全文获取类型
收费全文 | 53篇 |
免费 | 3篇 |
国内免费 | 1篇 |
专业分类
化学 | 29篇 |
晶体学 | 3篇 |
力学 | 4篇 |
数学 | 8篇 |
物理学 | 13篇 |
出版年
2022年 | 1篇 |
2021年 | 1篇 |
2019年 | 2篇 |
2016年 | 1篇 |
2015年 | 1篇 |
2014年 | 3篇 |
2013年 | 5篇 |
2012年 | 5篇 |
2011年 | 1篇 |
2010年 | 3篇 |
2009年 | 3篇 |
2008年 | 2篇 |
2007年 | 2篇 |
2006年 | 4篇 |
2005年 | 2篇 |
2004年 | 2篇 |
2003年 | 1篇 |
2002年 | 5篇 |
2001年 | 1篇 |
2000年 | 1篇 |
1998年 | 1篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1991年 | 2篇 |
1984年 | 1篇 |
1980年 | 1篇 |
1978年 | 1篇 |
1971年 | 1篇 |
1966年 | 1篇 |
1965年 | 1篇 |
排序方式: 共有57条查询结果,搜索用时 31 毫秒
1.
Wnuk SF Companioni DR Neschadimenko V Robins MJ 《The Journal of organic chemistry》2002,67(25):8794-8797
Stereoselective pyramidalization of free radicals by a vicinal fluorine substituent, the beta-fluorine effect, was invoked to rationalize a 77:23 anti/syn ratio of 2-deuterio-1-fluorocyclopentanes obtained by radical reduction of trans-2-fluoro-1-bromocyclopentane with tributyltin deuteride (Dolbier, W. R., Jr.; Bartberger, M. D. J. Org. Chem. 1995, 60, 4984-4985). We have evaluated analogous reductions of the four possible stereoisomers of some adenine 2'(3')-fluoro-3'(2')-O-phenoxythiocarbonyl nucleoside derivatives. In all cases, the steric effect of adenine on the beta face directs deuterium transfer from the stannane to C2'(C3') on the alpha face of the furanose ring. However, the beta-fluorine effect enhances ratios of deuterium transfer anti to the vicinal fluorine substituent. 相似文献
2.
Treatment of ethyl 2-(pyridin-2-ylsulfonyl)hexanoate with tributylstannane and azobis(2-methyl-2-propanitrile) (AIBN) in benzene at reflux for 36 h resulted in hydrogenolysis to give ethyl hexanoate (60%), whereas no reaction was observed after 48 h at reflux with ethyl 2-(phenylsulfonyl)hexanoate. Ethyl 2-(pyrimidin-2-ylsulfonyl)hexanoate underwent quantitative hydrogenolysis within 1 h under these conditions. This represents a mild new methodology for removal of the synthetically useful sulfone moiety. Substitution of Bu(3)SnD for Bu(3)SnH gave access to alpha-deuterium-labeled esters. Treatment of the alpha-(pyrimidin-2-ylsulfonyl) enolates derived from several esters with Selectfluor gave high yields of the 2-fluoro-2-(pyrimidin-2-ylsulfonyl)alkanoates, which were smoothly desulfonylated [Bu(3)SnH (2 equiv)/AIBN/benzene/Delta] to give 2-fluoroalkanoates. "Catalytic" tin hydride, generated from tribuytltin chloride (0.15 equiv) and excess polymethylhydrosiloxane in the presence of potassium fluoride, also effected removal of the pi-deficient alpha-(pyrimidin-2-ylsulfonyl) moiety from acid derivatives in high yields. Desulfonylation is suggested to proceed via alkoxy ketyl-type radicals and tin enolates. 相似文献
3.
Thermolysis of a 2'-[(16)O]-O-benzoyl-[(17)O]-5'-O-(tert-butyldimethylsilyl)-O(2),3'-cyclouridine derivative gave the more stable 3'-[(17)O]-O-benzoyl-[(16)O]- 5'-O-(tert-butyldimethylsilyl)-O(2),2'-cyclouridine isomer, which was converted into 3'-[(17)O]-2'-azido-2'-deoxyuridine by deprotection and nucleophilic ring opening at C2' with lithium azide. The 5'-diphosphate was prepared by nucleophilic displacement of the 5'-O-tosyl group with tris(tetrabutylammonium) hydrogen pyrophosphate. Model reactions gave (16)O and (18)O isotopomers, and base-promoted hydrolysis of an O(2),2'-cyclonucleoside gave stereodefined access to 3'-[(18)O]-1-(beta-D-arabinofuranosyl)uracil. Inactivation of ribonucleoside diphosphate reductase with 2'-azido-2'-deoxynucleotides results in appearance of EPR signals for a nitrogen-centered radical derived from azide, and 3'-[(17)O]-2'-azido-2'-deoxyuridine 5'-diphosphate provides an isotopomer to perturb EPR spectra in a predictable manner. 相似文献
4.
