Réactivité chimique et électrochimique de clusters de palladium vis-à-vis d'halogénures organiques. Applications en électrocatalyse.

La chimie des clusters organométalliques est en continuel essor, comme en témoigne le nombre toujours croissant de publications qui leur sont consacrées. Cependant, les travaux sont dans leur grande majorité dévolus à la recherche d'architectures nouvelles et à leur caractérisation. Dans ce contexte, l'un des thèmes privilégiés de l'équipe « Electrosynthèse Organométallique » concerne l'élaboration de nouvelles formes de clusters, mais également l'étude de leur réactivité chimique et électrochimique et, plus encore, leur mise en oeuvre dans des processus d'électrocatalyse et/ou d'électrosynthèse. Précisément inscrit dans cette démarche, le travail présenté dans ce mémoire est consacré à l’activation de la liaison carbone-halogène par des clusters de palladium de formule Pd[indice]3(dppm)[indice]3(CO)[exposant]n+ (n = 0, 1, 2). Dans la première partie de notre mémoire, après avoir rappelé les différentes propriétés électroniques et structurales du complexe parent (n = 2) ainsi que certains aspects remarquables de sa réactivité, nous présenterons le comportement électrochimique des clusters Pd[indice]3(dppm)[indice]3(CO)[exposant]n+ et Pd[indice]3(dppm)[indice]3(CO)(X)[exposant]+ (X = I, Br, Cl). La seconde partie concernera l’étude de la réactivité du complexe trimétallique vis-à-vis des halogénures d’alkyle et des chlorures d’acide. Dans certains cas, le mécanisme intime de la réaction a pu être précisé par le biais d’études cinétiques (suivi électroanalytique ou spectrophotométrique). Nous montrerons également qu'on peut orienter sélectivement la réaction vers une voie ionique ou radicalaire selon l'état d'oxydation du complexe de départ. De plus, nous avons pu mettre en évidence que la transformation peut être induite par voie électrochimique dans le cas des halogénures d’alkyle. Enfin, la dernière partie de notre mémoire fait état de l’exploitation de cette réactivité en électrocatalyse et électrosynthèse organique. Au départ des chlorures d'acide, un procédé électrochimique a pu être mis au point et appliqué à différentes réactions d’acylation. Dans d'autres conditions, le cluster s'avère catalyser la réduction des halogénures organiques en leur radical

Effect of Additional Respiratory Muscle Endurance Training in Young Well- Trained Swimmers

International audienceWhile some studies have demonstrated that respiratory muscle endurance training (RMET) improves performances during various exercise modalities, controversy continues about the transfer of RMET effects to swimming performance. The objective of this study was to analyze the added effects of respiratory muscle endurance training (RMET; normocapnic hyperpnea) on the respiratory muscle function and swimming performance of young well-trained swimmers. Two homogenous groups were recruited: ten swimmers performed RMET (RMET group) and ten swimmers performed no RMET (control group). During the 8-week RMET period, all swimmers followed the same training sessions 5-6 times/week. Respiratory muscle strength and endurance , performances on 50-and 200-m trials, effort perception , and dyspnea were assessed before and after the intervention program. The results showed that ventilatory function parameters , chest expansion, respiratory muscle strength and endurance, and performances were improved only in the RMET group. Moreover, perceived exertion and dyspnea were lower in the RMET group in both trials (i.e., 50-and 200-m). Consequently , the swim training associated with RMET was more effective than swim training alone in improving swimming performances. RMET can therefore be considered as a worthwhile ergogenic aid for young competitive swimmers

Investigation of photocurrents resulting from a living unicellular algae suspension with quinones over time

International audiencePlants, algae, and some bacteria convert solar energy into chemical energy by using photosynthesis. In light of the current energy environment, many research strategies try to benefit from photosynthesis in order to generate usable photobioelectricity. Among all the strategies developed for transferring electrons from the photosynthetic chain to an outer collecting electrode, we recently implemented a method on a preparative scale (high surface electrode) based on a Chlamydomonas reinhardtii green algae suspension in the presence of exogenous quinones as redox mediators. While giving rise to an interesting performance (10-60 mA cm À2) in the course of one hour, this device appears to cause a slow decrease of the recorded photocurrent. In this paper, we wish to analyze and understand this gradual fall in performance in order to limit this issue in future applications. We thus first show that this kind of degradation could be related to over-irradiation conditions or side-effects of quinones depending on experimental conditions. We therefore built an empirical model involving a kinetic quenching induced by incubation with quinones, which is globally consistent with the experimental data provided by fluorescence measurements achieved after dark incubation of algae in the presence of quinones

Allometric scaling of the elevation of maternal energy intake during lactation

In most mammals, lactating mothers dramatically increase their food intake after parturition and reach a peak intake rate after a certain time while their offspring continue to grow. A common view, perpetuated by the metabolic theory of ecology, is that the allometric scaling of maternal metabolic rate with body mass limits the changes in energy intake and expenditure. Therefore these potential effects of metabolic scaling should be reflected in the elevation of maternal energy intake during lactation. To test this hypothesis, we collected published data on 24 species (13 domesticated) and established scaling relationships for several characteristics of the patterns of energy intake elevation (amplitude of the elevation, time to peak, and cumulative elevation to peak). A curvilinear allometric scaling relationship with maternal body mass (in double-logarithmic space) was found for the amplitude of maternal energy intake elevation, similarly to what has been observed for scaling relationships of basal metabolic rate in non-breeding mammals. This result indirectly supports the metabolic theory of ecology. However, this curvilinear allometric scaling does not seem to drive the scaling relationships found for the other characteristics of maternal energy intake. Both the duration and shape of the energy intake patterns showed substantial variation independently of species’ body mass. Data available for a few mammals, mostly domesticated, provides little evidence for the hypothesis that a single law of metabolic scaling governs the elevation of maternal energy intake after parturition. Obtaining further food intake data in wild species will be crucial to unravel the general mechanisms underlying variation in this unique adaptation of mammalian females

