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11.
Johann Guilleminot Christian Soize Djimedo Kondo Christophe Binetruy 《International Journal of Solids and Structures》2008,45(21):5567-5583
Many engineering materials exhibit fluctuations and uncertainties on their macroscopic mechanical properties. This randomness results from random fluctuations observed at a lower scale, especially at the meso-scale where microstructural uncertainties generally occur. In the present paper, we first propose a complete theoretical stochastic framework (that is, a relevant probabilistic model as well as a non-intrusive stochastic solver) in which the volume fraction at the microscale is modelled as a random field whose statistical reduction is performed using a Karhunen–Loeve expansion. Then, an experimental procedure dedicated to the identification of the parameters involved in the probabilistic model is presented and relies on a non-destructive ultrasonic method. The combination of the experimental results with a micromechanical analysis provides realizations of the volume fraction random field. In particular, it is shown that the volume fraction can be modelled by a homogeneous random field whose spatial correlation lengths are determined and may provide conditions on the size of the meso-volumes to be considered. 相似文献
12.
The syntheses of two rigid organic molecular rods bearing a nitronyl-nitroxide radical and a terminal nitrogen-based functionality like a pyridine or a cyano group are reported. Both new paramagnetic molecules are fully characterized, including crystal structure analysis. Furthermore their magnetic behaviours in the crystalline state are investigated and their spin concentration corroborate their excellent purity. While the pyridine functionalized rod is synthesized by converting the corresponding benzaldehyde to the phenyl-nitronyl-nitroxide radical, the synthesis of the cyano functionalized rod demonstrates the accessibility of highly sophisticated spin-labelled molecules via cross-coupling reaction with a meta-iodo-phenyl-nitronyl-nitroxide moiety. 相似文献
13.
14.
We consider some boundary value problems in self-similar ramified domains, with Laplace and Helmholtz equations. We discuss transparent boundary conditions. These conditions permit computing the restriction of the solutions to domains obtained by stopping the geometric construction after a finite number of steps. To cite this article: Y. Achdou et al., C. R. Acad. Sci. Paris, Ser. I 342 (2006). 相似文献
15.
Christophe Cuny 《Journal of multivariate analysis》2006,97(8):1842-1869
Let (Xm,n)(m,n)∈Z2 be a Cp-valued wide sense stationary process. We study the prediction theory of such processes according to different total orders on Z2. In the case of a “rational order”, we give the spectral distribution of the resulting evanescent component and prove that for two different rational orders, the resulting evanescent components are mutually orthogonal. 相似文献
16.
[structure: see text] 2,6-Disubstituted pyridines, 6-substituted 2,2'-bipyridines, and 6,6'-disubstituted 2,2'-bipyridines are readily prepared under mild conditions from 5-(dimethylamino)-1-naphthalenesulfonamide chloride (DANS-Cl) and chloromethyl-nitronyl nitroxide (CH(2)Cl-NIT) starting materials and adequately functionalized building blocks. The syntheses of the pyridine molecules bearing two radicals and a DANS fragment first required the attachment of the aliphatic radical onto an aldehyde-protected dansylated compound, followed by the construction of the second aromatic radical. 相似文献
17.
Christophe Curty Norbert Engel Jos Iturraspe Albert Gossauer 《Photochemistry and photobiology》1995,61(6):552-556
Photooxygenation of (pyropheophorbidato a methyl ester)cadmium (II) was studied using 18,18O2 labeling of the molecular oxygen required for cleavage of the macrocycle. After reductive demetallation of the primary oxidation product (4,5-dioxo-4,5-secopyropheophorbidato a methyl ester)cadmium (II), the isotope content of formylbilinone 4a was analyzed by repeated-scan fast atom bombardment mass spectrometry. Comparison of the spectroscopic data of the labeled pigment 4a with the statistical probabilities of18 O isotope incorporation calculated for four possible reaction mechanisms clearly proves that photooxidative ring cleavage occurred by the one-molecule mechanism, i.e. the terminal oxygen atoms of 4a were derived from one oxygen molecule. Furthermore, a study of the exchange of the18 O-labeled atoms revealed that no exchange occurs within the pH 4.5–9.5 range. In stronger alkaline or acidic solutions, only the oxygen atom of the formyl group is exchanged. Hydrolysis of the methyl ester group of 4a was achieved, without loss of the18 O label on the formyl group, at pH 7.2 in the presence of pig liver esterase. 相似文献
18.
Wu T Froeyen M Kempeneers V Pannecouque C Wang J Busson R De Clercq E Herdewijn P 《Journal of the American Chemical Society》2005,127(14):5056-5065
19.
Schmitt C da Silva TP Bovay C Rami-Shojaei S Frossard P Kolodziejczyk E Leser ME 《Langmuir : the ACS journal of surfaces and colloids》2005,21(17):7786-7795
The electrostatic complexation between beta-lactoglobulin and acacia gum was investigated at pH 4.2 and 25 degrees C. The binding isotherm revealed a spontaneous exothermic reaction, leading to a DeltaHobs = -2108 kJ mol(-1) and a saturation protein to polysaccharide weight mixing ratio of 2:1. Soluble electrostatic complexes formed in these conditions were characterized by a hydrodynamic diameter of 119 +/- 0.6 nm and a polydispersity index of 0.097. The effect of time on the interfacial and foaming properties of these soluble complexes was investigated at a concentration of 0.1 wt % at two different times after mixing (4 min, referred as t approximately 0 h and t = 24 h). At t approximately 0 h, the mixture is mainly made of aggregating soluble electrostatic complexes, whereas after 24 h these complexes have already insolubilize to form liquid coacervates. The surface elasticity, viscosity and phase angle obtained at low frequency (0.01 Hz) using oscillating bubble tensiometry revealed higher fluidity and less rigidity in the film formed at t approximately 0 h. This observation was confirmed by diminishing bubble experiments coupled with microscopy of the thin film. It was thicker, more homogeneous and contained more water at t approximately 0 h as compared to t = 24 h (thinner film, less water). This led to very different gas permeability's of Kt approximately 0 h = 0.021 cm s(-1) and Kt=24 h) = 0.449 cm s(-1), respectively. Aqueous foams produced with the beta-lactoglobulin/acacia gum electrostatic complexes or coacervates exhibited very different stability. The former (t approximately 0 h) had a stable volume, combining low drainage rate and mainly air bubble disproportionation as the destabilization mechanism. By contrast, using coacervates aged for 24 h, the foam was significantly less stable, combining fast liquid drainage and air bubble destabilization though fast gas diffusion followed by film rupture and bubble coalescence. The strong effect of time on the air/water interfacial properties of the beta-lactoglobulin/acacia gum electrostatic complexes can be understood by their reorganization at the interface to form a coacervate phase that is more fluid/viscous at t approximately 0 h vs rigid/elastic at t = 24 h. 相似文献
20.
[reaction: see text] The Cp(2)TiCl-mediated deoxygenation of leurosine (1) afforded anhydrovinblastine (4) in good yield. Furthermore, as the reaction proceeded via a carbon-centered radical intermediate, this transient was also trapped by a hydrogen-atom donor to afford selectively reduced alkaloid 10. 相似文献