Specific cationic photoinitiators for near UV and visible LEDs: Iodonium versus ferrocenium structures

Two iodonium salts based on a coumarin chromophore are investigated for polymerization upon light emitting diode irradiations (LEDs). They work as one‐component photoinitiators. They initiate the cationic polymerization of epoxides (under air) and vinylethers (laminate) upon exposure to violet LEDs (385 and 405 nm). Excellent polymerization profiles are recorded. Their efficiency is quite similar to that of a ferrocenium salt. Interpenetrating polymer networks can also be obtained through a concomitant cationic/radical photopolymerization of an epoxy/acrylate blend monomer. The light absorption properties of these new salts as well as the involved photochemical mechanisms are investigated for the first time through electron spin resonance, laser flash photolysis, steady state photolysis experiments. Molecular orbital calculations are also used to shed some light on the initiation mechanisms. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42759.     

Microwave-Assisted Synthesis of Phenothiazine and Quinoline Derivatives

Application of a dynamic microwave power system in the chemical synthesis of some phenothiazine and quinoline derivatives is described. Heterocyclic ring formation, aromatic nucleophilic substitution and heterocyclic aldehydes/ketones condensation reactions were performed on solid support, or under solvent free reaction conditions. The microwave-assisted Duff formylation of phenothiazine was achieved. Comparison of microwave-assisted synthesis with the conventional synthetic methods demonstrates advantages related to shorter reaction times and in some cases better reaction yields.     

Sequestration and metabolism of protoxic pyrrolizidine alkaloids by larvae of the leaf beetle Platyphora boucardi and their transfer via pupae into defensive secretions of adults

Several neotropical leaf-beetles of the genus Platyphora ingest and specifically metabolize plant acquired pyrrolizidine alkaloids (PAs) of the lycopsamine type (e.g., rinderine or intermedine) and enrich the processed alkaloids in their exocrine defensive secretions. In contrast to the related palaearctic leaf beetles of the genus Oreina, which absorb and store only the non-toxic alkaloid N-oxides, Platyphora sequesters PAs exclusively as protoxic tertiary amines. In this study, the ability of P. boucardi larvae to accumulate PAs was investigated. Tracer studies with [¹⁴C]rinderine and its N-oxide revealed that P. boucardi larvae, like adult beetles, utilize the two alkaloidal forms with the same efficiency, but accumulate the alkaloid as a tertiary amine exclusively. Ingested rinderine is rapidly epimerized to intermedine, which is localized in the hemolymph and all other tissues; it is also detected on the larval surface. Like adults, larvae are able to synthesize their own alkaloid esters (beetle PAs) from orally administered [¹⁴C]retronecine and endogenous aliphatic 2-hydroxy acids. These retronecine esters show the same tissue distribution as intermedine. A long-term feeding experiment lasting for almost four months revealed that retronecine esters synthesized from [¹⁴C]retronecine in the larvae are transferred from larvae via pupae into the exocrine glands of adult beetles. Pupae contain ca. 45% of the labeled retronecine originally ingested, metabolized, and stored by larvae; ca. 12% of larval radioactivity could be recovered from the defensive secretions of adults sampled successively over two and a half months. Almost all of this radioactivity is found in the insect-made retronecine esters that are highly enriched in the defensive secretions, i.e., more than 200-fold higher concentration compared to pupae.     

Numerical Simulations of the Effect of Conical Dimension on the Hydrodynamic Behaviour in Spouted Beds

The flow behaviours of gas‐solids were predicted by means of a hydrodynamic model of dense gas‐solid flow in spouted beds. Constitutive equations describing the particulate solids pressure and viscosity were implemented into a hydrodynamic simulation computer program. The effect of operating conditions (inclined angle and gas spouting velocity) on particle velocity and concentration in the spout, annulus and fountain regions were numerical studied. Both vertical and horizontal particle velocities increased with increasing spouting gas velocity. The diameter of the spout increases with decreasing the inclination angle. As the inclination angle is set greater than 60°, the spout cross‐section starts becoming bottlenecked, limiting the upwards flow of solids.     

Nitrogen transformations and retention in planted and artificially aerated constructed wetlands

Nitrogen (N) processing in constructed wetlands (CWs) is often variable, and the contribution to N loss and retention by various pathways (nitrification/denitrification, plant uptake and sediment storage) remains unclear. We studied the seasonal variation of the effects of artificial aeration and three different macrophyte species (Phragmites australis, Typha angustifolia and Phalaris arundinacea) on N processing (removal rates, transformations and export) using experimental CW mesocosms. Removal of total nitrogen (TN) was higher in summer and in planted and aerated units, with the highest mean removal in units planted with T. angustifolia. Export of ammonium (NH₄⁺), a proxy for nitrification limitation, was higher in winter, and in unplanted and non-aerated units. Planted and aerated units had the highest export of oxidized nitrogen (NO_y), a proxy for reduced denitrification. Redox potential, evapotranspiration (ETP) rates and hydraulic retention times (HRT) were all predictors of TN, NH₄⁺ and NO_y export, and significantly affected by plants. Denitrification was the main N sink in most treatments accounting for 47-62% of TN removal, while sediment storage was dominant in unplanted non-aerated units and units planted with P. arundinacea. Plant uptake accounted for less than 20% of the removal. Uncertainties about the long-term fate of the N stored in sediments suggest that the fraction attributed to denitrification losses could be underestimated in this study.     

