Enhanced selectivity of the isolation of basic drugs from body fluids by means of extraction minicolumns and sophisticated elution schemes.

The paper presents results and experience obtained in the isolation of a number of basic polar/non-polar solutes (drugs, their metabolites and structural derivatives) from biological samples by using the separation minicolumns Separcol SI and Separcol SI C18 L/T. The aim was to provide insight into some simple procedures yielding optimal selectivity/specificity of the isolation of the studied solutes either by proper selection of the sorbent or by applying sophisticated elution schemes which use to advantage different properties of the eluents/solvents.     

Thickness dependence of free‐standing thin films

Below a critical thickness, of about 60 nm, the glass transition temperature of polystyrene (PS) films decreases with film thickness, as demonstrated using free‐standing films. A geometrical model is developed here describing this phenomenon in the case of ideal (Gaussian) chains. This model, which can be considered as an application of the free volume model, assumes that the decrease of the glass transition temperature from thick to ultrathin films is due to the modification of the interpenetration between neighboring chains. The theoretical curve deduced from the model is in excellent agreement with the PS experimental results, without using any adjustable parameters. From these results, it can be concluded that new chain motions, usually buried in bulk samples, are expressed by the presence of the surface. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 10–17, 2007     

Analysis and finite element simulations of a second‐order fluid model in a bounded domain

This article is concerned with the equations governing the steady motion of a viscoelastic incompressible second‐order fluid in a bounded domain. A new proof of existence and uniqueness of strong solutions is given. In addition, using appropriate finite element methods to approximate a coupled equivalent problem, sharp error estimates are obtained using a fixed point argument. The method is applied to the two‐dimensional lid‐driven cavity problem, at low Reynolds number and in a certain range of values of the viscoelastic parameters, to analyze the combined effects of inertia and viscoelasticity on the flow. © 2007 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq, 2007     

The LEM exponential integrator for advection–diffusion–reaction equations

We implement a second-order exponential integrator for semidiscretized advection–diffusion–reaction equations, obtained by coupling exponential-like Euler and Midpoint integrators, and computing the relevant matrix exponentials by polynomial interpolation at Leja points. Numerical tests on 2D models discretized in space by finite differences or finite elements, show that the Leja–Euler–Midpoint (LEM) exponential integrator can be up to 5 times faster than a classical second-order implicit solver.     

Near-infrared laser photoacoustic detection of methane: the impact of molecular relaxation

A photoacoustic sensor has been developed for trace-gas monitoring using a near-infrared semiconductor laser emitting in the 2ν₃ band of methane at 1.65 μm. The apparatus was designed for on-line process control in the manufacturing of the novel low-water-peak fibres developed for optical telecommunications. The importance of collisional relaxation processes in the generation of the photoacoustic signal is reported in the particular case of CH₄ detection in dry O₂ and O₂–N₂ mixtures. The negative influence of these effects results in a strongly reduced and phase-shifted photoacoustic signal, induced by a fast resonant coupling between the vibrational states of methane and oxygen, associated with the slow relaxation of the excited oxygen molecules. An unusual parabolic response of the sensor with respect to the methane concentration has been observed and is discussed. Finally, the beneficial effect of several species, including water vapour and helium, acting as a catalyst to hasten the relaxation of the CH₄–O₂ system, is demonstrated. PACS 42.62.Fi; 33.20.Ea; 34.50.Ez     

Towards an universal classification of scale invariant processes

We consider fields which take random values over several decades. Starting from physical examples, we postulate that scale is not an absolute quantity. We then establish the equivalence between two existing approaches based on scale symmetry arguments as general as possible. This yields a classification of log-infinitely divisible laws, possibly universal. The physical significance of the parameters entering in the classification is discussed. Received: 7 November 1997 / Received in final form: 26 March 1998 / Accepted: 30 March 1998     

Collisions for the quantum Coulomb Hamiltonian

We study the propagation of phase space singularities for the time dependent Schrödinger equation with potential having Coulomb-type singularities in space dimension equal tothree. We prove that the singularities (frequency set) of the solution are reflected by a Coulomb center exactly as in the classical problem, i.e. the frequency set follows theregularized trajectories of Classical Mechanics after a collision.     

Synthesis and cationic photopolymerization of new fluorinated,polyfunctional propenyl ether oligomers

New fluorinated, polyfunctional propenyl ether functionalized resins were synthesized, and their behavior in cationic photopolymerization was investigated. The photopolymerization proceeded efficiently with a high double‐bond conversion (>90%), giving rise to UV‐cured coatings characterized by low glass‐transition temperatures (?33 °C ≤ glass‐transition temperature ≤ ?15 °C) and hydrophobic surface properties. A fluorinated additive was also employed as a reactive additive in the cationic photopolymerization of trimethylolpropane tripropenyl ether, increasing the double‐bond conversion, polymer network flexibility, thermal stability, and surface hydrophobicity. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6943–6951, 2006     

Critical thickness and stress relaxation in YBaCuO (123) strained epitaxial layers and YBaCuO based strained superlattices

An energy model has been used to calculate the critical thickness h _c of YBaCuO thin films and YBaCuO based superlattices within an isotropic or anisotropic approximation. The critical thickness of single layers calculated from the anisotropic model (16 nm) is in good agreement with the previously published experimental values which are spread out from 4 to 20 nm. In the case of superlattices, relaxation appears to be governed by the critical thickness of the elementary sub-layers and is then better evaluated through the calculation performed for YBaCuO single layers. XRD measurements on YBa₂Cu₃O₇/PrBa₂Cu_3?xGa_xO₇ superlattices grown on {100{ SrTiO₃ have evidenced a tetragonal stress in the YBaCuO ab plane which remains expanded when the YBaCuO elementary layer thickness is lower than 4.8 nm (4 YBaCuO cells). However the critical temperature of the shortest period superlattices is only slightly affected by this expanded stress in contrast to the effect of an elastic stress externally applied along the ab plane of YBaCuO thin films.