全文获取类型
收费全文 | 492篇 |
免费 | 17篇 |
国内免费 | 1篇 |
专业分类
化学 | 393篇 |
晶体学 | 7篇 |
力学 | 4篇 |
数学 | 22篇 |
物理学 | 84篇 |
出版年
2021年 | 3篇 |
2020年 | 11篇 |
2019年 | 12篇 |
2018年 | 7篇 |
2017年 | 6篇 |
2016年 | 18篇 |
2015年 | 9篇 |
2014年 | 10篇 |
2013年 | 17篇 |
2012年 | 24篇 |
2011年 | 43篇 |
2010年 | 13篇 |
2009年 | 9篇 |
2008年 | 31篇 |
2007年 | 31篇 |
2006年 | 26篇 |
2005年 | 21篇 |
2004年 | 15篇 |
2003年 | 13篇 |
2002年 | 16篇 |
2001年 | 14篇 |
2000年 | 10篇 |
1999年 | 7篇 |
1998年 | 8篇 |
1997年 | 3篇 |
1996年 | 5篇 |
1995年 | 5篇 |
1994年 | 3篇 |
1993年 | 6篇 |
1992年 | 3篇 |
1991年 | 4篇 |
1990年 | 3篇 |
1989年 | 10篇 |
1988年 | 9篇 |
1987年 | 17篇 |
1986年 | 4篇 |
1985年 | 8篇 |
1984年 | 7篇 |
1980年 | 3篇 |
1979年 | 3篇 |
1978年 | 2篇 |
1977年 | 3篇 |
1976年 | 5篇 |
1975年 | 2篇 |
1974年 | 4篇 |
1973年 | 4篇 |
1970年 | 2篇 |
1968年 | 3篇 |
1966年 | 4篇 |
1965年 | 3篇 |
排序方式: 共有510条查询结果,搜索用时 15 毫秒
1.
A thin-layer two-phase microcell was fabricated without an adhesive, which showed no fluorescence and resisted acids. The lower hollow of the microcell was thin (0.18 mm), which was in the range of the working distance of the used objective of high magnification (60x) and high numerical aperture (1.2). A reflection method using probe light was newly employed for focusing the objective on a transparent dodecane/water interface strictly with an inverted microscope. The system was applied to in situ fluorescence microscopic measurements of the dynamics of single DNA molecules (165600 base pairs) at the dodecane/water interface. 相似文献
2.
The mechanism of the asymmetric hydrogenation of 2-acyl-1-alkylidene-1,2,3,4-tetrahydroisoquinolines, the first reported reaction with the Noyori-Takaya Ru(CH3COO)2(binap) complex, has been investigated by means of deuterium labeling, kinetics, and NMR analysis. A series of experiments has revealed that (1) a monohydride-unsaturated mechanism operates involving the initial formation of RuH followed by reaction with the enamide substrate, (2) the hydride transfer from RuH to the olefinic double bond is endothermic and reversible, and (3) the rate is determined in the hydrogenolysis step. This view is consistent with that of proposed for the BINAP-Ru catalyzed Kagan reaction. 相似文献
3.
Adachi I Aihara H Dijkstra HB Enomoto R Fujii H Fujii K Fujii T Fujimoto J Fujiwara N Hayashii H Higashi S Iida N Imanishi A Ikeda H Ishii T Itoh R Iwasaki H Iwata S Kajikawa R Kamae T Kato S Kawabata S Kichimi H Kishida T Kobayashi M Kuroda S Kusuki N Maruyama A Maruyama K Masuda H Matsuda T Miyamoto A Morimoto T Nakamura K Nitoh O Noguchi S Ochiai F Okuno H Okusawa T Ohshima T Ozaki H Sato T Sai F Shimonaka J Shimozawa K Shirahashi A Sugahara R Sugiyama A Suzuki S Suwada T Takahashi K 《Physical review letters》1988,60(2):97-100
4.
