A difluorosulfide as a Freon-free source of phosphonodifluoromethyl carbanion

The synthesis of difluoromethylphosphonates is becoming difficult due to environmental protective laws restricting the use of HCFCs and CFCs as starting chemicals. To circumvent this limitation, we report the preparation of a thioether as a new source of the lithiodifluoromethylphosphonate. This methodology avoiding the use of HCFCs involves a selective fluorination of sulfide followed by a thiaphilic addition of an organometallic reagent, which offers an alternative route to obtain phosphonodifluoromethyl carbanion. A contrasted reactivity, due to a medium effect, was also noted which allows addition of a wide range of electrophiles including nitroalkenes and DMF to thioethers.     

Cyclizations of 4-pentenyl, 5-hexenyl, 6-heptenyl, and 7-octenyl fluorinated radicals: a density functional theory theoretical study

The cyclization reactions of the 4-pentenyl, 5-hexenyl, 6-heptenyl, and 7-octenyl fluorinated and ether radicals have been studied by a hybrid Hartree-Fock density functional method. The reliability of this approach has been confirmed in agreement with experimental data and post-Hartree-Fock projected M?ller-Plesset second-order method. The analysis of the theoretical results shows that two factors are crucial for the determination of the regiochemistry and the reactivity of these reactions. The first factor is the ability of the starting radical to have a stable conformation in position to form the transition state, and the second one is the enthalpic effect of the reaction through the stability of the resulting cyclized radical. It should be pointed out that these factors are not linked to the polarity of the radicals due to the presence of CF2 groups.     

Optical extinction spectroscopy of single silver nanoparticles

The extinction spectrum of single silver nanoparticles with size ranging from 20 to 80 nm is investigated with the spatial modulation spectroscopy technique using either a tunable laser or a white lamp as the broadband source. Results are in good agreement with the prediction of the Mie theory, permitting to extract the nanoparticle size from the measured absolute value of the optical extinction cross-section. In contrast, the deduced refractive index of the nanoparticle environment and the reduction of the electron mean free path show a large dependence on the precise value of the bulk silver dielectric function.     

Precision of degree of polarization estimation in the presence of additive Gaussian detector noise

We address the problem of degree of polarization (DOP) estimation in images limited by additive Gaussian detector noise. We derive and analyze the probability density function (PDF) of the pixelwise DOP estimate, which is shown to have significantly different statistical properties than when noise is Gamma distributed (speckle). We then determine the Cramer-Rao Lower Bound and the maximum likelihood estimator of the DOP. We deduce from this study practical solutions for characterizing and reducing the noise in these images.     

Two-mode dynamics in dispersed systems: the case of particle-stabilized foams studied by diffusing wave spectroscopy

The stabilization of aqueous foams solely by solid particles is an active field of research. Thanks to controlled particle chemistry and production devices, we are able to generate large volumes of such foams. We previously investigated some of their unique properties, especially the strongly reduced coarsening. Here we report another type of study on these foams: performing diffusing wave spectroscopy (DWS), we investigate for the first time the internal dynamics on the scales of both the particles and the bubbles. When compared to surfactant foams, unusual features are observed; in particular, two well-separated modes are found in the dynamics, both evolving with foam aging. We propose an interpretation of these specificities, taking into account both the scattering by free particles in the foam fluid (fast mode), and by the foam structure (slow mode). To validate our interpretation, we show that independent measurements of the interstitial fluid scattering length, obtained indirectly on the foam and directly on the drained liquid, are in good agreement. We have also identified the experimental conditions required to observe such two-process dynamics. Counter-intuitively, the fraction of free particles within the foam interstitial fluid has to be very low to get an optimal signature of these particles on the DWS correlation curves. This study also sheds light on the partitioning of the particles inside the foams and at the interfaces, as the foam ages. Lastly, the results shown here (obtained by analyzing the fluctuations of the transmitted light) implement the previous ones (obtained by analyzing the mean transmitted intensity), and prove that the foam structure is actually not fully frozen.     

Structural characterization of phosphatidylcholines by atmospheric pressure photoionization mass spectrometry

The potential of atmospheric pressure photoionization was investigated for the structural analysis of phosphatidylcholine lipids (PCs). [M+H]+ ions of high abundance were obtained, along with several fragment ions. Three of these dissociation products corresponded to quite unusual fragmentation pathways but allowed the determination of both the nature and the position on the glycerol backbone (sn-1 or sn-2) of the fatty acyl chains. The loss of a methyl group from the choline head was also observed. These results suggest a complex ionization mechanism in APPI. However, this method proved to be very powerful for the rapid structural analysis of PC species without using MS/MS experiments.     

Numerical vibroacoustic analysis of plates with constrained-layer damping patches

A numerical vibroacoustic model that can manage multilayered plates locally covered with damping patches is presented. All the layers can have an on-axis orthotropic viscoelastic behavior. Continuity of displacements and transverse shear stresses at each interface is enforced, which permits to write the entire displacement field in function of the displacements of the--common--first layer, leading to a two-dimensional plate model. The problem is then discretized by Rayleigh-Ritz's method using a trigonometric basis that includes both sine and cosine functions in order to treat various boundary conditions. The excitation can be of mechanical kind (concentrated or distributed forces) or of acoustic kind (plane wave of any incidence, diffuse field, etc.). The model permits to compute different vibroacoustic indicators: the mean square velocity of the plate, the radiation efficiency, and the transmission loss. Comparisons between the present model and numerical results from literature or finite element computations show that the model gives good results in both mechanical and acoustical aspects. Then, a comparison of the effects of different distributions of patches is presented. The role of the surface covering rate is first discussed, followed by a study involving different geometries for the same surface covering rate.     

Des extensions sextiques de ℚ de clôture galoisienne engendrée par deux corps cubiques linéairement disjoints

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