Dental calculus analysis can be a valuable source of archaeological knowledge, since it preserves not only microbial and host biomolecules but also dietary and environmental debris, as well as metabolic products likely originating from dietary and craft activities. Here we described GC-MS analysis of a set of historic dental calculus samples from the front teeth of the mandibles of seven individuals found in 17th- and 18th-century graves in the city of Rzeszow, located in South-eastern Poland. We have found that only saturated fatty acids, which are characteristic for fats of animal origin, were present in the tested samples. Our preliminary results indicate that the diet of modern-period inhabitants of Rzeszow was rich in animal products, such as meat and dairy products. 相似文献
5.
A. Wnuk M. Kaczkan R. Piramidowicz R. Mahiou G. Bertrand M.-F. Joubert 《辐射效应与固体损伤》2013,168(1-6):469-473
The dynamics of up-conversion, green emission under excitation at different infra-red wavelength in Ho3? doped ZBLAN fiber is reported. Under infrared, 890 nm quasi cw pumping the complicated temporal behavior of the up-conversion signal is strongly influenced by the intermediate 5I5 state cross relaxation. The mechanisms of the observed up-conversion processes are proposed and the time evolution of the 5S2 population is described by the rate equation model. Parameters of the model are determined and numerical simulations of the excited state dynamics are performed. 相似文献
6.
7.
8.
The paper is devoted to a question if the Levi property is preserved by direct sums and quotients. The three-space problem for the Levi and Lebesgue properties in topological Riesz spaces is also investigated. 相似文献
9.
Basic concept underlying Griffith’s theory of fracture of solids was that, similar to liquids, solids possess surface energy and, in order to propagate a crack by increasing its surface area, the corresponding surface energy must be compensated through the externally added or internally released energy. This assumption works well for brittle solids, but is not sufficient for quasi-brittle and ductile solids. Some new forms of energy components must be incorporated into the energy balance equation, from which the input of energy needed to propagate the crack and subsequently the stress at the onset of fracture can be determined. The additional energy that significantly dominates over the surface energy is the irreversible energy dissipated by the way of the plastic strains that precede the leading edge of a moving crack. For stationary cracks the additional terms within the energy balance equation were introduced by Irwin and Orowan. An extension of these concepts is found in the experimental work of V. Panin, who has shown that the irreversible deformation is primarily confined to the prefracture zones associated with a stationary or a slowly growing crack. The present study is based on the structured cohesive crack model equipped with the “unit step growth” or “fracture quantum”. This model is capable to encompass all the essential issues such as stability of subcritical cracks, quantization of the fracture process and fractal geometry of crack surfaces, and incorporate them into one consistent theoretical representation. 相似文献
10.
Dr. Long Zhao Dr. Bo Xu Dr. Utuq Ablikim Dr. Wenchao Lu Dr. Musahid Ahmed Mikhail M. Evseev Prof. Dr. Eugene K. Bashkirov Prof. Dr. Valeriy N. Azyazov A. Hasan Howlader Prof. Dr. Stanislaw F. Wnuk Prof. Dr. Alexander M. Mebel Prof. Dr. Ralf I. Kaiser 《Chemphyschem》2019,20(6):791-797
For the last decades, the hydrogen-abstraction−acetylene-addition (HACA) mechanism has been widely invoked to rationalize the high-temperature synthesis of PAHs as detected in carbonaceous meteorites (CM) and proposed to exist in the interstellar medium (ISM). By unravelling the chemistry of the 9-phenanthrenyl radical ([C14H9].) with vinylacetylene (C4H4), we present the first compelling evidence of a barrier-less pathway leading to a prototype tetracyclic PAH – triphenylene (C18H12) – via an unconventional hydrogen abstraction–vinylacetylene addition (HAVA) mechanism operational at temperatures as low as 10 K. The barrier-less, exoergic nature of the reaction reveals HAVA as a versatile reaction mechanism that may drive molecular mass growth processes to PAHs and even two-dimensional, graphene-type nanostructures in cold environments in deep space thus leading to a better understanding of the carbon chemistry in our universe through the untangling of elementary reactions on the most fundamental level. 相似文献