全文获取类型
收费全文 | 252篇 |
免费 | 9篇 |
专业分类
化学 | 248篇 |
数学 | 2篇 |
物理学 | 11篇 |
出版年
2023年 | 1篇 |
2022年 | 1篇 |
2021年 | 2篇 |
2020年 | 3篇 |
2019年 | 3篇 |
2018年 | 1篇 |
2016年 | 5篇 |
2015年 | 5篇 |
2014年 | 7篇 |
2013年 | 4篇 |
2012年 | 19篇 |
2011年 | 18篇 |
2010年 | 15篇 |
2009年 | 10篇 |
2008年 | 22篇 |
2007年 | 24篇 |
2006年 | 24篇 |
2005年 | 20篇 |
2004年 | 17篇 |
2003年 | 15篇 |
2002年 | 18篇 |
2001年 | 5篇 |
2000年 | 3篇 |
1999年 | 4篇 |
1997年 | 2篇 |
1996年 | 1篇 |
1993年 | 1篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1987年 | 2篇 |
1985年 | 1篇 |
1979年 | 1篇 |
1977年 | 1篇 |
1974年 | 1篇 |
1972年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有261条查询结果,搜索用时 171 毫秒
71.
Organotin perfluorooctanesulfonates as air-stable Lewis acid catalysts: synthesis, characterization, and catalysis 总被引:1,自引:0,他引:1
An de L Peng Z Orita A Kurita A Man-e S Ohkubo K Li X Fukuzumi S Otera J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(6):1642-1647
The reactions of 1,3-dichloro-1,1,3,3-tetrabutyldistannoxane and dialkyltin dihalides with silver perfluorooctanesulfonate provided the corresponding sulfonates as hydrates. The number of water molecules (n) of hydration was dependent on the conditions. The distannoxane derivative was identified as n from 0.5 to 6, while in the hydrated mononuclear species and DMSO complexes n varied widely from 4 to 13. 119Sn NMR spectroscopy and conductivity measurements indicated the ionic dissociation of these compounds in solution. These compounds exhibited unusually high solubility in polar organic solvents. The ionic dissociation together with facile hydration probably causes the unusual solubility. The Lewis acidity of these compounds was found to be high among organotin derivatives on the basis of ESR spectra of superoxide/metal-ion complexes. In contrast to well-known organotin triflates, these compounds suffered no hydrolysis upon storage in open air. The high catalytic activity of the distannoxane 1 was exemplified for various carbon-carbon bond-forming reactions, such as Mukaiyama-aldol as well as -Michael reactions and allylation of aldehydes. 相似文献
72.
Nakata S Morishima S Ichino T Kitahata H 《The journal of physical chemistry. A》2006,110(50):13475-13478
The photosensitive Belousov-Zhabotinsky (BZ) reaction was investigated on a circular ring, which was drawn using computer software and then projected on a film soaked with BZ solution using a liquid-crystal projector. Under the initial conditions, a chemical wave propagated with a constant velocity on the black ring under a bright background. When the background was rapidly changed to dark, coexistence of the oscillation on part of the ring and propagation of the chemical wave on the other part was observed. These experimental results are discussed in relation to the nature of the photosensitive BZ reaction and theoretically reproduced based on a reaction-diffusion system using the modified Oregonator model. 相似文献
73.
The propagation of chemical waves in the photosensitive Belousov-Zhabotinsky (BZ) reaction was investigated using an excitable field composed of two rings in slight contact, which were drawn using computer software and then projected on a film soaked with BZ solution using a liquid-crystal projector. When the initial phase difference between the two chemical waves in the individual rings was smaller than a critical value, this initial value was maintained after collision of the chemical waves. However, when the initial phase difference was larger than this critical value, the phase difference converged to the same value after the second collision. The critical value increased with an increase in the thickness of the rings. These experimental results on the geometry of the excitable field are discussed in relation to the nature of chemical wave propagation. These results suggest that the photosensitive BZ reaction may be useful for creating spatiotemporal patterns that depend on the geometric arrangement of excitable fields. 相似文献
74.
