全文获取类型
收费全文 | 84篇 |
免费 | 0篇 |
专业分类
化学 | 45篇 |
力学 | 1篇 |
数学 | 22篇 |
物理学 | 16篇 |
出版年
2020年 | 1篇 |
2016年 | 1篇 |
2014年 | 1篇 |
2013年 | 2篇 |
2011年 | 1篇 |
2009年 | 1篇 |
2008年 | 2篇 |
2007年 | 1篇 |
2006年 | 2篇 |
2005年 | 1篇 |
2004年 | 2篇 |
2003年 | 1篇 |
2002年 | 1篇 |
2001年 | 2篇 |
2000年 | 3篇 |
1998年 | 2篇 |
1997年 | 3篇 |
1996年 | 2篇 |
1995年 | 2篇 |
1994年 | 3篇 |
1993年 | 5篇 |
1992年 | 1篇 |
1991年 | 2篇 |
1990年 | 1篇 |
1988年 | 2篇 |
1985年 | 2篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1981年 | 9篇 |
1980年 | 4篇 |
1978年 | 3篇 |
1977年 | 1篇 |
1976年 | 3篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1973年 | 1篇 |
1972年 | 4篇 |
1971年 | 2篇 |
1969年 | 1篇 |
1967年 | 2篇 |
排序方式: 共有84条查询结果,搜索用时 31 毫秒
1.
The isomerization of 1,2-epcxycyclopentane ( 1 ) to enantiomerically enriched (R)-cyclopent-2-enol ( 2 ) in protic solvents is catalyzed by cob(I)alamin. The enantiomeric excess (e.e.) of (R)- 2 is usually ca. 60%; it is only slightly dependent on the temperature, but increases with decreasing dielectric constant ε of the solvent. Standard kinetic methods show the reaction to be first order in vitamin B12 and zero order in 1 . The rate constant increases exponentially with increasing ε of the solvent. An Arrhenius plot at ε = 40 gives activation parameters ΔH≠ = 78 ± 4 kJ·mol?1 and ΔS≠ = ?49 ± 1 J·mol?1·K?1. The isomerization 1 → 2 proceeds in two steps (Schemes 2 and 7): (i) The epoxide ring is first opened by the proton-assisted fast and irreversible nucleophilic attack of the chiral CoI catalyst to form diastereoisomeric (1R,2R)- and (1S,2S)-(2-hydroxycyclo-pentyl)cob(III)alamins 6 in a ratio of ca. 4:1 which are the dominant species in the steady state; (ii) The intermediates 6 then decompose in the rate-limiting step to form 2 and recycled catalyst. Experiments with specifically 2H-labeled 1 showed the hydro-cobalt elimination 6 → 2 to be non-stereoselective. It proceeds via reversible Co? C bond homolysis to a free 2-hydroxycyclopentyl radical from which stereoelectronically controlled H-abstraction by Co11 takes place. 相似文献
2.
R. Scheffold 《Helvetica chimica acta》1967,50(5):1419-1422
For a number of nucleophiles L an approximate linear correlation between the logarithms of the stability constants of methylmercury-complexes of L and the nuclear spin-spin-coupling constants J of Ch3HgL was found. 相似文献
3.
Enantioselective Reactions on Porphine Type Nickel Complexes The thermodynamically controlled addition of alcohols to (+)-(1R)-[1-methyl-8H-HDP]nickelperchlorate ( 1 ; e.e. 92%) yields exclusively the corresponding cis-1,11-disubstituted porphinoids. Chemical transformation of functional groups in the alkoxy side-chain of the chiral addition product followed by acid catalyzed elimination yields the derived alcohols and 1 . By this procedure, the following enantioselective transformations were studied: methylation of meso-2,3-butandiol ( 5 ) to (+)-(2R,3S)-3-methoxy-2-butanol ( 8a ; e.e. 87%), diimide reduction of 2-ethylallyl alcohol ( 9 ) to (+)-(2R)-2-methyl-1-butanol ( 12a ; e.e. 15%), and hydride reduction of 4-hydroxy-2-butanone ( 13 ) to (+)-(3S)-1,3-butandiol ( 16a ; e.e. 20%). Addition of 2,2-dimethyl-1,3-propandiol ( 17 ) to 4 , followed by esterification of the free hydroxy group with trifluoromethanesulfonic anhydride and solvolysis of the sulfonate 19 yielded a bridged complex with unrearranged alkyl chain for which structure 20 is proposed. 相似文献
4.