Chemometric analysis of combined NIR and MIR spectra to characterize French olives

Chemometric treatment of near‐infrared (NIR) and mid‐infrared (MIR) combined spectra was used firstly to predict oil and water contents in fresh olive fruit samples (n = 223) and secondly to classify these samples into five principal French cultivar origins (Aglandau, Cailletier, Olivière, Salonenque, and Tanche). The study was carried out during four crop years (2005/2006 to 2008/2009) to take into account the seasonal variations. The comparison of the results obtained in the combined range (REP = 2.6% for the water content and 3.5% for the oil content) provides an obvious advantage compared to the NIR and MIR techniques used separately. Fresh olive fruit cultivars were satisfactorily classified with the partial least squares‐discriminant analysis (PLS‐DA) method in the combined range. After use of the K‐means clustering on the PLS‐DA scores, all the samples were well classified into their five groups of origin. The use of infrared combined spectra allows a considerable improvement in estimating olive fruit quality (oil and water contents, varietal origins).     

Naturalistic study of rider's behaviour in initial training in France: Evidence of limitations in the educational content

This paper analyses motorcycle educational content in a number of French motorcycle schools on the basis of a naturalistic study of riders’ and trainers’ behaviour. The aim is to specify the situations delivered in motorcycle schools and to study the rider's activity in these situations. The methodology includes ethnographic observation within the motorcycle schools and the longitudinal monitoring of 14 trainee motorcyclists during their initial training. The training situations were described by the combination of audio–visual recordings and interviews data (i.e. concomitant or interruptive verbalization, and self-confrontation data). The results permit to (1) compare the “real” and “official” durations of track and on-road training, (2) characterize the real training situations, (3) describe the preferred forms of instruction, and (4) conduct an in-depth analysis of the situations used during training in traffic. The discussion show, in first, the poverty of the training situations which are based on the repetition of the exercises in the test, and, in second, disparities between the riding situations encountered during training and the demands made by riding in natural traffic. The usefulness and the applications of this type of approach – based on the integration of the rider's point of view notably by self-confrontation interview – for understanding real riding behaviours and how such approaches could supplement vehicle-based data are discussed in a large conclusion.     

Statistical analysis of concrete transport properties

Results of a statistical analysis of transport properties measurements carried out on a number of concrete mixtures are presented. Migration and drying experiments were performed to evaluate the ionic diffusion coefficients and permeability of concrete mixtures. Seven concrete mixtures were tested. The mixtures were either batched under laboratory conditions or sampled from construction sites. For each mixture, approximately eighty concrete samples from a single batch were tested. Ionic diffusion coefficients were calculated by analyzing the evolution of the electrical current passing through concrete samples during the migration tests. Calculations took into account the volume of permeable pores of the materials and the pore solution chemistry. Permeability was calculated from mass loss measured during drying tests. The study indicates that the coefficient of variation of ionic diffusion coefficients is 11.1 % on average, with a maximum of 23.5 %, and that the coefficient of variation of permeability is 20.6 % on average, with a maximum of 37.3 %.     

L'Alphabétisation technoscientifique et la démocratisation de la démocratie

Résumé

La métaphore du changement de guide proposée par Fensham (2002a) constitue un véritable faux‐fuyant. Cette solution aux présumés problèmes d'une alphabétisation technoscientifique pour tous et toutes fait l'impasse sur une interrogation plus générale à propos de la socialite des technosciences. Ainsi, l'auteur reconduit la séculaire séparation entre le monde de la science et celui de la société, qui justifie que seuls des ? experts ?, scientifiques ou sociétaux, puissent servir de médiateurs entre ces univers incommensurables. Il élimine donc d'emblée, en évoquant la complexité des problèmes, la possibilité pour les citoyens et les citoyennes ordinaires de s'engager dans les controverses sociotechniques qui traversent inévitablement nos sociétés. En conséquence, il se rabat sur une forme d'alphabétisation technoscientifique à deux vitesses ; l'une pour la populace, l'autre pour une élite qui, à terme, aura le privilège de pénétrer dans l'univers mystérieux et ésotérique de la science. Autrement dit, les contenus des curriculums pourront varier sans que la hiérarchie sociale des savoirs, de même que les pouvoirs forcément politiques des experts, soient menacés.