Kinetic modelling of radiochemical ageing of ethylene–propylene copolymers

A non-empirical kinetic model has been built for describing the general trends of radiooxidation kinetics of ethylene–propylene copolymers (EPR) at low γ dose rate and low temperature. It is derived from a radical chain oxidation mechanism composed of 30 elementary reactions: 19 relative to oxidation of methylene and methyne units plus 11 relative to their eventual cooxidation. The validity of this model has been already checked successfully elsewhere for one homopolymer: polyethylene (PE) (Khelidj et al., 2006a, Khelidj et al., 2006b; Colin et al., 2007). In the present study, it is now checked for polypropylene (PP) and a series of three EPR differing essentially by their mole fraction of ethylene (37%, 73% and 86%) and their crystallinity degree (0%, 5% and 26%). Predicted values of radiation-chemical yields are in good agreement with experimental ones published in the last half past century.     

Static portfolio choice under Cumulative Prospect Theory

We derive the optimal portfolio choice for an investor who behaves according to Cumulative Prospect Theory (CPT). The study is done in a one-period economy with one risk-free asset and one risky asset, and the reference point corresponds to the terminal wealth arising when the entire initial wealth is invested into the risk-free asset. When it exists, the optimal holding is a function of a generalized Omega measure of the distribution of the excess return on the risky asset over the risk-free rate. It conceptually resembles Merton’s optimal holding for a CRRA expected-utility maximizer. We derive some properties of the optimal holding and illustrate our results using a simple example where the excess return has a skew-normal distribution. In particular, we show how a CPT investor is highly sensitive to the skewness of the excess return on the risky asset. In the model we adopt, with a piecewise-power value function with different shape parameters, loss aversion might be violated for reasons that are now well-understood in the literature. Nevertheless, we argue that this violation is acceptable.     

Probing the interaction of the potassium channel modulating KCNE1 in lipid bilayers via solid‐state NMR spectroscopy

KCNE1 is known to modulate the voltage‐gated potassium channel α subunit KCNQ1 to generate slowly activating potassium currents. This potassium channel is essential for the cardiac action potential that mediates a heartbeat as well as the potassium ion homeostasis in the inner ear. Therefore, it is important to know the structure and dynamics of KCNE1 to better understand its modulatory role. Previously, the Sanders group solved the three‐dimensional structure of KCNE1 in LMPG micelles, which yielded a better understanding of this KCNQ1/KCNE1 channel activity. However, research in the Lorigan group showed different structural properties of KCNE1 when incorporated into POPC/POPG lipid bilayers as opposed to LMPG micelles. It is hence necessary to study the structure of KCNE1 in a more native‐like environment such as multi‐lamellar vesicles. In this study, the dynamics of lipid bilayers upon incorporation of the membrane protein KCNE1 were investigated using ³¹P solid‐state nuclear magnetic resonance (NMR) spectroscopy. Specifically, the protein/lipid interaction was studied at varying molar ratios of protein to lipid content. The static ³¹P NMR and T₁ relaxation time were investigated. The ³¹P NMR powder spectra indicated significant perturbations of KCNE1 on the phospholipid headgroups of multi‐lamellar vesicles as shown from the changes in the ³¹P spectral line shape and the chemical shift anisotropy line width. ³¹P T₁ relaxation times were shown to be reversely proportional to the molar ratios of KCNE1 incorporated. The ³¹P NMR data clearly indicate that KCNE1 interacts with the membrane. Copyright © 2017 John Wiley & Sons, Ltd.     

Stereocomplex formation between enantiomeric poly(α‐methyl‐α‐ethyl‐β‐propiolactones): Effect of molecular weight

Optically pure S(?) and R(+)‐poly(α‐methyl‐α‐ethyl‐β‐propiolactones) (PMEPLs) of controlled low molecular weights were synthesized by anionic polymerization of the corresponding optically active monomers, and characterized using gel permeation chromatography, Maldi‐TOF mass spectrometry, and NMR spectroscopy. Blends of PMEPLs of opposite configurations and different molecular weights were investigated. All blends lead to the formation of a stereocomplex and its crystallization prevails over a wide range of mixing ratios. The stereocomplex melts 30–40 °C above that of the corresponding pure polymers, depending on the molecular weight; pairs of polymers having similar molecular weights exhibit the highest melting temperatures and enthalpies of fusion. Finally, when the stereocomplex is dispersed in a PMEPL matrix, it acts as a very effective nucleation agent for the crystallization of the polymer in excess. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2380–2389, 2007     

Smooth solutions for the motion of a ball in an incompressible perfect fluid

In this paper we investigate the motion of a rigid ball surrounded by an incompressible perfect fluid occupying RN. We prove the existence, uniqueness, and persistence of the regularity for the solutions of this fluid-structure interaction problem.     

