全文获取类型
收费全文 | 1790篇 |
免费 | 66篇 |
国内免费 | 2篇 |
专业分类
化学 | 1464篇 |
晶体学 | 26篇 |
力学 | 17篇 |
数学 | 82篇 |
物理学 | 269篇 |
出版年
2023年 | 14篇 |
2022年 | 18篇 |
2021年 | 28篇 |
2020年 | 24篇 |
2019年 | 28篇 |
2018年 | 21篇 |
2017年 | 19篇 |
2016年 | 38篇 |
2015年 | 28篇 |
2014年 | 49篇 |
2013年 | 98篇 |
2012年 | 88篇 |
2011年 | 117篇 |
2010年 | 55篇 |
2009年 | 52篇 |
2008年 | 121篇 |
2007年 | 136篇 |
2006年 | 117篇 |
2005年 | 165篇 |
2004年 | 111篇 |
2003年 | 73篇 |
2002年 | 81篇 |
2001年 | 25篇 |
2000年 | 27篇 |
1999年 | 12篇 |
1998年 | 25篇 |
1997年 | 17篇 |
1996年 | 26篇 |
1995年 | 13篇 |
1994年 | 12篇 |
1993年 | 10篇 |
1992年 | 9篇 |
1991年 | 9篇 |
1990年 | 4篇 |
1989年 | 9篇 |
1988年 | 6篇 |
1987年 | 6篇 |
1986年 | 10篇 |
1985年 | 13篇 |
1984年 | 19篇 |
1983年 | 16篇 |
1982年 | 24篇 |
1981年 | 12篇 |
1980年 | 21篇 |
1979年 | 7篇 |
1978年 | 15篇 |
1977年 | 8篇 |
1976年 | 5篇 |
1975年 | 5篇 |
1974年 | 6篇 |
排序方式: 共有1858条查询结果,搜索用时 20 毫秒
41.
42.
43.
Sodium poly(styrenesulfonate)(polySSNa)-grafted polymer nanoparticles were synthesized by core-cross-linking of block copolymer micelles and subsequent chemical transformation. Block copolymers, poly(p-((1-methyl)silacyclobutyl)styrene-block-poly(neopentyl p-styrenesulfonate)s, polySBS-b-polySSPen, were synthesized by nitroxy-mediated living radical polymerization. The block copolymers formed micelles (Rh=15-23 nm, where Rh represents the hydrodynamic radius) with a polySBS core and polySSPen shell in acetone. The micelle core was cross-linked by ring-opening polymerization of silacyclobutyl groups in polySBS. Hydrolysis of the neopentyl groups provided polySSNa-grafted nanoparticles. The Rh of the particles before the hydrolysis ranged from 12 to 21 nm in acetone, while they varied to the range from 50 to 110 nm in water after the hydrolysis. 相似文献
44.
The ruthenium-catalysed double addition of trimethylsilyldiazomethane to alkynes developed by Dixneuf and co-workers was applied to the synthesis of 2-alkyl- or 2-aryl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,4-bis(trimethylsilyl)-1,3-butadienes by use of alkynylboronates instead of alkynes. Di- and tetrasubstituted 1,3-butadienes were prepared from a 2-boryl-1,4-disilyl-1,3-butadiene, using the Suzuki-Miyaura coupling reaction, iodolysis of the alkenylsilane moieties with N-iodosuccinimide and hydrolysis of the carbon-silicon bonds with trifluoroacetic acid. The same compound was converted also to a bicyclic compound, a trisubstituted 1,3-butadiene and a dienone through the Diels-Alder reaction, oxidation of the alkenylboronate moiety and the Mukaiyama aldol reaction. 相似文献
45.
Poly(ethylene oxide-)-poly(1, 1-dimethyl-2, 2-dihexyldisilene) block copolymers (PEO-b-PMHS) were synthesized by the anionic polymerization of masked disilenes initiated with the potassium alkoxide of poly(ethylene glycol). The block copolymer self-assembled into polymer micelles in water accompanied by a transition in the polysilane conformation. 相似文献
46.
Alkenylation reaction of alpha-halo carbonyl compounds with alkenylindiums proceeded via a radical process in the presence of triethylborane. Unactivated alkene moieties as well as a styryl group could be introduced by this method. The geometry of the carbon-carbon double bonds of the alkenylindiums was retained. Preparation of an alkenylindium via a hydroindation of 1-alkyne followed by radical alkenylation established an efficient one-pot strategy. [reaction: see text] 相似文献
47.
Tsuchimoto T Kamiyama S Negoro R Shirakawa E Kawakami Y 《Chemical communications (Cambridge, England)》2003,(7):852-853
A palladium-indium triflate catalyst was found to be much more active for the dimerization of vinylarenes compared with generally used cationic palladium(II) catalysts. 相似文献
48.
Cordonier CE Satake K Atarashi M Kawamoto Y Okamoto H Kimura M 《The Journal of organic chemistry》2005,70(9):3425-3436
[reaction: see text] The reaction of 2-methoxy-3H-azepines, in the presence or absence of a nucleophile, with N-bromosuccinimide (NBS) gave a regioselective 1,4-adduct from which the corresponding 2H-azepine derivatives were formed via base-promoted hydrogen bromide elimination, generally in moderate to quantitative yield. Competitive formation of 4-bromo-2-methoxy-3H-azepine by electrophilic substitutuion or 3H-azepin-2-yl 2H-azepin-2-yl ether by transetherification was minimized at lower reaction temperatures. Quantitative substitution of 2-(2',4',6'-trichlorophenoxy)-2H-azepine derivatives, formed in moderate yield from the respective 3H-azepine and NBS in the presence of 2,4,6-trichlorophenol (TCP), by various nucleophiles gave the corresponding 2-substituted 2H-azepine. Among these nucleophiles were alkanethiol and alkylamine that are not tolerated in the reaction of 3H-azepine and NBS. 相似文献
49.
Treatment of 1,4‐disubstituted 1,2,3‐triazoles with aryl chlorides in the presence of potassium carbonate under palladium catalysis and microwave irradiation at 250 °C for 15 min leads to arylation of the triazole at the 5‐position. A variety of functional groups, including ester and hydroxy groups, are compatible. The procedure is suitable for the regioselective preparation of trisubstituted triazoles. Microwave irradiation accelerates the reaction, thus allowing the rapid synthesis of trisubstituted triazoles, which are difficult to synthesize selectively. 相似文献
50.
Shirakawa S Lombardi PJ Leighton JL 《Journal of the American Chemical Society》2005,127(28):9974-9975
A highly diastereo- and enantioselective [3 + 2] acylhydrazone-enol ether cycloaddition mediated by a simple chiral silane Lewis acid is described. The reactions are highly practical, as demonstrated by a larger scale (5 g of the hydrazone) reaction in which the product was obtained after recrystallization in 93% yield and 99% ee. Evidence for a stepwise mechanism and a model for the asymmetric induction are presented, as well. 相似文献