Vitamin-B12-Catalyzed C, C-Bond Formation: Synthesis of Jasmonates via Sequential Radical Reaction The Cbl-catalyzed electroreduction of 3-(2′-bromo-1′-ethoxyethoxy)cyclopenten ( 1a ) in presence of 1-cyanovinyl-acetate ( 8 ) gave, in a sequential radical reaction (5-exo-trig-cyclization of 1a followed by addition to 8 ), 1-cyano-2-(2′-ethoxy-hexahydro-2′H-cyclopenta[b] furan-4′-yl)ethyl acetate ( 10a ). This intermediate was transformed to methyl jasmonate ( 7 ; four steps) and epituberolide ( 9 ; three steps) in 20 and 31% yield, respectively, from cyclopent-2-en-l-ol. 相似文献
5.
The method of linear frequency modulation of a continuous wave (FM-CW) in sound-echo experiments is demonstrated at a sound frequency of 70 GHz. A reflex klystron with a cw power of only 300 mW and a planar Hertzian resonator are used for the piezoelectric sound excitation. Applying homodyne detection, spectral echo signals are detected in the kHz range by means of a spectral analyzer. The detected echoes show an excellent signal-to-noise ratio. Details of the experimental setup and the underlying theory of the FM-CW sound experiments are presented. We observe experimentally two excited needle-like sound beams in 65 m distance, each about 30 m in diameter. 相似文献
6.
(–)-Carbovir ((–)- 1 ) was synthesized via the cyclic carbonate 2 in four steps starting from enantiomerically enriched (–)-(S)-(cyclopent-2-enyl)methanol ((–)- 3 ). 相似文献
7.
On the Mechanism of Sequential Radical Cyclization of (Bromomethyl)silyl Ethers of Terpernoid Alcohols The cyclic products of the Bu3SnH-promoted radical reaction of (E)-1-[(bromomethyl)dimethylsilyloxy]-2-methylhept-2-ene ( 6 ) consists to 98% of a 1:2 mixture of (±)-(4RS,5RS)- and (±)-(4-RS,5SR)-4-butyl-2,2,5-trimethyl-1-oxa-2-silacyclohexane ( 8a and 8b , respectively). It is, therefore, concluded that the 6-‘endo’→5-‘exo’ tandem cyclization of the 5-mehtyl-3-oxa-2-siladeca-5,9-dien-l-yl radical (reaction 1 → 2 ) is not necessarily a concerted process, but may be explained as a sequence of individual steps via free-radical intermediates. 相似文献
8.
Cindy Strehl Timo Gaber Manuela Jakstadt Martin Hahne Paula Hoff Cornelia M. Spies Alexander Scheffold Gerd-Rüdiger Burmester Frank Buttgereit 《Journal of fluorescence》2013,23(3):509-518
Flow cytometry has become a widely-used and powerful tool for the characterization of cells according to their expression of specific proteins. However, sensitivity of this method is still limited since conventionally labeled antibodies can be conjugated with at maximum 1–10 dye molecules. This fact resulted in the need to develop new techniques in order to identify molecules which are expressed in very low but functionally relevant amounts. In the past, we have successfully used a liposome-based high-sensitivity immunofluorescence technique to measure the expression of low abundant membrane bound glucocorticoid receptors (mGR) on different cell types. The use of this technique allows the detection of as few as 50–100 antigen molecules per cell which is due to a 100-fold to 1000-fold increase in fluorescence signal intensity compared with conventional methods. The higher sensitivity is achieved since thousands of dye molecules can be enclosed in liposomes. Another modern high-sensitivity immunofluorescence staining method is the purchasable Fluorescence Amplification by Sequential Employment of Reagents (FASER) procedure. Here, we aimed at comparing sensitivity and specificity of these two techniques for the detection of the mGR. Our data demonstrate the FASER technique to be more sensitive and also more specific for the detection of mGR as compared to the liposome technique. However, both methods have advantages and disadvantages which are discussed in detail. 相似文献
9.
10.