Atmospheric pressure photoionization coupled to porous graphitic carbon liquid chromatography for the analysis of globotriaosylceramides. Application to Fabry disease

Globotriaosylceramides (Gb(3)) are biological compounds implicated in Fabry disease, a lysosomal storage disease due to the deficient activity of alpha-D-galactosidase A, which results in an accumulation of Gb(3) in many organs. The naturally occurring samples are composed of mixtures of several molecular species differing by the structure of the alkyl chains and the nature of the sphingoid base. Atmospheric pressure photoionization mass spectrometry (APPI-MS) proved to be an efficient method for the analysis of globotriaosylceramide molecular species, both in direct injection and by coupling with liquid chromatography (LC). In the positive ion mode, in-source fragmentations yield very precious information that can be used to determine the structure of the alkyl chains. In the negative ion mode, the chloroform solvent participates to the analyte ionization by forming an adduct with chloride ions generated in situ. Combination of LC on a Porous Graphitic Carbon stationary phase and APPI-MS allowed the detection of a great number of species from biological samples isolated from Fabry patients. This method could be an interesting analytical tool for the biochemical investigation of (sphingo) lipid metabolism.     

POD investigation of the unsteady turbulent boundary layer developing over porous moving flexible fishing net structure

Particle image velocimetry (PIV) measurements are made to investigate the boundary layer developing over a modeled bottom trawl. The random motion of the fishing net structure as well as the flexibility and the porosity of this structure means that it is not enable to access the main characteristics of such a flow, using classical post-processing mathematical tools. An innovative post-treatment tool based on proper orthogonal decomposition (POD) is then developed to extract the mean velocity flow field from each available PIV instantaneous unsteady velocity field. In order to do so, the whole available velocity database is used to compute POD eigenfunctions and the first POD modes are identified as representing the mean flow field. It is then possible to deduce the mean boundary layer flow field for each position of the fishing net structure during PIV measurements. It is then observed that the mean flow field strongly depends on multiple parameters such as surface curvature, structure porosity, random motion of the structure. Streamwise evolution of classical thicknesses of boundary layer flow are also analyzed. The present work also provides benchmark PIV data of the unsteady flow developing on fishing net porous structures, which helps the progress in unsteady numerical codes for this investigation.     

Chemically triggered C–ON bond homolysis in alkoxyamines. Part 7. Remote polar effect

In a recent work (Org. Lett. 2012, 14, 358–361), we showed that the activation by benzylation of alkoxyamine 1 (diethyl (1‐(tert‐butyl(1‐(pyridin‐4‐yl)ethoxy)amino)‐2,2‐dimethylpropyl)phosphonate) afforded a surprisingly large C–ON bond homolysis rate constant k_d. Taking advantage of the easy preparation of para‐X‐benzyl‐activated alkoxyamines 2 and of the presence of a shielding methylene group between the two aromatic moieties, we investigated the long range (10 bonds between the X group and the C–ON bond) polar effect for X = H, F, OMe, CN, NO₂, NMe₂, ⁺NHMe₂,Br^?. It was observed that the effect was weak (4‐fold) and mainly due to the zwiterionic mesomeric forms generated by the presence of group X on the para position, i.e. k_d increased for CN and NO₂ and decreased for OMe, NMe₂ and ⁺NMe₂H,Br^?. DFT calculations at the B3LYP/6‐31G(d,p) level were performed to determine orbital interactions (natural bond orbital (NBO) analysis), Mulliken and NBO charges which support the reactivity described. Copyright © 2014 John Wiley & Sons, Ltd.     

Bilinear Dispersive Estimates Via Space Time Resonances,Dimensions Two and Three

Consider a bilinear interaction between two linear dispersive waves with a generic resonant structure (roughly speaking, space and time resonant sets intersect transversally). We derive an asymptotic equivalent of the solution for data in the Schwartz class, and bilinear dispersive estimates for data in weighted Lebesgue spaces. An application to water waves with infinite depth, gravity and surface tension is also presented.     