Smooth Lyapunov Functions for Discontinuous Stable Systems

It has been proved that a differential system d x / d t = f(t, x) with a discontinuous right-hand side admits some continuous weak Lyapunov function if and only if it is robustly stable. This paper focuses on the smoothness of such a Lyapunov function. An example of an (asymptotically) stable system for which there does not exist any (even weak) Lyapunov functions of class C ¹ is given. In the more general context of differential inclusions, the existence of a weak Lyapunov function of class C ¹ (or C ) is shown to be equivalent to the robust stability of some perturbed system obtained in introducing measurement error with respect to x and t. This condition is proved to be satisfied by most of the robustly stable systems encountered in the literature. Analogous results are given for the Lagrange stability. As an application to the study of the links between internal and external stability for control systems, an extension of a result by Bacciotti and Beccari is obtained by means of a smooth Lyapunov function associated with a robustly Lagrange stable system.     

Synthesis and Opiate Activity in vitro of Five New p-Nitrophenylalanine4-Enkephalin-like Peptides

Converging data obtained in biochemical and pharmacological bioassays for opiate activity are presented for five new enkephalin-like peptides. The main structural features of the analogues, the synthesis of which is described in detail, were the presence of D -alanine or D -serine in position 2, p-nitrophenylalanine in position 4 and of a free C-terminal carboxylic function. Confirming our previous observations [1], the substitution of phenylalanine by p-nitrophenylalanine enhanced the overall opiate activity but decreased the selectivity towards m?/δ-receptor sites. Tyrosyl-D -alanyl-glycyl-p-nitrophenylalanyl-adamantylalanine was particularly potent in all assays while tyrosyl-D -seryl-glycyl-p-nitrophenylalanyl-leucyl-threonine was very selective in the bioassays on isolated tissues and moderately selective in the binding assay. These results will have to be taken into account in future photoaffinity labelling and quantitative structure-activity relationships (QSAR) studies.     

Reagent-injection flow analysis: application to the determination of nanomolar levels of hydrogen peroxide in seawater

A reagent-injection flow technique, which allows automatic control of the volume of reagent to be injected, is described. The sensitivity of the measurements can be adjusted over a wide range by changing the injection volume. This technique also eliminates problems in photometric determinations arising from refractive index effects and from light scattering by suspended particles in the sample. Consequently, absorbances as small as 0.00004 can be measured. The capabilities of this reagent-injection flow technique were tested by using it to determine hydrogen peroxide in seawater at nanomolar levels with photometric detection. The concentration of hydrogen peroxide was determined as the colored condensation product of N-ethyl-N-(sulfopropyl)aniline and 4-aminoantipyrene; the detection limit was 12 nM.     

Model studies of colloidal silica precipitation using biosilica extracts from<Emphasis Type="Italic"> Equisetum telmateia</Emphasis>

Structural materials containing silicon are produced in single celled organisms through to higher plants and animals. Hydrated amorphous silica is a colloidal mineral of infinite functionality that is formed into structures with microscopic and macroscopic form. Proteins and proteoglycans are suggested to play a critical role in the catalysis of silica polycondensation and in structure direction during the formation of these magnificent structures. This article extends knowledge on the effect of protein containing biosilica extracts from Equisetum telmateia on the kinetics of silica formation and structure regulation. Utilising potassium silicon catecholate as the source of soluble silicon, bioextracts obtained from plant silica by dissolution of the siliceous phase with aqueous HF following extensive acid digestion of the plant cell wall were found to modify the kinetic rate constants for the formation of small silicic acid oligomers under circumneutral pH conditions and to modify the solubility of silicic acid in solution. Addition of the bioextracts at ca. 1 wt% to the reaction medium reduced the sizes and range of sizes of the fundamental silica particles formed and led to the formation of crystalline polymorphs of silica under conditions of ca. neutral pH, room temperature and in the absence of multiply charged cations, conditions assumed to be relevant to the biological mineralization environment. The ability of biological organisms to regulate the formation of silica structures with prevention of crystallinity is discussed as are the implications of this study in terms of the generation of new materials with specific form and function for industrial application.