorogenic acid adsorbed strongly and irreversibly on the surface of electrode. The cyclic voltammetry of the resulting modified CCE prepared at optimum conditions shows a well-defined stable reversible redox couple due to hydroquinone/quinone system in both acidic and basic solutions. The modified electrode showed excellent electrocatalytic activity toward NADH oxidation and it also showed a high analytical performance for amperometric detection of NADH. The catalytic rate constant of the modified carbon ceramic electrode for the oxidation of NADH is determined by cyclic voltammetry measurement. Under the optimised conditions the calibration curve is linear in the concentration range 1-120 μm. The detection limit (S/N = 3) and sensitivity are 0.2 μM and 25 nA μM−1.The results of six successive measurement-regeneration cycles show relative standard deviations of 2.5% for electrolyte solution containing 1 mM NADH, indicating that the electrode renewal gives a good reproducible and antifouling surface. The advantages of this amperometric detector are: high sensitivity, excellent catalytic activity, short response time t < 2 s, remarkable long-term stability, simplicity of preparation at short time and good reproducibility. 相似文献
6.
Nanocrystalline TiO2-HClO4,as newly reported catalyst,has been used as an efficient and reusable catalyst for the chemoselective N-Boc protection of amines.The clean,mild acidity condition, quantitative yields of products,short reaction time and low reaction temperature are attractive features of this reaction.In practice,this method is a combination of a satisfactory synthesis and more significantly easy product isolation and purification. 相似文献
7.
8.
9.
Farhad Shirini Manouchehr Mamaghani Seyyed Vahid Atghia 《Journal of the Iranian Chemical Society》2013,10(3):415-420
Nanoporous Na+-montmorillonite sulfonic acid was found to be an efficient and green catalyst for the synthesis of various 14-aryl-14H-dibenzo[a,j]xanthenes and 1,8-dioxo-dodecahydroxanthene derivatives by the reaction of aldehydes with 2-naphthol and 1,3-cyclohexanedione, respectively. This novel synthetic method has the advantages of high yields, short reaction times and recyclability of the catalyst, simplicity and easy workup compared to the conventional methods reported in the literature. 相似文献
10.