全文获取类型
收费全文 | 1083篇 |
免费 | 91篇 |
国内免费 | 78篇 |
专业分类
化学 | 1208篇 |
力学 | 2篇 |
综合类 | 1篇 |
物理学 | 41篇 |
出版年
2024年 | 1篇 |
2023年 | 11篇 |
2022年 | 17篇 |
2021年 | 16篇 |
2020年 | 40篇 |
2019年 | 22篇 |
2018年 | 30篇 |
2017年 | 25篇 |
2016年 | 47篇 |
2015年 | 49篇 |
2014年 | 54篇 |
2013年 | 102篇 |
2012年 | 43篇 |
2011年 | 80篇 |
2010年 | 53篇 |
2009年 | 77篇 |
2008年 | 67篇 |
2007年 | 56篇 |
2006年 | 67篇 |
2005年 | 73篇 |
2004年 | 78篇 |
2003年 | 49篇 |
2002年 | 23篇 |
2001年 | 15篇 |
2000年 | 16篇 |
1999年 | 15篇 |
1998年 | 13篇 |
1997年 | 21篇 |
1996年 | 13篇 |
1995年 | 13篇 |
1994年 | 7篇 |
1993年 | 6篇 |
1992年 | 16篇 |
1991年 | 4篇 |
1990年 | 9篇 |
1989年 | 2篇 |
1988年 | 5篇 |
1987年 | 2篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1984年 | 5篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1977年 | 1篇 |
1972年 | 1篇 |
排序方式: 共有1252条查询结果,搜索用时 31 毫秒
41.
Gopa KarAnil K. Saikia Upasana BoraSanjoy K. Dehury Mihir K. Chaudhuri 《Tetrahedron letters》2003,44(24):4503-4505
The bright yellow crystalline cetyltrimethylammonium tribromide (CTMATB) reagent has been synthesized from the reaction of CTMAB and KBr with H2MoO4·H2O, H2O2 and H2SO4 in the molar ratio 1:2:0.01:4:0.93. CTMATB selectively oxidizes a variety of dialkyl and alkyl aryl sulfides to the corresponding sulfoxides in high yields under mild conditions. 相似文献
42.
A highly atom-efficient synthetic protocol for hydroarylation of terminal-aryl alkynes and styrene through the regioselective CC bond formation via the electrophilic addition of naphthols and substituted phenols has been developed using alumina-sulfuric acid as a heterogeneous supported solid acid catalyst. This methodology shows excellent regioselectivity and affords the desired product in good to excellent yield. The heterogeneous catalyst can also be recycled efficiently without much loss of activity. 相似文献
43.
Sm(II)-modified periodic mesoporous silica (PMS), Sm[N(SiHMe2)2]2(THF)x@MCM-41, was used for the synthesis of Sm(II) alkyl, alkoxide, and indenyl surface species via secondary ligand exchange. The performance of the novel Sm(II)-based organometallic–inorganic hybrid materials as initiators for the graft polymerization of methyl methacrylate (MMA) is reported. All of the Sm(II) hybrid materials including the new PMMA–PMS composites were characterized via N2 physisorption, elemental analysis, FTIR spectroscopy, and scanning electron microscopy (SEM). The organic–inorganic composites revealed complete pore blockage as well as enrichment and strong adhesion of the polymer at the exterior of the porous silica material. 相似文献
44.
Summary The elution behavior of alkali and earth alkaline cations has been studied on a newly synthesized weak cationexchanger (WCX). Applying this stationary phase isocratic separation of these cations is possible. The dependence of retention on competing ion concentration is described via a simple model. The influence of crown ethers as well as organic eluent additives on selectivity and peak efficiency is demonstrated. With optimized separation such cations can be determined with detection limits of about 0.5 ppm using a conductivity detector without ion suppression. 相似文献
45.
Zhibo Ma 《Tetrahedron letters》2006,47(27):4721-4724
One-step and highly efficient syntheses of 2-aryl-1-benzazocines via Beckmann rearrangement of 5H-benzocyclohepten-5-one oxime mesylates in dry toluene was described, in which aryl Grignard reagents were used for the first time to induce Beckmann rearrangement directly without any additional protic agents. Iodotrimethylsilane was also employed to promote Beckmann rearrangement of the mesylates, followed by the treatment of the intermediate imidoyl iodide with phenylmagnesium bromide to complete the synthesis of benzazocines. 相似文献
46.
Jan Bräckow 《Tetrahedron》2006,62(10):2395-2404
An unprecedented method for the preparation of 4,4-disubstituted 1,4-dihydropyridines is presented. It is based on the trapping reaction of 4-substitued N-silylpyridinium ions. When performed with dialkylmagnesium reagents, such as iPr2Mg, silyl protected 4,4-disubstituted 1,4-dihydropyridines were obtained in up to quantitative yields. High 1,4-selectivity was found for sterically demanding nucleophiles, whereas small nucleophiles (Me2Mg) tend to yield 1,2-addition-products. Grignard, dialkylzinc and organocopper reagents were found to give either no addition products or less favorable results. Reduction of the obtained 1,4-dihydropyridine with NaCNBH3 in the presence of HCl, followed by treatment with tert-butyl dicarbonate provided the corresponding N-Boc protected piperidines with high yields. 相似文献
47.
Bhaskar Dhotare 《Tetrahedron letters》2005,46(17):3103-3105
(R)-2,3-Cyclohexylideneglyceraldehyde 1 has been used in a simple and efficient synthesis of (−)-muricatacin 10. The required chiron, syn-alkanetriol 2a was prepared by the reduction of a ketone 3 derived from 1. 相似文献
48.
In order to detect small variations in 13C isotopomers concentrations, high sensitivity, accuracy and precision have to be achieved. To assess such criteria, when using 13C NMR, 13C bi-labelled ethanol has been proposed as a molecular probe. Advantage has been taken of the pre-established structural relationship between the peak areas of the 13C NMR spectrum of this molecule, i.e. the ratio of signal areas is set to a fixed value. It is shown that the quality performance, required by quantitative 13C NMR spectroscopy, is not affected by a large reduction of the repetition delay using relaxation reagents. 相似文献
49.
The effect of steric interactions on the regioselectivity of fluorination of para alkyl substituted phenols was investigated and the strong effect of size of the alkyl substituent, the structure of the F-N reagent and the solvent on the site of fluorination was established. The course of reaction obeyed a second order rate equation, while the fluorination process required higher ΔH≠ activation than oxidation or oxidative demethylation. Solvent polarity variations had a small effect on the rate of functionalisation, while an excellent Hammett correlation with ρ+=−2.3 was determined. 相似文献
50.
Herein, we present a novel way for the production of self-healing hydrogels with stretch beyond 4200% than their initial length and relatively high tensile strength(0.1?0.25 MPa). Furthermore, the hydrogel was insensitive to notch. Even for the samples containing V-notches, a stretch of 2300% was demonstrated. The hydrogels were developed by in situ crosslinking of the self-assembled colloidal poly(acrylic acid)(PAA)/functionalized polyhedral oligomeric silsesquioxane(POSS) micelles. This was achieved by the addition of functionalized polyhedral oligomeric silsesquioxane with tertiary amines and hydroxyls(POSS-AH) into the PAA reaction solution. The POSS-AH led to micellar growth, then the dualcrosslinked network was constructed. One type of crosslink was formed by hydrogen-bonding and ionic interactions between PAA chains and POSS-AH, the other type of crosslink was formed by covalent bonds between PAA and bis(N,N'-methylenebis-acrylamide). 相似文献