Self-modelling analysis applied to nanosecond transient absorption spectroscopy of flavone: an aid to elucidate and characterise reaction intermediates

A nanosecond transient absorption spectroscopy study of flavone performed with a 248 nm pump radiation has been investigated with the support of a chemometric treatment: SIMPLISMA. The experimental spectra obtained in various solvent with a pump-probe delay lower than about 2 micros are in quite good concordance with those already presented in the literature. Nevertheless after about 10 micros, the spectrum pattern significantly evolves as a function of time particularly for the methanolic solution. A qualitative analysis together with a SIMPLISMA chemometric treatment of the experimental data allowed to elucidate and characterise two interdependent transient species in the alcoholic medium: the lowest T1 triplet state of flavone and the ketyl radical forming by H-abstraction reaction from the solvent. In cyclohexane and acetonitrile, the same species seem to be produced in the studied time-scale but the radical form is generated with variable quantum yield depending on the solvent polarity. The pure spectrum and the photochemical kinetics of each reaction intermediate could have been determined with the help of the second derivative SIMPLISMA calculation procedure.     

The configurations in solution of the biliverdin TXγ phorcabilin and isophorcabilin dimethyl esters

The configurations in solution of the title compounds have been attributed by ¹H NMR. Correlations with the absorption spectra show the importance of conformational restraints in the spectroscopic properties of the bilatriene system which is usually chosen as chromophore model for the phytochrome phototransformation.     

A simple model to explain the complex kinetic behavior of epoxy/anhydride systems

A survey of the literature dealing with the kinetics of epoxy/anhydride polymerizations initiated by tertiary amines, shows inconsistencies in results reported by several authors. Both first-order and autocatalytic expressions have been used to fit experimental results. In the former case, significantly different values of apparent activation energies were found in isothermal and nonisothermal experiments. A simple kinetic model is proposed to explain these inconsistencies, based on the following steps: (a) a reversible reaction transforming an inactive initiator species into an active one, (b) a propagation step, and (c) a chain transfer step regenerating the active initiator (step not relevant to the kinetic analysis). The simple model explains both the first-order and autocatalytic behaviors reported in the literature. It also leads to the experimental values of the apparent activation energies obtained under different conditions. It is also shown that isoconversional methods should not be applied to obtain fundamental kinetic parameters in systems where the reaction rate depends on the concentration of an active species that varies independently of the conversion of functional groups. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2799–2805, 1999     

New dispersion process for submicronic fillers in thermoplastics

The addition of sufficiently small‐sized fillers in thermoplastics is supposed to allow an increase in stiffness while maintaining a good resilience. However, it is often difficult to obtain a good impact resistance because the dispersion of fine fillers is not perfect ‐ even using a powerful tool like a corotating twin screw extruder. This implies that the material will inevitably contain agglomerates that will cause a drastic drop in the material's resistance, bringing it down to the level of that of a coarse‐filler containing material. CERDATO, jointly with APPRYL, has designed a patented process for the dispersion of fine fillers in an extruder that allows this problem to be solved. The originality of this process lies in the optimization of the deagglomeration of the filler before its feeding into the extruder. As an example, polypropylene/submicronic calcium carbonate compounds show a joint gain in stiffness and impact resistance, while a traditional incorporation process (fillers fed in the melt) leads to an important loss in impact resistance.     

Geographic origins and compositions of virgin olive oils determinated by chemometric analysis of NIR spectra

The authentication of virgin olive oil samples requires usually the use of sophisticated and time consuming analytical techniques. There is a need for fast and simple analytical techniques for the objective of a quality control methodology. Virgin olive oils present characteristic NIR spectra. Chemometric treatment of NIR spectra was assessed for the quantification of fatty acids and triacylglycerols in virgin olive oil samples (n=125) and for their classification (PLS1-DA) into five very geographically closed registered designations of origin (RDOs) of French virgin olive oils ("Aix-en-Provence", "Haute-Provence", "Nice", "Nyons" and "Vallée des Baux"). The spectroscopic interpretation of regression vectors showed that each RDO was correlated to one or two specific components of virgin olive oils according to their cultivar compositions. The results were quite satisfactory, in spite of the similarity of cultivar compositions between two denominations of origin ("Aix-en-Provence" and "Vallée des Baux"). Chemometric treatments of NIR spectra allow us to obtain similar results than those obtained by time consuming analytical techniques such as GC and HPLC, and constitute a help fast and robust for authentication of those French virgin olive oils.     

