Application des relation de Mislow et Raban a la determination de configuration (mesothreo) par resonance magnetique nucleaire

The meso or threo configuration of diastereoisomeric molecules is elucidated on the basis of respective NMR spectra of either isomers. The symmetry relationship (according to Raban and Mislow) between protons or groups are not identical in each isomer, and the consequent differences in chemical shifts and spin-coupling constants permit assignment of configurations.     

Molecular Recognition by Hydrogen Bonding in Polyelectrolyte Multilayers

Functional polyanions were prepared by copolymerization of sulfopropyl acrylate and sulfopropyl methacrylate with monomers bearing triaminopyrimidine or barbituric acid functionalities, respectively. Functionalized polyelectrolyte multilayers were assembled from these copolymers by stepwise alternating adsorption with poly(choline methacrylate). These multilayers are suited for molecular recognition of substrates that are complementary to the functional groups incorporated. Thus, multilayers containing triaminopyrimidine moieties selectively bind barbituric acid, and vice versa, when exposed to solutions of the 1:1 complex of barbituric acid and triaminopyrimidine. The molecular recognition process was monitored by UV/Vis spectroscopy, time-of-flight secondary ion mass spectroscopy (ToF-SIMS), and photoelectron spectroscopy (XPS). Remarkably, after successful recognition and binding of the complementary substrates to the multilayers, the stepwise layering could be continued.     

Degradations photothermiques de polyethylenes reticules—I: Influence de noirs de carbone commerciaux

Introduction of small quantities (<1%) of carbon black in branched polyethylene induces a photothermic degradation at temperatures >70°. An interpretation of variations in the rate of degradation, measured by i.r. absorption or by deformation, with the percentage of carbon black has been given. The effects of different commercial samples of carbon black have been compared.     

Ab initio mechanistic study of radical reactions: The regioselectivity of the addition of atomic hydrogen to fluoroacetylene and 1,1-difluoroethylene

Ab initio molecular orbital calculations of the transition states and barrier heights for the addition of atomic hydrogen to fluoroactylene and 1,1-difluoroethylene are presented. The relative reactivity of these compounds and the regioselectivity of the addition reactions are analyzed in terms of chemically interpretable contributions by means of the energy decomposition scheme proposed by Morokuma. The usual PMO approach of the problem is discussed in this context. A rationalization of some of the experimental rules of radical reactivity is given.     

Modelization of photocatalyzed oxidation of polyolefins. II. ZnO and TiO2 photocatalyzed decomposition of tert-butyl hydroperoxide and atactic polypropylene hydroperoxides

Direct evidence of the TiO₂ and ZnO photocatalytic decomposition of tert-butyl hydroperoxide and atactic polypropylene hydroperoxides in solution is reported. Molecular and macromolecular hydroperoxides behaved similarly. Untreated TiO₂ in the rutile form was a far more efficient photocatalyst than ZnO in solution; the photoactivities of both pigments were limited on preferential absorption sites. In the solid state no preferential reaction sites were observed. When added to preoxidized atactic polypropylene both pigments were photocatalysts of the formation of macromolecular hydroperoxides and of their decomposition. The photoreactivities of untreated TiO₂ and ZnO varied less than in solution.     

Towards large eddy simulations of flame extinction and carbon monoxide emission in compartment fires

The general objective of this research is to adapt current combustion modeling capabilities used in computational fluid dynamics solvers to the treatment of under-ventilated compartment fires. More specifically, we consider in the present study two models proposed to describe: diffusion flame extinction due to air vitiation; and the emission of carbon monoxide (CO) and unburnt hydrocarbon (HC) mass in a compartment fire. The flame extinction model is based on a flammability diagram parametrized in terms of vitiated air properties. The CO/HC mass model is based on: a transport equation for fuel mass; a comparison of this fuel mass to a Burke–Schumann chemical-equilibrium expression; and an interpretation of the difference as a measure of incomplete combustion. Both models are implemented into a large eddy simulation solver developed by the National Institute of Standards and Technology, USA. The models performance is tested via detailed comparisons with an experimental database corresponding to reduced-scale compartment fires. The study considers two cases that correspond to different values of the fire room global equivalence ratio and are representative of strikingly different flame behaviors. The comparative tests serve to evaluate the general ability of the models to describe the transition from extinction-free conditions to conditions in which the flame experiences partial or total quenching, as well as the transition from fire regimes with no or little CO emission to regimes that emit hazardous levels.     

On Fractional Brownian Processes

We use Liouville spaces in order to prove the existence of some different fractional -Brownian motion ( 0 < 1 ), or fractional ( , )-Brownian sheets. There are also applications to the Wiener stochastic integral with respect to these -Brownian.     

In situ isobaric lipid mapping by MALDI–ion mobility separation–mass spectrometry imaging

The highly diverse chemical structures of lipids make their analysis directly from biological tissue sections extremely challenging. Here, we report the in situ mapping and identification of lipids in a freshwater crustacean Gammarus fossarum using matrix‐assisted laser desorption/ionization (MALDI) mass spectrometry imaging (MSI) in combination with an additional separation dimension using ion mobility spectrometry (IMS). The high‐resolution trapped ion mobility spectrometry (TIMS) allowed efficient separation of isobaric/isomeric lipids showing distinct spatial distributions. The structures of the lipids were further characterized by MS/MS analysis. It is demonstrated that MALDI MSI with mobility separation is a powerful tool for distinguishing and localizing isobaric/isomeric lipids.     

High-harmonic generation from plasma mirrors at kilohertz repetition rate

We report the first demonstration of high-harmonic generation from plasma mirrors at a 1 kHz repetition rate. Harmonics up to nineteenth order are generated at peak intensities close to 101? W/cm2 by focusing 1 mJ, 25 fs laser pulses down to 1.7 μm FWHM spot size without any prior wavefront correction onto a moving target. We minimize target surface motion with respect to the laser focus using online interferometry to ensure reproducible interaction conditions for every shot and record data at 1 kHz with unprecedented statistics. This allows us to unambiguously identify coherent wake emission as the main generation mechanism.