Mathematical discretization of size-exclusion chromatograms applied to commercial corn maltodextrins

Discretization of a size-exclusion chromatography (SEC) chromatogram is shown here to be an important calculation for characterizing the distribution of a polydisperse polymer, especially when the polydispersity is large. Commercial poly-glucose maltodextrins are known to have such a polydispersity. A mathematical discretization method with Gaussian peaks centered on each individual degree of polymerization is proposed and is performed on the entire SEC chromatogram for three different grades of corn maltodextrins. Because SEC and high-performance anion exchange chromatography with pulsed amperometric detection (HPAEC-PAD) are based on different separation mechanisms, they can be considered orthogonal techniques, and HPAEC-PAD was therefore used to validate the SEC discretization procedure. Because this validation proved satisfactory for all commercially available oligomers, the discretization is extended to all of their SEC chromatograms. Comparing the number-average molar weight and the weight-average molar weight before and after the mathematical discretization verifies that such a mathematical treatment does not denaturate the chromatogram. This approach tentatively leads to a more exhaustive characterization of a broadly polydisperse sample, such as maltodextrins, than was previously available, as it (i) gets rid of the apparent, chemically irrelevant, continuous molar weight distribution obtained by raw SEC and (ii) addresses the current detection and quantitation limits of the HPAEC-PAD technique without any sample treatment.     

Groupes Moyennables, Dimension Topologique Moyenne et sous-décalages

Let G be an infinite countable residually finite amenable group. In this paper we construct a continuous action of G on a compact metrisable space X such that the dynamical system (X, G) cannot be embedded in the G-shift on [0,1] ^G . This result generalizes a construction due to E. Lindenstrauss and B. Weiss (Mean topological dimension, Israel J. Math. 115 (2000), 1–24) for .     

An alternative to modal analysis for material stiffness and damping identification from vibrating plates

This paper presents an alternative to modal analysis to extract stiffness and damping parameters from thin vibrating plates. Full-field slope measurements are performed through a deflectometry technique on a plate vibrating at a given frequency. Images are recorded in phase and at π/2 lag from the excitation. From this information, deflection fields are computed by integration and curvature fields are obtained by differentiation. This information is then input into the principle of virtual work to extract both stiffness and damping parameters. This procedure, known as the Virtual Fields Method, is detailed in the paper and the notion of special optimized virtual fields is extended to the present problem. Validation on simulated data is performed before moving to experimental data. One of the main advantages of this technique is that it is completely insensitive to the damping coming from the boundary conditions. This is illustrated experimentally on two tests where a viscoelastic layer and rubber washers are added in the experimental set up.     

Phosphorus-based nanothermites: A new generation of energetic materials

Thermites are energetic materials that are classically made of a transition metal oxide mixed with a reducing metal. Contrary to explosives, thermites do not detonate because their combustion is relatively slow and their reaction by-products are often solid or liquid. The use of nanoparticles to prepare superthermites is very promising. The dramatic changes observed in their reactivity were reported by numerous recent papers dealing with the use of aluminium as fuel.Red phosphorus is widely used in pyrotechnic devices. Highly explosive compositions are classically obtained by mixing this substance with strong oxidizers such as oxygenated potassium salts (chlorate, nitrate). But to our knowledge, the idea to prepare P-nanothermites with metallic oxide nanoparticles was never reported before. In order to illustrate this new concept of energetic formulations, P-nanothermites were prepared from nickel oxide (NiO), iron oxide (Fe₂O₃), and copper oxide (CuO) nanopowders. The reactivity of these compositions was studied by thermogravimetric analysis, impact and friction tests, electrostatic discharge and high-speed cinematography. P-nanothermites are very insensitive to thermal and impact stress. Their combustion rates strongly depend on the nature of the oxide (NiO <Fe₂O₃?CuO). The SEM observation of the microstructure of the residues produced by the combustion clearly indicates that they were formed by the solidification of molten phases. In other words, the energy released by the combustion of P-nanothermites provokes the melting of the reaction products. The temperatures reached are thus high enough to cause the gasification of phosphoric anhydride produced by the combustion. For this reason, P-nanothermites can be considered gas-generating materials.     

Kinetics and dynamics of the S(1D2) + H2 → SH + H reaction at very low temperatures and collision energies

We report combined studies on the prototypical S(1D2) + H2 insertion reaction. Kinetics and crossed-beam experiments are performed in experimental conditions approaching the cold energy regime, yielding absolute rate coefficients down to 5.8 K and relative integral cross sections to collision energies as low as 0.68 meV. They are supported by quantum calculations on a potential energy surface treating long-range interactions accurately. All results are consistent and the excitation function behavior is explained in terms of the cumulative contribution of various partial waves.     