Non-ergodicity transition and multiple glasses in binary mixtures: on the accuracy of the input static structure in the mode coupling theory

We examine the question of the accuracy of the static correlation functions used as input in the mode coupling theory (MCT) of non-ergodic states in binary mixtures. We first consider hard-sphere mixtures and compute the static pair structure from the Ornstein-Zernike equations with the Percus-Yevick closure and more accurate ones that use bridge functions deduced from Rosenfeld's fundamental measures functional. The corresponding MCT predictions for the non-ergodicity lines and the transitions between multiple glassy states are determined from the long-time limit of the density autocorrelation functions. We find that while the non-ergodicity transition line is not very sensitive to the input static structure, up to diameter ratios D(2)/D(1)?=?10, quantitative differences exist for the transitions between different glasses. The discrepancies with the more accurate closures become even qualitative for sufficiently asymmetric mixtures. They are correlated with the incorrect behavior of the PY structure at high size asymmetry. From the example of ultra-soft potential it is argued that this issue is of general relevance beyond the hard-sphere model.     

On the experimental study of the flow around a fishing net

Selectivity of fishing gears like trawls is obviously conditioned by the fish behaviour but also by the net and the flow. As well, flow may affect fish behaviour. With the aim of a better understanding of the flow in presence of a net and a catch, we suggest, through the experimental study below, to determine and to analyze the flow over a rigid cod-end in two configurations: with a closed and an open net entrance. Trials took place in a free surface flume tank and the flow characteristics were determined from velocity measurements obtained by laser velocimetry (inside, outside and through the meshes of the stiff cod-end). The experimental device, the measures and their analyzes are given here.     

Hydrogeological responses in tropical mountainous springs

This study presents a hydrogeochemical analysis of spring responses (2013–2017) in the tropical mountainous region of the Central Valley of Costa Rica. The isotopic distribution of δ¹⁸O and δ²H in rainfall resulted in a highly significant meteoric water line: δ²H?=?7.93·δ¹⁸O?+?10.37 (r^2? =?0.97). Rainfall isotopic composition exhibited a strong amount-dependent seasonality. The isotopic variation (δ¹⁸O) of two springs within the Barva aquifer was simulated using the FlowPC program to determine mean transit times (MTTs). Exponential-piston and dispersion distribution functions provided the best-fit to the observed isotopic composition at Flores and Sacramento springs, respectively. MTTs corresponded to 1.23?±?0.03 (Sacramento) and 1.42?±?0.04 (Flores) years. The greater MTT was represented by a homogeneous geochemical composition at Flores, whereas the smaller MTT at Sacramento is reflected in a more variable geochemical response. The results may be used to enhance modelling efforts in central Costa Rica, whereby scarcity of long-term data limits water resources management plans.     

Energetics of Water/Cyclodextrins Interactions

The heat capacities of solid -CD, 8.1 H₂O and -CD, 6.0 H₂O have been measured between 10 and 300 K by adiabatic calorimetry. Using earlier results obtained in similar experiments with anhydrous cyclodextrins and with -CD, 9.7 H₂O, a comparative analysis has been developed. The energetic behaviours of anhydrous and hydrated cyclodextrins (CDs) have been compared in order to investigate the role of water molecules in the stabilization of the cyclodextrin's rings and on their reactivities. Calculations, based on the additivity of thermodynamic properties, provide the energetic and entropic average contributions of water molecules in each cyclodextrin. From these results, we assumed that the water–water and water–CD interactions are rather different according to the cyclodextrin. In the (-CD, 9.7 H₂O) structure, the water molecules seem to be better organised in a relatively independent network. Concerning hydrated -CD and -CD, stronger water–CD interactions probably prevent an optimal organisation of the water–water bonds network. Differential scanning calorimetry was also used to follow the evolution of the thermal behaviour of -CD, nH₂O versus hydration ratio between 170 and 300 K. Our results indicate that the -CD ring needs at least 1.6 water molecules to be stabilized in the solid state.