Impact of hypoventilation training on muscle oxygenation, myoelectrical changes, systemic [K+], and repeated-sprint ability in basketball players

This study investigated the impact of repeated-sprint (RS) training with voluntary hypoventilation at low lung volume (VHL) on RS ability (RSA) and on performance in a 30-15 intermittent fitness test (30-15IFT). Over 4 weeks, 17 basketball players included eight sessions of straight-line running RS and RS with changes of direction into their usual training, performed either with normal breathing (CTL, n = 8) or with VHL (n = 9). Before and after the training, athletes completed a RSA test (12 × 30-m, 25-s rest) and a 30-15IFT. During the RSA test, the fastest sprint (RSAbest), time-based percentage decrement score (RSASdec), total electromyographic intensity (RMS), and spectrum frequency (MPF) of the biceps femoris and gastrocnemius muscles, and biceps femoris NIRS-derived oxygenation were assessed for every sprint. A capillary blood sample was also taken after the last sprint to analyse metabolic and ionic markers. Cohen's effect sizes (ES) were used to compare group differences. Compared with CTL, VHL did not clearly modify RSAbest, but likely lowered RSASdec (VHL: −24.5% vs. CTL: −5.9%, group difference: −19.8%, ES −0.44). VHL also lowered the maximal deoxygenation induced by sprints ([HHb]max; group difference: −2.9%, ES −0.72) and enhanced the reoxygenation during recovery periods ([HHb]min; group difference: −3.6%, ES −1.00). VHL increased RMS (group difference: 18.2%, ES 1.28) and maintained MPF toward higher frequencies (group difference: 9.8 ± 5.0%, ES 1.40). These changes were concomitant with a lower potassium (K+) concentration (group difference: −17.5%, ES −0.67), and the lowering in [K+] was largely correlated with RSASdec post-training in VHL only (r = 0.66, p < 0.05). However, VHL did not clearly alter PO2, hemoglobin, lactate and bicarbonate concentration and base excess. There was no difference between group velocity gains for the 30-15IFT (CTL: 6.9% vs. VHL: 7.5%, ES 0.07). These results indicate that RS training combined with VHL may improve RSA, which could be relevant to basketball player success. This gain may be attributed to greater muscle reoxygenation, enhanced muscle recruitment strategies, and improved K+ regulation to attenuate the development of muscle fatigue, especially in type-II muscle fibers

Evf, a virulence factor produced by the Drosophila pathogen Erwinia carotovora, is an S-palmitoylated protein with a new fold that binds to lipid vesicles

Erwinia carotovora are phytopathogenic Gram-negative bacteria of agronomic interest as these bacteria are responsible for fruit soft rot and use insects as dissemination vectors. The Erwinia carotovora carotovora strain 15 (Ecc15) is capable of persisting in the Drosophila gut by the sole action of one protein, Erwinia virulence factor (Evf). However, the precise function of Evf is elusive, and its sequence does not provide any indication as to its biochemical function. We have solved the 2.0-angstroms crystal structure of Evf and found a protein with a complex topology and a novel fold. The structure of Evf confirms that Evf is unlike any virulence factors known to date. Most remarkably, we identified palmitoic acid covalently bound to the totally conserved Cys209, which provides important clues as to the function of Evf. Mutation of the palmitoic binding cysteine leads to a loss of virulence, proving that palmitoylation is at the heart of Evf infectivity and may be a membrane anchoring signal. Fluorescence studies of the sole tryptophan residue (Trp94) demonstrated that Evf was indeed able to bind to model membranes containing negatively charged phospholipids and to promote their aggregation

Reception Test of Petals for the End Cap TEC+ of the CMS Silicon Strip Tracker

The silicon strip tracker of the CMS experiment has been completed and was inserted into the CMS detector in late 2007. The largest sub system of the tracker are its end caps, comprising two large end caps (TEC) each containing 3200 silicon strip modules. To ease construction, the end caps feature a modular design: groups of about 20 silicon modules are placed on sub-assemblies called petals and these self-contained elements are then mounted onto the TEC support structures. Each end cap consists of 144 such petals, which were built and fully qualified by several institutes across Europe. Fro

Integration of the End Cap TEC+ of the CMS Silicon Strip Tracker

The silicon strip tracker of the CMS experiment has been completed and inserted into the CMS detector in late 2007. The largest sub-system of the tracker is its end cap system, comprising two large end caps (TEC) each containing 3200 silicon strip modules. To ease construction, the end caps feature a modular design: groups of about 20 silicon modules are placed on sub-assemblies called petals and these self-contained elements are then mounted into the TEC support structures. Each end cap consists of 144 petals, and the insertion of these petals into the end cap structure is referred to as TEC integration. The two end caps were integrated independently in Aachen (TEC+) and at CERN (TEC--). This note deals with the integration of TEC+, describing procedures for end cap integration and for quality control during testing of integrated sections of the end cap and presenting results from the testing