A General Approach to Deboronative Radical Chain Reactions with Pinacol Alkylboronic Esters

The generation of carbon‐centered radicals from air‐sensitive organoboron compounds through nucleohomolytic substitution at boron is a general method to generate non‐functionalized and functionalized radicals. Due to their reduced Lewis acidity, alkylboronic pinacol esters are not suitable substrates. We report their in situ conversion into alkylboronic catechol esters by boron‐transesterification with a substoichiometric amount of catechol methyl borate combined with an array of radical chain processes. This simple one‐pot radical‐chain deboronative method enables the conversion of pinacol boronic esters into iodides, bromides, chlorides, and thioethers. The process is also suitable the formation of nitriles and allylated compounds through C?C bond formation using sulfonyl radical traps. The power of combining radical and classical boron chemistry is illustrated with a modular 5‐membered ring formation using a combination of three‐component coupling and protodeboronative cyclization.     

A microscopic model for the fluctuations of local field and spontaneous emission of single molecules in disordered media.

We develop a microscopic model to describe the observed temporal fluctuations of the fluorescence lifetime of single molecules embedded in a polymer at room temperature. The model represents the fluorescent probe and the macromolecular matrix on the sites of a cubic lattice and introduces voids in the matrix to account for its mobility. We generalize Lorentz's approach to dielectrics by considering three domains of electrostatic interaction of the probe molecule with its nanoenvironment: (1) the probe molecule with its elongated shape and its specific polarizability, (2) the first few solvent shells with their discrete structure and their inhomogeneity, (3) the remainder of the solvent at larger distances, treated as a continuous dielectric. The model is validated by comparing its outcome for homogeneous systems with those of existing theories. When realistic inhomogeneities are introduced, the model correctly explains the observed fluctuations of the lifetimes of single molecules. Such a comparison is only possible with single-molecule observations, which provide a new access to local field effects.     

Théorème limite pour une équation différentielle à coefficient aléatoire à mémoire longue

We consider an ordinary differential equation depending on a small parameter and with a long-range random coefficient. We establish that the solution of this ordinary differential equation converges to the solution of a stochastic differential equation driven by a fractional Brownian motion. The index of the fractional Brownian motion depends on the asymptotic behavior of the covariance function of the random coefficient. The proof of the convergence uses the T. Lyons theory of “rough paths”. To cite this article: R. Marty, C. R. Acad. Sci. Paris, Ser. I 338 (2004).     

Granular Rayleigh-Taylor instability: experiments and simulations

A granular instability driven by gravity is studied experimentally and numerically. The instability arises as grains fall in a closed Hele-Shaw cell where a layer of dense granular material is positioned above a layer of air. The initially flat front defined by the grains subsequently develops into a pattern of falling granular fingers separated by rising bubbles of air. A transient coarsening of the front is observed right from the start by a finger merging process. The coarsening is later stabilized by new fingers growing from the center of the rising bubbles. The structures are quantified by means of Fourier analysis and quantitative agreement between experiment and computation is shown. This analysis also reveals scale invariance of the flow structures under overall change of spatial scale.     

Optical low-coherence reflectometry for complete chromatic dispersion characterization of few-mode fibers

A phase-sensitive optical low-coherence reflectometry (OLCR) technique is demonstrated to simultaneously measure the absolute chromatic dispersion values of each guided LP mode of a few-mode fiber. We show that the OLCR technique requires only short samples of fiber (<1 m) and has no need for high-ratio mode converters to reach an accurate wavelength-dependent group delay evolution of every mode. As an example we present for the first time to our knowledge a direct and complete analysis of few-mode fibers with high, low, positive, and negative modal dispersion values, leading to chromatic dispersion parameters in good agreement with theoretical predictions.     

Transport in superlattices of magnetic nanoparticles: coulomb blockade, hysteresis, and switching induced by a magnetic field

We report on magnetotransport measurements on millimetric superlattices of Co-Fe nanoparticles surrounded by an organic layer. At low temperature, the transition between the Coulomb blockade and the conductive regime becomes abrupt and hysteretic. The transition between both regimes can be induced by a magnetic field, leading to a novel mechanism of magnetoresistance. Between 1.8 and 10 K, a high-field magnetoresistance attributed to magnetic disorder at the surface of the particles is also observed. Below 1.8 K, this magnetoresistance abruptly collapses and a low-field magnetoresistance is observed.     

