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71.
The use of 4.2 nm gold nanoparticles wrapped in an adsorbates shell and embedded in a TiO2 metal oxide matrix gives the opportunity to investigate ultrafast electron-electron scattering dynamics in combination with electronic surface phenomena via the surface plasmon lifetimes. These gold nanoparticles (NPs) exhibit a large nonclassical broadening of the surface plasmon band, which is attributed to a chemical interface damping. The acceleration of the loss of surface plasmon phase coherence indicates that the energy and the momentum of the collective electrons can be dissipated into electronic affinity levels of adsorbates. As a result of the preparation process, gold NPs are wrapped in a shell of sulfate compounds that gives rise to a large density of interfacial molecules confined between Au and TiO2, as revealed by Fourier-transform-infrared spectroscopy. A detailed analysis of the transient absorption spectra obtained by broadband femtosecond transient absorption spectroscopy allows separating electron-electron and electron-phonon interaction. Internal thermalization times (electron-electron scattering) are determined by probing the decay of nascent nonthermal electrons (NNEs) and the build-up of the Fermi-Dirac electron distribution, giving time constants of 540 to 760 fs at 0.42 and 0.34 eV from the Fermi level, respectively. Comparison with literature data reveals that lifetimes of NNEs measured for these small gold NPs are more than four times longer than for silver NPs with similar sizes. The surprisingly long internal thermalization time is attributed to an additional decay mechanism (besides the classical e-e scattering) for the energy loss of NNEs, identified as the ultrafast chemical interface scattering process. NNEs experience an inelastic resonant scattering process into unoccupied electronic states of adsorbates, that directly act as an efficient heat bath, via the excitation of molecular vibrational modes. The two-temperature model is no longer valid for this system because of (i) the temporal overlap between the internal and external thermalization process is very important; (ii) a part of the photonic energy is directly transferred toward the adsorbates (not among "cold" conduction band electrons). These findings have important consequence for femtochemistry on metal surfaces since they show that reactions can be initiated by nascent nonthermal electrons (as photoexcited, out of a Fermi-Dirac distribution) besides of the hot electron gas. 相似文献
72.
A generalized fractional programming problem is specified as a nonlinear program where a nonlinear function defined as the maximum over several ratios of functions is to be minimized on a feasible domain of
n
. The purpose of this paper is to outline basic approaches and basic types of algorithms available to deal with this problem and to review their convergence analysis. The conclusion includes results and comments on the numerical efficiency of these algorithms.This research was supported by NSERC (grant A8312) and Cooperation franco-québécoise (projet 20-02-13). Paper presented at Workshop on Mathematical Programming Catholic University of Rio de Janeiro, Brazil, October 10–14, 1988. 相似文献
73.
Dr. Jean-Pierre Kahane 《Monatshefte für Mathematik》1982,93(4):289-292
Given a non-empty closed subsetF of the unit circle |z|=1, and a Möbius transformationM(z) of the unit disc |z|1, such thatM(0)0, there exists a functionf(z) holomorphic in the unit disc,F being the singular set at the boundary, whose Taylor coefficients tend to zero while the Taylor coefficients off(M(z)), do not tend to zero. 相似文献
74.
Pascal Brunerie Jean-Pierre Clrier Huguette Petit Grard Lhommet 《Journal of heterocyclic chemistry》1986,23(4):1183-1188
The reaction of acyl chlorides with cyclic five-membered β-enaminoesters gave exclusively N-acylated products while reaction of acyl chlorides with cyclic seven-membered β-enaminoesters gave only C-acylated products. In the case of cyclic six-membered β-enaminoesters, the reaction of acyl chlorides gave a mixture of N-acylated and C-acylated products. 相似文献
75.
Use of gel-permeation chromatography in the determination of the composition of two-polymer mixtures
Jean-Pierre Menin Ren Roux 《Journal of polymer science. Part A, Polymer chemistry》1972,10(3):855-866
The possibility of evaluating with acceptable accuracy the composition of a two-polymer mixture which is well separated by GPC, was studied by using mixtures of high molecular weight polybutadiene (M?w = 4.5 × 105) and low molecular weight polyiso-butylene (M?n in the range of 103). It was concluded that a satisfactory evaluation of the composition of a polymer mixture can be achieved, provided that the variations of the refractive index with the molecular weight are taken into account for the low molecular weight polymer (the polyisobutylene). 相似文献
76.