Several types of organic reactions were accelerated by immediate evaporation of solvents because of remarkable enhancement of molecule-to-molecule contacts between reactants. 相似文献
75.
A new type of fluorous distannoxanes, [XRf2SnOSnRf2Y]2 (Rf = C6F13C2H4; X, Y = C6F13SO3 (2) and (C6F13SO2)2N, Cl (3)) was prepared successfully as hydrates from the reaction of [ClRf2SnOSnRf2Cl]2 with C6F13SO3Ag and (C6F13SO2)2NAg, respectively. Despite their high fluorine content (59.85 and 59.27% F), these distannoxanes were completely insoluble in fluorocarbons as well as hydrocarbons and halo alkanes. In contrast to this, fluorous distannoxanes 2 and 3 were soluble in polar organic solvents, such as EtOAc, acetone, and THF. When 2 and 3 were added to a two-phase mixture of fluorocarbon and EtOAc, the mixture turned miscible in proportion to the amount of 2 and 3 added, and finally, the mixture turned to a homogeneous solution. 相似文献
76.
Noguchi E Fujiwara Y Matsushita S Ikeda T Ono M Nohara T 《Chemical & pharmaceutical bulletin》2006,54(9):1312-1314
Pregnane glycosides have been isolated in small amounts, along with the major components furostanol and spirostanol glycosides, from Dioscoreaceae, Taccaceae, and Solanaceae, suggesting that pregnane glycosides might be biosynthesized from furostanol and spirostanol glycosides. Recently, commercial natural foods composed of diosgenin have been used for the treatment of diseases such as osteoporosis and premenstrual syndrome in women. It is anticipated that diosgenin would be metabolized into a type of steroidal hormone, for instance progesterone, however, this metabolism has not been confirmed. Therefore, we have examined the metabolites in the urine of subjects who ingested tomatoes, which contain a considerable amount of the steroidal glycoside esculeoside A. The occurrence of steroidal hormones in the metabolites has been recognized. It has been proven that when a steroidal glycoside is administered, it is partly metabolized into a type of steroidal hormone exhibiting various physiological activities. 相似文献
77.
Jing-Kun Fang De-Lie An Kan Wakamatsu Tetsuo Iwanaga Shin-ichi Akita Akihiro Orita Junzo Otera 《Tetrahedron》2010,66(29):5479-5485
To gain insight into substituent electronic effect on charge-transfer excitation of acetylenic π-systems, phenylene-(poly)ethynylenes substituted by Ph2N or Ph2N/cyano groups were synthesized by combination of Sonogashira coupling and double elimination protocol of β-substituted sulfones. These substituted phenyleneethynylenes showed large molar absorption coefficients ?, and emitted strong fluorescence upon UV light irradiation. Phenylene-(poly)ethynylenes, which involve butadiyne or hexatriyne motifs, emitted fluorescence in remarkably lower fluorescence quantum yields ΦF as their polyethynylene motifs -(CC)n- expanded. The drastic decrease of fluorescence quantum yields ΦF were explained in terms of increasing nonradiative reaction rate constants knr, which had been determined by the corresponding fluorescence quantum yields ΦF and lifetime values τ. The emission underwent a large bathochromic shift in polar solvents because the charge-separated excited state is more stabilized than the ground state. Comparison of slope values ρ in Lippert/Mataga plot for the Ph2N and Ph2N/cyano-substituted phenylene-(poly)ethynylenes revealed that the latter underwent large change of dipole moments upon photo-excitation although highly expanded acetylenic π-systems with cyano group did little. 相似文献
78.
79.
80.
The 1,4-elimination reaction of 1-allyloxy-4-methoxy-(2Z)-alkenes with n-butyllithium is shown to proceed in a marked preference to the [2,3] Wittig rearrangement to afford the allylic (1Z,3E)-dienyl ethers in high stereoselectivities. The synthetic utility of this method is demonstrated by the Claisen rearrangement of the dienyl ethers thus obtained. 相似文献