Chemoenzymatic synthesis of highly enantiomerically enriched secondary alcohols with a thiazolic core

Stereoselective preparative enzymatic acylation and hydrolysis/methanolysis of various C-substituted rac-thiazol-2-yl-methanols were achieved for the preparation of enantiopure or enantiomerically enriched, naturally occurring 2-hydroxymethylthiazoles. The absolute configurations of the resulting secondary alcohols were determined by a detailed ¹H NMR study of Mosher’s derivatives.     

Multiaxial mechanical behavior of aramid fibers and identification of skin/core structure from single fiber transverse compression testing

The transverse and longitudinal mechanical properties of aramid fibers like Kevlar? 29 (K29) fibers are strongly linked to their highly oriented structure. Mechanical characterization at the single fiber scale is challenging especially when the diameter is as small as 15 µm. Longitudinal tensile tests on single K29 fibers and single fiber transverse compression test (SFTCT) have been developed. Our approach consists of coupling morphological observations and mechanical experiments with SFTCT analysis by comparing analytical solutions and finite element modeling. New insights on the analysis of the transverse direction response are highlighted. Systematic loading/unloading compression tests enable to experimentally determine a transverse elastic limit. Taking account of the strong anisotropy of the fiber, the transverse mechanical response sheds light on a skin/core architecture. More importantly, results suggest that the skin of the fiber, typically representing a shell of one micrometer in thickness, has a transverse apparent modulus of 0.2 GPa. That is around more than fifteen times lower than the transverse modulus of 3.0 GPa in the core. By comparison, the measured longitudinal modulus is about 84 GPa. The stress distribution in the fiber is explored and the critical areas for damage initiation are discussed. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 374–384     

The Lyapunov Exponent of Products of Random 2×2 Matrices Close to the Identity

We study products of arbitrary random real 2×2 matrices that are close to the identity matrix. Using the Iwasawa decomposition of SL(2,?), we identify a continuum regime where the mean values and the covariances of the three Iwasawa parameters are simultaneously small. In this regime, the Lyapunov exponent of the product is shown to assume a scaling form. In the general case, the corresponding scaling function is expressed in terms of Gauss’ hypergeometric function. A number of particular cases are also considered, where the scaling function of the Lyapunov exponent involves other special functions (Airy, Bessel, Whittaker, elliptic). The general solution thus obtained allows us, among other things, to recover in a unified framework many results known previously from exactly solvable models of one-dimensional disordered systems.     

Advances in the measurements of the mass attenuation coefficients

The knowledge of atomic fundamental parameters, such as mass attenuation coefficients or fluorescence yields with low uncertainties, is of decisive importance in elemental quantification involving X-ray fluorescence analysis techniques. Several databases providing the mass attenuation coefficients are accessible and frequently used within a large community of users. These compilations are most often in good agreement for photon energies in the hard X-ray ranges. However, they significantly differ for low photon energies and around the absorption edges of the elements. Mass attenuation coefficients of several elements were determined experimentally in the photon energy range from 100 eV to 35 keV by using monochromatized radiation at the SOLEIL synchrotron (France). The application of high-accuracy experimental techniques resulted in low uncertainty mass attenuation coefficients. The results are compared with tabulated data.     

Dynamic Molecular Metamorphism Involving Palladium-Assisted Dimerization of π-Cation Radicals

A dynamic supramolecular approach is developed to promote the π-dimerization of viologen radicals at room temperature and in standard concentration ranges. The approach involves cis- or trans-protected palladium centers serving as inorganic hinges linking two functionalized viologens endowed with metal-ion coordinating properties. Based on detailed spectroscopic, electrochemical and computational data, we show that the one-electron electrochemical reduction of the viologen units in different dynamic metal/ligand mixtures leads to the formation of the same intramolecular π-dimer, regardless of the initial environment around the metallic precursor and of the relative ratio between metal and ligand initially introduced in solution. The large-scale electron-triggered reorganization of the building blocks introduced in solution thus involves drastic changes in the stoichiometry and stereochemistry of the palladium/viologen complexes proceeding in some cases through a palladium centered trans→cis isomerization of the coordinated ligands.     

A Note on Convergence of the Equi-Energy Sampler

This paper studies maximum likelihood estimation for a parameterised elliptic diffusion in a manifold. The focus is on asymptotic properties of maximum likelihood estimates obtained from continuous time observation. These are well known when the underlying manifold is a Euclidean space. However, no systematic study exists in the case of a general manifold. The starting point is to write down the likelihood function and equation. This is achieved using the tools of stochastic differential geometry. Consistency, asymptotic normality and asymptotic optimality of maximum likelihood estimates are then proved, under regularity assumptions. Numerical computation of maximum likelihood estimates is briefly discussed.