Herv Bouchard Jean-Pierre Pulicani Marc Vuilhorgne Jean-Dominique Bourzat Alain Commer on 《Tetrahedron letters》1994,35(52):9713-9716
A new route to semisynthetic 19-nor-7β, 8β-methylene taxoids, such as compound 8, from the 7-O-trifluoromethanesulfonyl derivative 6 is reported. Evidence for a dissociation of the triflate to form a carbocation at C-7 under the reaction conditions is presented. Electrochemical reduction of the cyclopropane taxoid 8 gives, besides the expected 10-dehydroxy-cyclopropane analog 10, the 7-membered C-ring derivative 11. 相似文献
77.
Siham El FangourAlexandre Guy Jean-Pierre VidalJean-Claude Rossi Thierry Durand 《Tetrahedron letters》2003,44(10):2105-2108
The first synthesis of the two enantiomers of phytoprostane F1 methyl ester 1 and 2 is described using the syn-anti-syn alcoxy ester 3 as starting material. 相似文献
78.
Leclaire J Dagiral R Fery-Forgues S Coppel Y Donnadieu B Caminade AM Majoral JP 《Journal of the American Chemical Society》2005,127(45):15762-15770
The synthesis of a new family of phosphorus dendrimers built from an octasubstituted metal-free phthalocyanine core is described up to generation 5. This core is used as a sensor and a probe for analyzing the properties of the internal structure and the influence of each structural part (core, branches, surface) upon the whole structure. UV-visible spectra show both a hyperchromic and bathochromic effect on the Q-bands with increasing generation, indicating that the chromophore is more isolated, and that the dendritic shell mimics a highly polar solvent. There is no evidence for aggregation, except for generation 0, showing again the isolation of the core. However, the dendritic shell is permeable to aqueous acids and bases, as demonstrated by the reversible splitting of the Q-band in an acidic medium (neutral form of the phthalocyanine) and the single Q-band in a basic medium (dianionic form), even for generation 4. The fluorescence quantum yield for the neutral form increases with increasing generation. The dianionic form of generation 0 is poorly fluorescent, whereas generations 3 and 4 (G3 and G4) exhibit better fluorescence. The cores of G3 and G4 are highly sensitive optical sensors for H3O+ and OH-. These experiments are carried out in THF/water mixtures, and the influence of water on the structure has been checked. The hydrodynamic radius of generation 4 is measured by NMR diffusion (pulse gradient spin-echo) experiments. R(H) varies from 35.4 A at 4 mol % of water to 32.5 A at 64 mol % of water in THF, indicating the hydrophobic nature of these dendrimers. 相似文献
79.
Anne-Marie Caminade Jean-Pierre Majoral Valérie Maraval Rosa-Maria Sebastián 《Phosphorus, sulfur, and silicon and the related elements》2013,188(6-7):1493-1497
Several series of phosphorus-containing dendrimers have been designed to study the variation of their properties, depending on the type, the location (surface, branches, core, and cavities), and the number of functions implied. 相似文献
80.
Foaming constitutes one of the most important industrial activities in polymer engineering to produce efficient thermal insulating materials. In particular, rigid insulating boards are produced worldwide on a large scale using blowing agents which eventually are released in the environment where they adversely impact the natural friendly stratospheric ozone layer. Concomitantly, the chemicals used as blowing agents contribute to the creation of the unfriendly tropospheric ozone layer generating the disastrous green house effect around our planet. The traditional foaming intermediates currently named freons, like chlorofluorocarbons (CFCs) currently used as blowing agents as well as the hydrochlorofluorocarbons (HCFCs) often considered as alternative blowing agents, must be banned from industrial processes and new (friendly) foaming agents have to be suggested and evaluated in terms of both easy engineering and environmental neutrality. Undoubtedly thermodynamics plays a major role in assessing the effective capability of those chemicals. Some CFCs still accepted and other possible simple gases like carbon dioxide and nitrogen have been considered. The in-depth thermodynamic investigation has been made possible thanks to new experimental developments to determine gas solubility in polymers and associated swelling as well as the thermodynamic properties of (gas + polymer) systems, including the thermophysical properties of polymers under gas sorption. Pertinent data have been generated for such properties over extended T and p ranges. 相似文献