In solution sensitization of Er(III) luminescence by the 4-tetrathiafulvalene-2,6-pyridinedicarboxylic acid dimethyl antenna ligand

In the [Er(hfac)(3)(L)](2) complex (1) (L = 4-tetrathiafulvalene-2,6-pyridinecarboxylic acid dimethyl ester), the Er(III) ion is bonded to the tridentate coordination site. Electrochemical and photophysical measurements in solution reveal that the tetrathiafulvalene moiety is a versatile antenna for erbium luminescence sensitization at 6540 cm(-1) upon excitation in the low-energy charge transfer transition (donor to acceptor charge transfer) at 16600 cm(-1) assigned via time-dependent density functional theory calculations.     

The Horizontal Heat Kernel on the Quaternionic Anti-De Sitter Spaces and Related Twistor Spaces

Potential Analysis - The geometry of the quaternionic anti-de Sitter fibration is studied in details. As a consequence, we obtain formulas for the horizontal Laplacian and subelliptic heat kernel...     

A constitutive model for semi-crystalline polymer deformation involving lamellar fragmentation

The mechanism of lamellar fragmentation in the semi-crystalline polymers with spherulitic structure, is observed at the beginning of plastic flow. It causes significant damage. This elementary mechanism is considered here as a result of plastic deformation coupled with damage, in the framework of generalized standard materials. The simplicity and the efficiency of the proposed approach come from the fact that the semi-crystalline polymers are considered as a macromolecular network bridled by intra-lamellar cohesive forces. Tensile tests and relaxation tests demonstrate the usefulness of a damage–plasticity coupled model.     

Effect of the ionic strength of salts on retention and overloading behavior of ionizable compounds in reversed-phase liquid chromatography II. Symmetry-C18

In a companion paper, we describe the influence of the concentration and the nature of salts dissolved in the mobile phase (methanol:water, 40:60, v/v) on the adsorption behavior of propranolol (R'-NH2+ -R, Cl-) on XTerra-C18. The same experiments were repeated on a Symmetry-C18 column to compare the adsorption mechanisms of this ionic compound on these two very different RPLC systems. Frontal analysis (FA) measurements were first carried out to determine the best isotherm model accounting for the adsorption behavior of propranolol hydrochloride on Symmetry with a mobile phase without salt (and only 25% methanol to compensate for the low retention in the absence of salt). The adsorption data were best modeled by the bi-Moreau model. Large concentration band profiles of propranolol were recorded with mobile phases having increasing KCl concentrations (0, 0.002, 0.005, 0.01, 0.05, 0.1 and 0.2 M) and the best values of the isotherm coefficients were determined by the inverse method (IM) of chromatography. The general effect of a dissociated salt in the mobile phase was the same as the one observed earlier with XTerra-C18. Increasing the salt concentration increases the two saturation capacities of the adsorbent and the adsorption constant on the low-energy sites. The adsorption constant on the high-energy sites decreases and the adsorbate-adsorbate interactions tend to vanish with increasing salt concentration of the mobile phase. The saturation capacities decrease with increasing radius of the monovalent cation (Na+, K+, Cs+, etc.). Using sulfate as a bivalent anion (Na2SO4) affects markedly the adsorption equilibrium: the saturation capacities are drastically reduced, the high-energy sites nearly disappear while the adsorption constant and the adsorbate-adsorbate interactions on the low-energy sites increase strongly. The complexity of the thermodynamics in solution might explain the different influences of these salts on the adsorption behavior.     

Effect of the temperature on the isotherm parameters of phenol in reversed-phase liquid chromatography

Adsorption isotherm data of phenol from an aqueous solution of methanol onto a C18-bonded silica (Symmetry-C18) were acquired by frontal analysis (FA) at six different temperatures, in a wide concentration range. The non-linear fitting of these data provided the bi-Langmuir model as best isotherm model, a conclusion further supported by the results of the calculation of the affinity energy distribution (AED). The isotherm parameters were obtained using several methods, the fitting of FA isotherm data, the calculation of the AED, and the inverse method, that uses overloaded elution band profiles. The different values obtained are in close agreement. They allow a quantitative investigation of the separate properties of the low- and the high-energy sites on the adsorbent surface. Increasing the temperature decreases the saturation capacity of the low-energy adsorption sites and the adsorption constant of the high-energy sites. In contrast, increasing the temperature does not cause any significant changes in either the saturation capacity of the high-energy sites or the adsorption constant of the low-energy sites.