High dose implantations of antimony for buried layer applicationsrrr

A computer simulation of low energy implantation is presented. The method of calculation takes into account the inelastic processes and vacancies in the crystal lattice.

The described simulation was used for a nitrogen implanted molybdenum single crystal. From the result of the calculation the possible positions of implanted nitrogen on the surface and in the bulk were obtained. The results of simulations are compared with those measured by SIMS and AES.     

Maximum likelihood estimation in a partially observed stratified regression model with censored data

The stratified proportional intensity model generalizes Cox’s proportional intensity model by allowing different groups of the population under study to have distinct baseline intensity functions. In this article, we consider the problem of estimation in this model when the variable indicating the stratum is unobserved for some individuals in the studied sample. In this setting, we construct nonparametric maximum likelihood estimators for the parameters of the stratified model and we establish their consistency and asymptotic normality. Consistent estimators for the limiting variances are also obtained.     

Attempts to separate (–)‐α‐thujone, (+)‐β‐thujone epimers from camphor enantiomers by enantioselective HPLC with polarimetric detection

In a first step, 26 chiral stationary phases (CSPs) have been screened for the separation of (–)‐α‐thujone, (+)‐β‐thujone epimers and camphor enantiomers by LC. The separations were monitored by a polarimeter detector. None of these CSPs provided a noticeable resolution for camphor enantiomers. The three components of a test mixture were clearly baseline separated on Chiralpak AS‐H, Chiralpak AZ‐H and TCI‐MBS (poly(N‐alpha‐(S)‐methylbenzylmaleimide) coated on silica gel) in a mobile phase composed of hexane/2‐PrOH (99:1 v/v). Interestingly, for a preparative application, the three CSPs produced different elution orders for the three constituents of the mixture. In a second step, it is shown that the use of online polarimetric detection constitutes an unprecedented method to reveal the occurrence and the relative content of thujone epimers and the chirality of the major camphor enantiomer in crude essential oils. A proof of concept is illustrated on crude essential oils from Rosmarinus tournefortii, Artemisia herba alba and A. arborescens, which grow in Morocco and have several traditional uses there. In a third step, pure (+)‐β‐thujone was quantitatively collected from A. arborescens crude oil by semi‐preparative HPLC on Chiralpak AZ‐H monitored by a polarimeter.     

Flow in wavy tube structure: asymptotic analysis and numerical simulationÉcoulement dans une structure tubulaire ondulée : analyse asymptotique et résolution numérique

This paper deals with the study of the stationary, incompressible, 2D flow of a fluid in a thin wavy tube. In this work, we consider a domain which is the union of two wavy tubes depending on a small parameter. The asymptotic expansion is constructed. The method of partial asymptotic decomposition is applied. The numerical implementation of this method for the extrusion process is developed. The new physical effects are discussed. To cite this article: A. Ainser et al., C. R. Mecanique 331 (2003).     

Asymptotic analysis for micropolar fluidsAnalyse asymptotique des fluides micropolaires

The flow of a micropolar fluid through a wavy constricted channel which depends on a small parameter ε?1 is considered. The asymptotic solution is built and justified thanks to a study of the boundary layers terms. The Stokes and Navier–Stokes problems set in a tube structure were previously considered. The method of partial asymptotic decomposition of domain (MAPPD) is also applied and justified for the micropolar flow problem. This method reduces the initial problem to the problem set in the boundary layers domain. To cite this article: D. Dupuy et al., C. R. Mecanique 332 (2004).