Quelques applications de la théorie générale des processus. I

Sans résuméEquipe de Recherche n^o 1 «Processus stochastiques et application» dépendant de la Section n^o 2 «Théories Physiques et Probabilités» associée au C.N.R.S.     

Correlating light and thermal stability of silver carboxylate complexes by infrared and 13C NMR spectroscopy

Bond nature of carboxylic groups can play an important role in Ag(I)-carboxylate compounds because light and thermal stability are important requirements for future applications such as antibacterial additives. A linear correlation between bond character and light stability of silver carboxylate complexes has been predicted by a direct relationship of infrared and ¹³C NMR spectroscopic data. This correlation is in agreement with the thermogravimetric analysis and provides a new approach to explore the interaction and the physical properties of metal-carboxylate bonds.     

On some variational properties of metric spaces

We use the basic formulation of Ekeland’s variational principle to establish characterizations of complete path metric spaces which, being described in terms of the strong slope, are called coherent as in [3]. We also provide some basic nonlinear error bound and metric regularity results, in the context of coherent spaces.     

Formal relations connecting different approaches to calculate relativistic effects on molecular magnetic properties

In the present work a set of formal relations connecting different approaches to calculate relativistic effects on magnetic molecular properties are proven. The linear response (LR) within the elimination of the small component (ESC), Breit Pauli, and minimal-coupling approaches are compared. To this end, the leading order ESC reduction of operators within the minimal-coupling four-component approach is carried out. The equivalence of all three approaches within the ESC approximation is proven. It is numerically verified for the NMR nuclear-magnetic shielding tensor taking HX and CH3X (X=Br,I) as model compounds. Formal relations proving the gauge origin invariance of the full relativistic effect on the NMR nuclear-magnetic shielding tensor within the LR-ESC approach are presented.     

New aspects in matrix-assisted laser desorption/ionization time-of-flight mass spectrometry: a universal solvent-free sample preparation

A method of solvent-free sample preparation is shown to be of universal applicability for matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). Results obtained were compared with those of traditional solvent-based sample preparation for MALDI-MS in order to demonstrate their similarities with respect to accuracy, sensitivity and resolution for polymers such as polystyrene and poly(methyl methacrylate) in a mass range from 2 to 100 kDa. The results revealed that there is fundamentally no difference in the quality of the obtained mass spectra, and we conclude that the mechanism of desorption and ionization remains unchanged. However, the solvent-free sample preparation turned out to have some advantages over the traditional method in certain cases: quick and easy applicability is shown for polyetherimide avoiding time-consuming optimization procedures. In particular, industrial pigments that are insoluble in common solvents were characterized without interfering signals from fragments. The method even showed improvements with respect to reproducibility and mass discrimination effects in comparison to traditional sample preparation. Additionally, this contribution provides new insight regarding the analyte/matrix preorganization for the desorption step which now appears to be independent of crystallinity.     

Thermodynamik des Systems n-Dekan—Aceton, 2. Mitt.

Zusammenfassung Die partielle Mischbarkeit im System n-Dekan—Aceton wird durch Senken der Temperatur vorgerichteter Proben bestimmt. Es wird versucht, diese Ergebnisse in symmetrischer Form darzustellen.

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Thermodynamics of the systeme n-decane—acetone

The partial miscibility of the system n-decane—acetone is measured by lowering the temperature of pre-prepared samples and an attempt to express these results in a symmetric form is made.

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Mit 3 Abbildungen

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Als Teil der Erfordernisse für den Titel eines Licenciado en Química der Pontificia Universidad Católica de Chile.     

Molecularly imprinted photocatalyst for glyceraldehyde production

Journal of Sol-Gel Science and Technology - In this work, a ZnO-based molecularly imprinted photocatalyst (MIP) bearing acid Lewis sites (Al) was evaluated for photocatalytic oxidation of glycerol....     

Evaluation of the molecular polarizability using the IPPP-CLOPPA-INDO/S method. Application to molecules of biological interest

The IPPP-CLOPPA-INDO/S method is introduced to investigate the static molecular polarizability in macromolecules. As an example of application, the polarizability of phospholipidic compounds, with and without the presence of water molecules has been estimated. The IPPP technique was employed to calculate the polarizability of the polar head and the hydrocarbon chains separately to analyze the feasibility of evaluating the total polarizability of the molecule by addition of these two projected results. INDO/S dipole moments of different fragments of the complex molecule were obtained by means of localized molecular orbitals in order to evaluate the charge transfer in the system.     

Short-time dynamics of a packing of polyhedral grains under horizontal vibrations

We analyze the dynamics of a 3D granular packing composed of particles of irregular polyhedral shape confined inside a rectangular box with a retaining wall subjected to horizontal harmonic forcing. The simulations are performed by means of the contact dynamics method for a broad set of loading parameters. We explore the vibrational dynamics of the packing, the evolution of solid fraction and the scaling of dynamics with the loading parameters. We show that the motion of the retaining wall is strongly anharmonic as a result of jamming and grain rearrangements. It is found that the mean particle displacement scales with inverse square of frequency, the inverse of the force amplitude and the square of gravity. The short-time compaction rate grows in proportion to frequency up to a characteristic frequency, corresponding to collective particle rearrangements between equilibrium states, and then it declines in inverse proportion to frequency.     

An example of stability for the minima of a sequence of dc functions: Homogenization for a class of nonlinear Sturm-Liouville problems

Combining the Clarke-Ekeland dual least action principle and the epi-convergence, we state an existence result and study the asymptotic behaviour for the periodic solution of a nonlinear Sturm-Liouville problem deriving from a convex subquadratic potential, when the data are perturbed in a suitable sense. The result appears like a stability result for the minimizers of a sequence of DC functions.