On the origin of the efficient nanoparticle mediated electron transfer across a self-assembled monolayer

Recent advances in bioelectrochemistry came from the elaboration of conducting electrodes modified by an organic layer onto which nanoparticles are adsorbed. Self-assembled monolayers on noble-metal electrodes are known to hinder the electrochemical kinetics of fast-transfer redox systems. Surprisingly, fast kinetics are recovered when metal nanoparticles are deposited on top of the monolayer. We show that this surprising behavior can be fully accounted for when realizing that electron transfer from metal to metal is intrinsically easier than transfer between metal and redox system by many orders of magnitude.     

Fractal Pattern for Multiscale Digital Image Correlation

Background:

Digital Image Correlation (DIC) is based on the matching, between reference and deformed state images, of features contained in patterns that are deposited on test sample surfaces. These features are often suitable for a single scale, and there is a current lack of multiscale patterns capable of providing reliable displacement measurements over a wide range of scales.

Objective:

Here, we aim to demonstrate that a pattern based on a fractal (self-affine) surface would make a suitable pattern for multiscale DIC.

Methods:

A method to numerically generate patterns directly from a desired auto-correlation function is introduced. It is then enhanced by a Mean Intensity Gradient (MIG) improvement process based on grey level redistribution. Numerical experiments at multiple scales are performed for two different imposed displacement fields and results for one of the patterns generated are compared with those obtained for a random pattern and a Perlin noise one.

Results:

The proposed pattern is shown to lead to DIC errors comparable to those found with the two others for the first scales, but has much greater robustness. More importantly, the pattern generated here exhibits stable errors and robustness with respect to the scale whereas these two outputs become significantly degraded for the other two patterns as the scale increases.

Conclusions:

As a result, scale invariance properties of the pattern based on fractal surfaces correspond to scale invariance in DIC errors as well. This is of great interest regarding the use of such patterns in multiscale DIC.

     

Testing the independence of maxima: from bivariate vectors to spatial extreme fields

Characterizing the behaviour of multivariate or spatial extreme values is of fundamental interest to understand how extreme events tend to occur. In this paper we propose to test for the asymptotic independence of bivariate maxima vectors. Our test statistic is derived from a madogram, a notion classically used in geostatistics to capture spatial structures. The test can be applied to bivariate vectors, and a generalization to the spatial context is proposed. For bivariate vectors, a comparison to the test by Falk and Michel (Ann Inst Stat Math 58:261–290, 2006) is conducted through a simulation study. In the spatial case, special attention is paid to pairwise dependence. A multiple test procedure is designed to determine at which lag asymptotic independence takes place. This new procedure is based on the bootstrap distribution of the number of times the null hypothesis is rejected. It is then tested on maxima of three classical spatial models and finally applied to two climate datasets.     

Couplage d'un modèle stochastique lagrangien sous-maille avec une simulation grandes échelles

A large eddy simulation (LES) is used to compute passive scalar dispersion in a turbulent flow. Instead of resolving the passive scalar transport equation, fluid particles are tracked in a Lagrangian way and a Langevin stochastic modelling is used for the small scale component of the velocity of fluid particles at a subgrid-scale level. The stochastic model is written in terms of subgrid-scale statistics. The specificity of this study resides in the coupling of a LES with a stochastic model using the filtered subgrid-scale statistics in inhomogeneous turbulence. The results are compared with the wind tunnel experiments of Fackrell and Robins [J. Fluid Mech. 117 (1982) 1–26]. To cite this article: I. Vinkovic et al., C. R. Mecanique 333 (2005).     

α-amylase production by free and immobilized Bacillus subtilis

The effect of glucose on the α-amylase production by Bacillus subtilis ATCC-21556 was studied. Initial glucose concentrations up to 20 g/L were found to be directly proportional to the specific α-amylase production in an immobilized-cell batch system, whereas a free-cell batch system presented an inversely proportional relationship with the initial glucose concentration. This might be owing to the α-amylase repression by the glucose present in the culture medium. Three hundred eighty-five percent of the specific α-amylase production with the free-cell system was produced by the immobilized-cell batch culture.     

Accurate measurements of thermodynamic properties of solutes in ionic liquids using inverse gas chromatography

Activity coefficients at infinite dilution of 29 organic compounds in two room temperature ionic liquids were determined using inverse gas chromatography. The measurements were carried out at different temperatures between 323.15 and 343.15K. To establish the influence of concurrent retention mechanisms on the accuracy of activity coefficients at infinite dilution for 1-butyl-3-methylimidazolium octyl sulfate and 1-ethyl-3-methylimidazolium tosylate, phase loading studies of the net retention volume per gram of packing as a function of the percent phase loading were used. It is shown that most of the solutes are retained largely by partition with a small contribution from adsorption on 1-butyl-3-methylimidazolium octyl sulfate and that the n-alkanes are retained predominantly by interfacial adsorption on 1-ethyl-3-methylimidazolium tosylate.     

Potassium silanide (KSiH3): a reversible hydrogen storage material

KSi silicide can absorb hydrogen to directly form the ternary KSiH₃ hydride. The full structure of α‐KSiD₃, which has been solved by using neutron powder diffraction (NPD), shows an unusually short Si? D lengths of 1.47 Å. Through a combination of density functional theory (DFT) calculations and experimental methods, the thermodynamic and structural properties of the KSi/α‐KSiH₃ system are determined. This system is able to store 4.3 wt % of hydrogen reversibly within a good P–T window; a 0.1 M Pa hydrogen equilibrium pressure can be obtained at around 414 K. The DFT calculations and the measurements of hydrogen equilibrium pressures at different temperatures give similar values for the dehydrogenation enthalpy (≈23 kJ mol^?1 H₂) and entropy (≈54 J K^?1 mol^?1 H₂). Owing to its relatively high hydrogen storage capacity and its good thermodynamic values, this KSi/α‐KSiH₃ system is a promising candidate for reversible hydrogen storage.     

Highly convergent synthesis of chiral bicyclophosphinates by domino hydrophosphinylation/Michael/Michael reaction

Diastereoselective domino reactions of iminoalcohols and allenyl H-phosphinates produce chiral phosphorus bicycles in a regio- and stereoselective fashion. A predictive model for diastereoselection is used for these new chiral phosphinic esters.