Analytical characteristics of a continuum-source tungsten coil atomic absorption spectrometer.

A continuum-source tungsten coil electrothermal atomic absorption spectrometer has been assembled, evaluated, and employed in four different applications. The instrument consists of a xenon arc lamp light source, a tungsten coil atomizer, a Czerny-Turner high resolution monochromator, and a linear photodiode array detector. This instrument provides simultaneous multi-element analyses across a 4 nm spectral window with a resolution of 0.024 nm. Such a device might be useful in many different types of analyses. To demonstrate this broad appeal, four very different applications have been evaluated. First of all, the temperature of the gas phase was measured during the atomization cycle of the tungsten coil, using tin as a thermometric element. Secondly, a summation approach for two absorption lines for aluminum falling within the same spectral window (305.5-309.5 nm) was evaluated. This approach improves the sensitivity without requiring any additional preconcentration steps. The third application describes a background subtraction technique, as it is applied to the analysis of an oil emulsion sample. Finally, interference effects caused by Na on the atomization of Pb were studied. The simultaneous measurements of Pb and Na suggests that negative interference arises at least partially from competition between Pb and Na atoms for H2 in the gas phase.     

A Grobman-Hartman theorem for general nonuniform exponential dichotomies

For a nonautonomous dynamics with discrete time given by a sequence of linear operators Am, we establish a version of the Grobman-Hartman theorem in Banach spaces for a very general nonuniformly hyperbolic dynamics. More precisely, we consider a sequence of linear operators whose products exhibit stable and unstable behaviors with respect to arbitrary growth rates ecρ(n), determined by a sequence ρ(n). For all sufficiently small Lipschitz perturbations Am+fm we construct topological conjugacies between the dynamics defined by this sequence and the dynamics defined by the operators Am. We also show that all conjugacies are Hölder continuous. We note that the usual exponential behavior is included as a very special case when ρ(n)=n, but many other asymptotic behaviors are included such as the polynomial asymptotic behavior when ρ(n)=logn.     

Transport properties of the A phase of superfluid 3He at low temperatures

The results of a calculation of transport properties of the A phase of superfluid ³He are reported. The temperature dependence of the normal fluid density, viscosity, thermal conductivity, and nuclear spin relaxation time are given.     

On removable singularities of locally solvable differential operators

We study removable sets of solutions of locally solvable partial differential operators with smooth coefficients and characterize them in terms of capacity in the sense of Harvey and Polking. For operators of order one we are able to give a geometric characterization of removable sets in terms of orbits in the sense of Sussmann. Oblatum 2-IX-1995 & 14-V-1996     

The mechanism of solvolysis of methyl perchlorate in hydroxylic solvents: calculation of the cavity terms

From standard Gibbs energies of transfer, corrected for cavity or nonelectrostatic effects, it is concluded that the solvolysis of methyl perchlorate takes place through a looser-than-usual S_N2 transition state with a charge separation of about 0.52 units.     

Action de l'AMP-c sur les monocouches mixtes de céphaéline-albumine d'œuf

Résumé En vue de vérifier si l'AMP-cyclique produit une action expansive lorsqu'il agit sur les monocouches de lipoprotéines mixtes ces monocouches insolubles ont été préparées avec de la céphaéline et de l'albumine dóeuf.Ces monocouches ont montré une bonne miscibilité entre les deux composants, et seules de faibles actions réciproques ont été observées.La pénétration de l'AMP-cyclique dans ces monocouches mixtes produit un effet expansif appréciable, son action atteignant le niveau maximal lorsque la concentration de l'AMP-cyclique dans la sous-phase est de 10^–6 M (concentration normale de la cellule).Un effet similaire sur les membranes mixtes de lipoprotéines de la paroi cellulaire est attribué a l'AMP-cyclique.

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With a view to checking whether cyclic-AMP produces an expansive action when acting on mixed lipoprotein monolayers, such insoluble monolayers were prepared with cephalin and egg albumin. These layers showed a good miscibility between the two components, with only weak interactions being observed.The penetration of cyclic-AMP in these mixed monolayers produces an appreciable expansive effect, its action reaching a maximum level when the cyclic-AMP concentration in the subphase is 10^–6 M (standard cell concentration).A similar effect on the lipoprotein mixed membranes of the cell wall is attributed to cyclic-AMP.

Directeur du Département: Prof. Dr. Serafín Garcia Fernández     

Fluorescent Properties of a Hybrid Cadmium Sulfide-Dendrimer Nanocomposite and its Quenching with Nitromethane

A fluorescent hybrid cadmium sulphide quantum dots (QDs) dendrimer nanocomposite (DAB-CdS) synthesised in water and stable in aqueous solution is described. The dendrimer, DAB-G5 dendrimer (polypropylenimine tetrahexacontaamine) generation 5, a diaminobutene core with 64 amine terminal primary groups. The maximum of the excitation and emission spectra, Stokes’ shift and the emission full width of half maximum of this nanocomposite are, respectively: 351, 535, 204 and 212 nm. The fluorescence time decay was complex and a four component decay time model originated a good fit (χ = 1.20) with the following lifetimes: τ ₁ = 657 ps; τ ₂ = 10.0 ns; τ ₃ = 59.42 ns; and τ ₄ = 265 ns. The fluorescence intensity of the nanocomposite is markedly quenched by the presence of nitromethane with a dynamic Stern-Volmer constant of 25 M⁻¹. The quenching profiles show that about 81% of the CdS QDs are located in the external layer of the dendrimer accessible to the quencher. PARAFAC analysis of the excitation emission matrices (EEM) acquired as function of the nitromethane concentration showed a trilinear data structure with only one linearly independent component describing the quenching which allows robust estimation of the excitation and emission spectra and of the quenching profiles. This water soluble and fluorescent nanocomposite shows a set of favourable properties to its use in sensor applications.