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11.
Jana Mikulova Francois Gérard Danielle Mesnard Charles Kappenstein Daniel Duprez 《Journal of solid state chemistry》2006,179(8):2511-2520
CeO2 doped with praseodymium, neodymium and/or zirconium atoms were prepared by coprecipitation and by the sol-gel method. Structural properties were investigated by in situ XRD and Raman spectroscopy while oxygen storage capacity (OSC) was measured by transient CO oxidation. All the compounds, except pure Nd2O3, have a fluorite-type structure as well as a Raman band at 560 cm−1 characteristic of the oxygen vacancies involving non-stoichiometric oxides. The lattice parameter under hydrogen, being dependent on the temperature, revealed two reduction mechanisms: one at a low temperature at the surface and another at a high temperature in the bulk. Ce-Nd binary oxides show a strong tendency towards crystallite aggregation, which reduces accessibility to gases and OSC properties. Zirconium improves the thermal resistance to sintering of both Ce-Nd and Ce-Pr oxides. The Zr-Ce-Pr-O followed by Zr-Ce-Nd-O compounds displaying high oxygen mobility at a low temperature, appear to be very promising for practical applications such as OSC materials. 相似文献
12.
Thin layers of cellulose I nanocrystals were spin-coated onto silicon wafers to give a flat model cellulose surface. A mild heat treatment was required to stabilize the cellulose layer. Interactions of this surface with polyelectrolyte layers and multilayers were probed by atomic force microscopy in water and dilute salt solutions. Deflection–distance curves for standard silicon nitride tips were measured for silicon, cellulose-coated silicon, and for polyelectrolytes adsorbed on the cellulose surface. Transfer of polymer to the tip was checked by running deflection–distance curves against clean silicon. Deflection–distance curves were relatively insensitive to adsorbed polyelectrolyte, but salt addition caused transfer of cationic polyelectrolyte to the tip, and swelling of the polyelectrolyte multilayers. 相似文献
13.
A simple and fast method for phospholipid analysis was developed using high-performance liquid chromatography-mass spectrometry with an atmospheric pressure ionization interface. Separation of the phospholipid molecular species was achieved using a linear gradient of a mixture of chloroform-10 mM ammonium acetate-methanol (30:5:65) on a silica column. Optimization of the mass spectrometer conditions has allowed the method to separate and detect the phospholipids mainly as protonated molecular species. In comparison to existing LC-MS methods, improvement in the total analysis time and sensitivity were achieved. Separation of all major phospholipid molecular classes was achieved in less than 6 min. Marked improvement was observed in the linearity of the response of the phospholipids studied providing a linear response over three orders of magnitude. Data supporting the validation of this method for the characterization of major phospholipids molecular species are also presented. 相似文献
14.
Maria de Fátima V. Marques Danielle Ramos Juliana D. Rego 《European Polymer Journal》2004,40(11):2583-2589
Ethylene and different amounts of 1,7-octadiene were copolymerized using the metallocene catalyst system ethylidene-bis(fluorenyl) zirconium dichloride and methylaluminoxane (MAO) at both 50 and 90 °C. The catalyst activity has slightly increased with the addition of low amounts of the diene in relation to the homopolymerization of ethylene. The obtained polymers were characterized according to their melting temperature (Tm) and crystallinity degree (xc) by differential scanning calorimetry (DSC). Weight-average molecular weight (Mw) and polydispersity were determined by gel permeation chromatography (GPC). Diene contents in the copolymer were obtained through the FTIR spectroscopy. The results indicated that at polymerization temperature of 90 °C, crosslinking bonds in the obtained copolymers were low, differently from what was observed at 50 °C. The diene content in the copolymer achieved more than 3 mol% and the comonomer conversion was around 15%. Moreover, the obtained copolymers have Mw around 100,000 and large polydispersity. 相似文献
15.
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
16.