Shibano M Tsukamoto D Inoue T Takase Y Kusano G 《Chemical & pharmaceutical bulletin》2001,49(4):504-506
Broussonetines are glycosidase-inhibitory alkaloids obtained from Broussonetia kazinoki. Feeding experiments using [1-13C]glucose and 13C-NMR spectroscopic studies showed that broussonetines are biosynthesized through routes similar to those of sphingosine and phytosphingosine. 相似文献
5.
K Yoshino K Goto T Kohno T Morita G Tsukamoto 《Chemical & pharmaceutical bulletin》1990,38(3):676-680
Various asymmetric or cyclic ester derivatives of the phosphonic acid moiety in the calcium antagonist fostedil (KB-944) were synthesized. The coronary vasodilator activity of these compounds was assessed by Langendorff's method. Among them, the ethyl isopropyl ester 12 showed the most potent activity, which was comparable to that of fostedil. 相似文献
6.
Kazuhisha Hiratani Shamsun Naher Michinori Karikomi Kazuo Haga 《Journal of heterocyclic chemistry》2005,42(4):575-582
Novel crownophanes with 27‐ and 28‐membered rings having two hydroxyl groups, two amide groups, and aromatic moieties such as naphthalene, pyridine, and phenyl rings were successfully synthesized by a one‐step reaction from the corresponding macrocyclic polyethers via “tandem Claisen rearrengement” in moderate yields. They can solubilize urea and its derivatives into chloroform solution, while the corresponding macrocyclic polyethers do not solubilize them. According to NMR studies, crownophanes 1 and 2 interact with urea and its derivatives forming 1:1 complexes. 相似文献
7.
Sakaki S Takayama T Sumimoto M Sugimoto M 《Journal of the American Chemical Society》2004,126(10):3332-3348
The Cp(2)Zr-catalyzed hydrosilylation of ethylene was theoretically investigated with DFT and MP2-MP4(SDQ) methods, to clarify the reaction mechanism and the characteristic features of this reaction. Although ethylene insertion into the Zr-SiH(3) bond of Cp(2)Zr(H)(SiH(3)) needs a very large activation barrier of 41.0 (42.3) kcal/mol, ethylene is easily inserted into the Zr-H bond with a very small activation barrier of 2.1 (2.8) kcal/mol, where the activation barrier and the energy of reaction calculated with the DFT(B3LYP) method are given and in parentheses are those values which have been corrected for the zero-point energy, hereafter. Not only this ethylene insertion reaction but also the coupling reaction between Cp(2)Zr(C(2)H(4)) and SiH(4) easily takes place to afford Cp(2)Zr(H)(CH(2)CH(2)SiH(3)) and Cp(2)Zr(CH(2)CH(3))(SiH(3)) with activation barriers of 0.3 (0.7) and 5.0 (5.4) kcal/mol, respectively. This coupling reaction involves a new type of Si-H sigma-bond activation which is similar to metathesis. The important interaction in the coupling reaction is the bonding overlap between the d(pi)-pi bonding orbital of Cp(2)Zr(C(2)H(4)) and the Si-H sigma orbital. The final step is neither direct C-H nor Si-C reductive elimination, because both reductive eliminations occur with a very large activation barrier and significantly large endothermicity. This is because the d orbital of Cp(2)Zr is at a high energy. On the other hand, ethylene-assisted C-H reductive elimination easily occurs with a small activation barrier, 5.0 (7.5) kcal/mol, and considerably large exothermicity, -10.6 (-7.1) kcal/mol. Also, ethylene-assisted Si-C reductive elimination and metatheses of Cp(2)Zr(H)(CH(2)CH(2)SiH(3)) and Cp(2)Zr(CH(2)CH(3))(SiH(3)) with SiH(4) take place with moderate activation barriers, 26.5 (30.7), 18.4 (20.5), and 28.3 (31.5) kcal/mol, respectively. From these results, it is clearly concluded that the most favorable catalytic cycle of the Cp(2)Zr-catalyzed hydrosilylation of ethylene consists of the coupling reaction of Cp(2)Zr(C(2)H(4)) with SiH(4) followed by the ethylene-assisted C-H reductive elimination. 相似文献
8.
9.
10.