CEC separation of aromatic compounds and proteins on hexylamine-functionalized N-acryloxysuccinimide monoliths

Reactive organic polymer monoliths were prepared in fused-silica capillaries by UV-initiated free radical polymerization of N-acryloxysuccinimide (NAS) as reactive monomer, ethylene dimethacrylate as crosslinker, azobisisobutyronitrile as initiator, and toluene as porogen. In a second synthetic step, chemical derivatization of the activated-ester moieties was performed in situ through alkylation reaction with alkylamines to afford monolithic stationary phases with potential reversed-phase properties. A correlation between the synthesis conditions--composition of the reactive solution--chemical characteristics of the reactive polymer monoliths--nitrogen/NAS content--and the reversed-phase separation properties of the functionalized monolithic columns--selectivity towards homologous series of akylbenzenes--was clearly established. This finding offers the possibility of adjusting the experimental conditions with respect to the target applications. The monolithic stationary phases with optimized chemical and porous structures were used for the CEC separation of alkylbenzenes, phenols, anilines, organic acids, amino acids, and proteins. The data indicate that depending on the nature of the analytes (charge, hydrophobic/hydrophilic balance, size) reversed-phase or mixed modes may account for the observed separation.     

Adaptation of the "in-gel release method" to N-glycome analysis of low-milligram amounts of material

Protein N-glycosylation is a post-translational modification which plays numerous crucial physiological roles. The N-glycan pattern varies depending on the species organs, tissues and even cell types and their respective physiological states. Obtaining enough starting material from a particular cell type or tissue for N-glycan purification by conventional methods can, in certain cases, be very difficult. Previously, a sensitive technique, the "in-gel release method" that allows the determination of N-glycans attached to a protein isolated by SDS-PAGE, has been developed in this and other laboratories. Here, we describe the adaptation of this method to obtain information on the N-glycome from minute amounts of tissue. The starting material, ranging from less than a milligram to a few milligrams of fresh tissue, is directly ground in Laemmli sample buffer and subject briefly to discontinuous Tris-glycine-SDS-PAGE. The Coomassie-stained band containing the majority of the proteins is subject to the "in-gel release method". The developed technique was used to analyze N-glycan patterns of different samples from Caenorhabditis elegans, Drosophila melanogaster, Spodoptera frugiperda, Trichoplusia ni, Nicotiana benthamiana, Arabidopsis thaliana, and Mus musculus. Furthermore, the technique was used to determine the effects of transient small-scale RNAi-mediated knock-down of a glycosylation-related gene in Drosophila Schneider 2 cell line.     

Early Main Group Metal Catalysis: How Important is the Metal?

Organocalcium compounds have been reported as efficient catalysts for various alkene transformations. In contrast to transition metal catalysis, the alkenes are not activated by metal–alkene orbital interactions. Instead it is proposed that alkene activation proceeds through an electrostatic interaction with a Lewis acidic Ca²⁺. The role of the metal was evaluated by a study using the metal‐free catalysts: [Ph₂N^?][Me₄N⁺] and [Ph₃C^?][Me₄N⁺]. These “naked” amides and carbanions can act as catalysts in the conversion of activated double bonds (C?O and C?N) in the hydroamination of Ar? N?C?O and R? N?C?N? R (R=alkyl) by Ph₂NH. For the intramolecular hydroamination of unactivated C?C bonds in H₂C?CHCH₂CPh₂CH₂NH₂ the presence of a metal cation is crucial. A new type of hybrid catalyst consisting of a strong organic Schwesinger base and a simple metal salt can act as catalyst for the intramolecular alkene hydroamination. The influence of the cation in catalysis is further evaluated by a DFT study.     

The Direct Heat Measurement of Mechanical Energy Storage Metal–Organic Frameworks

In any process, the heat exchanged is an essential property required in its development. Whilst the work related to structural transitions of some flexible metal–organic frameworks (MOFs) has been quantified and linked with potential applications such as molecular springs or shock absorbers, the heat related to such transitions has never been directly measured. This has now been carried out with MIL‐53(Al) using specifically devised calorimetry experiments. We project the importance of these heats in devices such as molecular springs or dampers.