Slootweg JC Vlaar MJ Vugts DJ Eichelsheim T Merhai W de Kanter FJ Schakel M Ehlers AW Lutz M Spek AL Lammertsma K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(16):4808-4818
Reaction of the transient phosphinidene complexes R-P=W(CO)5 with N-substituted-diphenylketenimines leads unexpectedly to the novel 2-aminophosphindoles, as confirmed by an X-ray crystal structure determined for one of the derivatives. Experimental evidence for a methylene-azaphosphirane intermediate was found by using the iron-complexed phosphinidene iPr2N-P=Fe(CO)4, which affords the 2-aminophosphindole together with the novel methylene-2,3-dihydro-1H-benzo[1,3]azaphosphole. Analysis of the reaction pathways with DFT indicates that the initially formed methylene-azaphosphirane yields both phosphorus heterocycles by way of a [1,5]- or [1,3]-sigmatropic shift, respectively, followed by a H-shift. Strain underlies both rearrangements, which causes these remarkably selective conversions that can be tuned by changing the substituents. 相似文献
17.
Julie P. Harmon Sanboh Lee J. C. M. Li 《Journal of polymer science. Part A, Polymer chemistry》1987,25(12):3215-3229
The effect of cold work on the transport of liquid methanol in crosslinked PMMA disks has been determined at temperatures from 35–56°C. Deformed samples absorb at fast rates with kinetics that approach those of Fickian diffusion. Undeformed samples sorb at lower rates and the kinetics tend toward those of Case II transport. Shape recovery accompanied swelling in deformed samples. Samples saturated with methanol were desorbed in cyclohexanol. Resorption of desorbed samples showed fast rates for both deformed and undeformed samples and matched those of the absorption cycle in deformed samples. An analogy is made between the microstructure due to cold work and due to swelling. 相似文献
18.
A reversed-phase high-performance liquid chromatography/electrospray ionisation mass spectrometry (HPLC/ESI-MS) method has been developed to conclusively differentiate the epimers betamethasone and dexamethasone and various esterification products (betamethasone and dexamethasone 21-acetate, betamethasone and dexamethasone 21-phosphate, betamethasone 17-valerate, betamethasone 21-valerate and betamethasone 17,21-dipropionate) in counterfeit drugs. Good separation with baseline resolution of all epimers or isomers was obtained on a Zorbax Eclipse XDB or Luna C8 column, using a step gradient with mobile phases of 0.05 M ammonium acetate and acetonitrile. Betamethasones can also be distinguished by the relative abundance of their m/z 279 ion in the positive electrospray tandem mass spectra. The LC/MS or LC/MS/MS method developed was successfully applied to the analysis of drug product samples, i.e. creams and tablets. 相似文献
19.
Yutaka Morita Manfred Hesse Hans Schmid Avijit Banerji Julie Banerji Asima Chatterjee Willi E. Oberhnsli 《Helvetica chimica acta》1977,60(4):1419-1434
Alstonia scholaris: The structure of the indole alkaloid nareline Besides the known akuammidine, picralinal, picrinine and pseudoakuammigine a new indole alkaloid called nareline (M=352) was isolated from Alstonia scholaris R. BR. , which belongs to the plant family of Apocynaceae. Its structure 2 was deduced by single crystal X-ray diffraction. 2 represents the absolute configuration. The spectroscopic data of 2 and its derivatives (Scheme 1) as well as their chemical behavior support this structure. In biogenetic sense nareline is related to the bases akuammiline ( 4 ) and picraline ( 5 ) (Scheme 2). In contrast to those the C-atom 5 is exocyclic and represents an aldehyde group which forms together with the oxygen atom of the N (4)-hydroxylamine group a cyclic half acetale. - By oxidation (CrO3/CH3COOH) of 2 the oxindol derivative 19 (oxonareline) is formed which contains a cyclic acetal as a partial structure element (Scheme 4). 相似文献
20.
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