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排序方式: 共有502条查询结果,搜索用时 15 毫秒
1.
2.
Danielle Mesnard Jean-Paul Charpentier Léone Miginiac 《Journal of organometallic chemistry》1981,214(2):135-143
Organolithium, organomagnesium and organozinc compounds react with α,α'-difunctional enynes: HOCH2CCCHCHCH2Y (Y OH, OCH3, N(CH3)2). This reaction produces one or two derivatives, according to the nature of the metallic group: mono- or di-functional allenes, mono- or di-functional dienes. 相似文献
3.
Photophysics of monodisperse platinum-acetylide oligomers: delocalization in the singlet and triplet excited states 总被引:1,自引:0,他引:1
Liu Y Jiang S Glusac K Powell DH Anderson DF Schanze KS 《Journal of the American Chemical Society》2002,124(42):12412-12413
A series of monodisperse Pt-acetylide polymers that contain the [-CC-(p-C6H4)-CC-(t-Pt(PBu3)2)-]n repeat unit has been prepared for n = 1, 2, 3, 4, 5, and 7. The photophysical properties of the series provide information concerning the relationship between the oligomer length and delocalization in the singlet and triplet excited states of the pi-conjugated electron system. The results imply that the singlet excited state is delocalized over approximately 6 repeat units; however, the triplet state is considerably more localized. The triplet energy is almost invariant with oligomer length, but the phosphorescence spectra and triplet nonradiative decay rates indicate that the electron-vibrational coupling in the triplet state decreases with increasing oligomer length. 相似文献
4.
Florence Robaut Alexandre Crisci Madeleine Durand-Charre Danielle Jouanne 《Microscopy and microanalysis》2006,12(4):331-334
The carbon contents in carburized steels were investigated by electron probe microanalysis (EPMA) for a range of carbon levels in the solid solution less than 1 wt%. This article describes the difficulties encountered with the classic analytical procedure using the k ratio of X-ray intensities and the phi(rhoz) model. Here, a suitable calibration curve method is presented with emphasis on the metallographic study of standard specimens and on the carbon decontamination of samples. 相似文献
5.
Benzylic fluorides, as well as five-membered heterocycles, have been obtained in high ee’s through cycloaddition reactions starting from easily accessible optically active propargylic fluorides. 相似文献
6.
Vugts DJ Jansen H Schmitz RF de Kanter FJ Orru RV 《Chemical communications (Cambridge, England)》2003,(20):2594-2595
In a multi-component reaction (MCR) of a phosphonate, nitriles, aldehydes and isocyanates, N3-functionalised dihydropyrimidines can be synthesised efficiently via a Horner-Emmons/aza Diels-Alder pathway. 相似文献
7.
Star-shaped azo-based dipolar chromophores: design, synthesis, matrix compatibility, and electro-optic activity 总被引:1,自引:0,他引:1
Gopalan P Katz HE McGee DJ Erben C Zielinski T Bousquet D Muller D Grazul J Olsson Y 《Journal of the American Chemical Society》2004,126(6):1741-1747
Three new azo-benzene-based push-pull chromophores with dendritic architecture were synthesized as active materials for electro-optic applications. These chromophores were synthesized in six or seven synthetic steps with an overall yield of around 80% per step and high purity. UV-vis spectroscopy showed significant influence of the transient dipole moment on the observed r(33) values. The chromophores were stable to photochemical oxidation in ambient light and air. The electrical poling conditions were optimized for each chromophore as the T(g) of the composite material varied significantly. The highest EO coefficient achieved was 22-25 pm/V at 1550 nm wavelength. STEM analysis of the blends enabled the correlation of the activity of these large chromophores with the blend morphology. An amorphous polycarbonate host effectively disperses the chromophores in 2-20 nm aggregates in the active materials. However, macrophase separation into 200-500 nm aggregates was observed in a methacrylate host matrix. 相似文献
8.
Buck SB Hardouin C Ichikawa S Soenen DR Gauss CM Hwang I Swingle MR Bonness KM Honkanen RE Boger DL 《Journal of the American Chemical Society》2003,125(51):15694-15695
Key derivatives and analogues of fostriecin were prepared and examined that revealed a fundamental role for the unsaturated lactone and confirmed the essential nature of the phosphate monoester. Thus, an identical 200-fold reduction in protein phosphatase 2A (PP2A) inhibition is observed with either the saturated lactone (7) or with an analogue that lacks the entire lactone (15). This 200-fold increase in PP2A inhibition attributable to the unsaturated lactone potentially may be due to reversible C269 alkylation within the PP beta12-beta13 active site loop accounting for PP2A/4 potency and selectivity. 相似文献
9.
The mass spectra of aliphatic aldehydes which contain a cyclopropane group included in the polymethylenic chain, in some instances, show two intense peaks, called A and B that are not encountered either in other cyclopropane-containing aliphatic compounds or in other aliphatic aldehydes. The intensity of peaks A and B is strictly dependent upon the distance between cyclopropane and aldehyde. When the number x of methylene groups between the two functions is equal to 4 or higher than 10, peaks A and B are intense, but when x is equal to 7, the peaks are small.Specific labelling shows that ion A contains the atoms of the cyclopropane ring, the polymethylenic chain between the two functions and the aldehyde function. Ion B also contains the aldehyde function and results from the expulsion of the polymethylenic interfunctional chain to which a hydrogen atom of the other part of the molecule is added. This hydrogen atom arises, to an extent of about 60%, from the methylene of the cyclopropane ring. A mechanism is proposed in which cyclization of the molecular ion occurs; ion A is obtained by direct α-cleavage to the ether function in the cyclic ion; ion B results from alternative ether-cleavage causing opening of the carbo-ring. One hydrogen from the cyclopropane ring is transferred leading to the elimination of the interfunctional chain.The fact that formulas of ions A and B correspond to [CnH2n-3O]+ and that their intensities are dependent of x make questionable any structural determination established only by mass spectral examination of cyclopropane aldehydes. 相似文献
10.
Danielle Giron S. Monnier M. Mutz P. Piechon T. Buser F. Stowasser K. Schulze M. Bellus 《Journal of Thermal Analysis and Calorimetry》2007,89(3):729-743
Adequate very sensitive quantification methods are needed for the development and are also now required for the monitoring
of undesirable solid form(s) as routine tests. The pre-requisite for quantitation are selectivity, sensitivity and most important
the purity of standards and their proper storage, what is a challenge for metastable forms.
Several analytical techniques are available such as X-ray diffraction, spectroscopy, thermal analysis and microcalorimetry.
The different steps of the validation of the analytical methods and problems to be solved are discussed. Examples illustrate
the different techniques and compare their possible advantages and limits. The relative standard deviation of measurements
should allow for checking the homogenization procedure of mixtures for calibration. The validation should be carried out following
ICH guidelines for validation of analytical methods. Comparison of different techniques in adequate concentration range add
confidence in the analytical results. 相似文献