La structure des copolyèdres au sens de Stamm

Sans résumé     

Combinatorial Templates Generated by Dip-Pen Nanolithography for the Formation of Two-Dimensional Particle Arrays

No Abstract     

Influence of the physical state of phospholipid monolayers on protein binding

Langmuir monolayers were used to characterize the influence of the physical state of phospholipid monolayers on the binding of protein Retinis Pigmentosa 2 (RP2). The binding parameters of RP2 (maximum insertion pressure (MIP), synergy and ΔΠ(0)) in monolayers were thus analyzed in the presence of phospholipids bearing increasing fatty acyl chain lengths at temperatures where their liquid-expanded (LE), liquid-condensed (LC), or solid-condensed (SC) states can be individually observed. The data show that a larger value of synergy is observed in the LC/SC states than in the LE state, independent of the fatty acyl chain length of phospholipids. Moreover, both the MIP and the ΔΠ(0) increase with the fatty acyl chain length when phospholipids are in the LC/SC state, whereas those binding parameters remain almost unchanged when phospholipids are in the LE state. This effect of the phospholipid physical state on the binding of RP2 was further demonstrated by measurements performed in the presence of a phospholipid monolayer showing a phase transition from the LE to the LC state at room temperature. The data collected are showing that very similar values of MIP but very different values of synergy and ΔΠ(0) are obtained in the LE (below the phase transition) and LC (above the phase transition) states. In addition, the binding parameters of RP2 in the LE (below the phase transition) as well as in the LC (above the phase transition) states were found to be indistinguishable from those where single LC and LE states are respectively observed. The preference of RP2 for binding phospholipids in the LC state was then confirmed by the observation of a large modification of the shape of the LC domains in the phase transition. Therefore, protein binding parameters can be strongly influenced by the physical state of phospholipid monolayers. Moreover, measurements performed with the α/β domain of RP2 strongly suggest that the β helix of RP2 plays a major role in the preferential binding of this protein to phospholipids in the LC state.     

Lewis base mediated dismutation of trichlorosilane

An abnormal N-heterocyclic carbene (aNHC) has been used as a Lewis base to initiate dismutation of trichlorosilane. This report presents the reactivity differences of a normal N-heterocyclic carbene (NHC) versus aNHC with heavier group 14 elements. Three novel compounds (NHC)(2)·SiCl(2)H(2) (2), aNHC·SiCl(2)H(2) (3), and aNHC·GeCl(2) (4) have been synthesized and characterized by single crystal X-ray analysis, solid-state NMR and DFT calculations.     

The probe profile and lateral resolution of scanning transmission electron microscopy of thick specimens

Lateral profiles of the electron probe of scanning transmission electron microscopy (STEM) were simulated at different vertical positions in a micrometers-thick carbon sample. The simulations were carried out using the Monte Carlo method in CASINO software. A model was developed to fit the probe profiles. The model consisted of the sum of a Gaussian function describing the central peak of the profile and two exponential decay functions describing the tail of the profile. Calculations were performed to investigate the fraction of unscattered electrons as a function of the vertical position of the probe in the sample. Line scans were also simulated over gold nanoparticles at the bottom of a carbon film to calculate the achievable resolution as a function of the sample thickness and the number of electrons. The resolution was shown to be noise limited for film thicknesses less than 1 μm. Probe broadening limited the resolution for thicker films. The validity of the simulation method was verified by comparing simulated data with experimental data. The simulation method can be used as quantitative method to predict STEM performance or to interpret STEM images of thick specimens.     

Progress in correlation spectroscopy at ultra-fast magic-angle spinning: basic building blocks and complex experiments for the study of protein structure and dynamics

Recent progress in multi-dimensional solid-state NMR correlation spectroscopy at high static magnetic fields and ultra-fast magic-angle spinning is discussed. A focus of the review is on applications to protein resonance assignment and structure determination as well as on the characterization of protein dynamics in the solid state. First, the consequences of ultra-fast spinning on sensitivity and sample heating are considered. Recoupling and decoupling techniques at ultra-fast MAS are then presented, as well as more complex experiments assembled from these basic building blocks. Furthermore, we discuss new avenues in biomolecular solid-state NMR spectroscopy that become feasible in the ultra-fast spinning regime, such as sensitivity enhancement based on paramagnetic doping, and the prospect of direct proton detection.     

The dark side of crystal engineering: creating glasses from small symmetric molecules that form multiple hydrogen bonds

Glasses made from compounds of low molecular weight are useful materials with many attractive features, including well-defined compositions. At present, there are no reliable ways to identify molecules that will form long-lived glasses, and efforts to design them have tended to rely on crude principles, such as avoiding small, symmetric, and relatively inflexible molecules that engage in strong intermolecular association. We have found that it is possible to make glasses from such molecules by turning to the dark side of crystal engineering and by making small but carefully selected structural modifications specifically designed to thwart established patterns of crystallization.     

Escape Rates and Physically Relevant Measures for Billiards with Small Holes

We study the billiard map corresponding to a periodic Lorentz gas in 2-dimensions in the presence of small holes in the table. We allow holes in the form of open sets away from the scatterers as well as segments on the boundaries of the scatterers. For a large class of smooth initial distributions, we establish the existence of a common escape rate and normalized limiting distribution. This limiting distribution is conditionally invariant and is the natural analogue of the SRB measure of a closed system. Finally, we prove that as the size of the hole tends to zero, the limiting distribution converges to the smooth invariant measure of the billiard map.     

Facile Protection of Lithium Metal for All-Solid-State Batteries

A nanolayer of reactive propyl acrylate silane groups was deposited on a lithium surface by using a simple dipping method. The polymerization of cross-linkable silane groups with a layer of ally-ether-ramified polyethylene oxide was induced by UV light. SEM analysis revealed a good dispersion of silane groups grafted on the lithium surface and a layer of polymer of about 4 μm was obtained after casting and reticulation. The electrochemical performance for the unmodified and modified lithium electrodes were compared in symmetrical Li/LLZO/Li cells. Stable plating/stripping and low interfacial resistance were obtained when the modified lithium was utilized, indicating that the combination of silane and polymer deposition is promising to increase Li-metal/garnet contact.