Structure of V(H2)n(+) Clusters for n = 1-6

Geometries, vibrational frequencies, spin states, H2 binding energies, and Delta(S) values have been determined for V(H2)n(+), for n = 1-6, using the B3LYP hybrid functional. The binding energies and Delta(S) values are in good agreement with experiment, thus showing that the B3LYP functional offers a reliable approach for optimizing the geometry and determining the H2 binding energies for this system. The calculations show that the increase in the binding energy and entropy associated with the addition of the sixth H2 to V(+) is due to a change in spin state from quintet for the smaller clusters to triplet for V(H2)6(+). The results for V(H2)n(+) are compared with those for CO(H2)n(+)

Use of synchronisation pattern to estimate geometric distortions

Publication in the conference proceedings of EUSIPCO, Toulouse, France, 200

Comparison between advected-field and level-set methods in the study of vesicle dynamics

International audiencePhospholipidic membranes and vesicles constitute a basic element in real biological functions. Vesicles are viewed as a model system to mimic basic viscoelastic behaviors of some cells, like red blood cells. Phase field and level-set models are powerful tools to tackle dynamics of membranes and their coupling to the flow. These two methods are somewhat similar, but to date no bridge between them has been made. This is a first focus of this paper. Furthermore, a constitutive viscoelastic law is derived for the composite fluid: the ambient fluid and the membranes. We present two different approaches to deal with the membrane local incompressibility, and point out differences. Some numerical results following from the level-set approach are presented

L’intégration d’une langue seconde dans l’enseignement des sciences physiques : quels termes pour quels savoirs en tronc commun et discipline non linguistique ?

Une discipline non linguistique (DNL) consiste en un enseignement optionnel en langue seconde d’une discipline aussi dispensée en langue maternelle au sein du tronc commun d’enseignements. L’article décrit une étude comparative du traitement d’un même objet de savoir de sciences physiques en tronc commun et DNL. L’étude est menée à l’échelle de séquences à l’aide d’un cadre sémiotique analysant les termes du discours de 4 enseignants de 2nde (2 de chaque section). Elle est ensuite renforcée par l’étude d’un extrait de chaque séquence. Toutes les observations convergent vers le constat d’un fort retrait, en DNL, du contenu disciplinaire. Ce résultat est discuté à la lumière de la littérature, et des contraintes sous lesquelles se tiennent les enseignements de DNL.Content and Language Integrated Learning (CLIL) is an optional class, given in L2, teaching a subject also taught in L1. The paper describes a comparative study of the same teaching module held within mainstream classes (L1) and CLIL classes (L2). First, the study is carried out on the scale of a full module using a semiotic frame analysing terms used in the speech of 4 teachers (2 in each context). It is completed by analyses of a short excerpt of each of the 4 modules. All our observations report a superficial presentation of the content in CLIL classes. The results are discussed with regard to the literature and to the constraints within which CLIL classes take place

Contrefaçon et ostentation

Le phénomène de contrefaçon fait l’objet de nombreuses études qui s’accordent sur les effets néfastes qu’engendre une telle activité sur les différents acteurs économiques. L’objectif de cet article est de montrer que dans certains cas, et particulièrement celui des biens de luxe, la contrefaçon peut être analysée différemment. La contrefaçon dans cette industrie répond à une défaillance du marché des biens de luxe à satisfaire une demande contrainte par le budget. Dans la mesure où les consommateurs ne sont pas trompés et que les producteurs ne peuvent introduire des produits de qualité inférieure, la contrefaçon peut être perçue comme un facteur d’efficience.In the last ten years, counterfeiting has drastically increased. It is generally argued that counterfeiting is economically harmful for both consumers and legal producers. The present paper aims at explaining in which circumstances counterfeiting is not that injurious from an economic perspective. In the case of luxury goods, that are attractive for counterfeiters, counterfeiting is a way to overcome the legal producer’s incapacity to satisfy the whole demand for budget constraints reasons. As long as counterfeit goods do not mislead consumers and legal producers are not able to supply lower quality goods, counterfeiting appears to improve efficiency

On the interaction between deprotonated Cytosine (C‐H) and Ba2+: Infrared multiphoton spectroscopy and dynamics

Gas-phase interactions between Ba2+ and deprotonated cytosine (C(−H)) were studied in [C(−H)Ba]+ and [C(−H)BaC]+ complexes by IRMPD spectroscopy coupled to tandem mass-spectrometry in combination with DFT calculations. For the [C(−H)BaC]+ complex only one [C(−H)KAN1O−Ba-Canti]+ isomer was found, although the presence of another structure cannot be excluded. This isomer features a central tetracoordinated Ba2+ that simultaneously interacts with keto-amino [C(−H)]− deprotonated on N1 and neutral keto-amino C. Both moieties are in different planes as a consequence of an additional NH…O=C hydrogen bond between C and [C(−H)]−. A sequential IRMPD dynamics is observed in this complex. For the [C(−H)Ba]+ complex produced by electrospray ionization two isomers ([C(−H)KAN1OBa]+ and [C(−H)KAN3OBa]+) were identified, in which Ba2+ interacts simultaneously with the C=O group and the N1 or N3 atom of the keto-amino [C(−H)]−, respectively. A comparison with the related [C(−H)Pb]+ complex (J. Y. Salpin et al., Chem. Phys. Chem. 2014, 15, 2959–2971) is also presented.Fil: Cruz Ortiz, Andres Felipe. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Taccone, Martín Ignacio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Maitre, Philippe. Universite de Paris XI. Laboratoire de Chimie Physique; FranciaFil: Rossa, Maximiliano. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Pino, Gustavo Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentin

Vibrational Spectroscopy of Platinum(II) Complexes Relevant in Antitumor Activity

International audienceCisplatin (cis-diamminedichloroplatinum(II) is the first platinum-based antitumor agent, and it is still widely used in chemotherapy. In the cytoplasm, the administered drug undergoes spontaneous hydrolysis by nucleophilic substitution of chloride with water. The cationic chloro-monoaqua form, cis-[PtCl(NH3)2(H2O)]+, characterized by a pKa value of 6.5, is the relevant intermediate at physiological pH, that can ultimately give rise to DNA and protein adducts through easy substitution of water by nitrogen/sulfur donor ligands. Electrospray ionization has allowed cis- and trans-[PtCl(NH3)2(H2O)]+ species to be obtained as free ions in the gas phase where they were sampled by infrared multiple photon dissociation (IRMPD) spectroscopy in the NH/OH stretching frequency range (3200−3800 cm−1), using a tabletop optical parametric oscillator/amplifier (OPO/OPA) laser system coupled to a quadrupole ion trap mass spectromete

Analyse critique de deux dispositifs pédagogiques de prototypage

International audienceCette contribution a pour objectif de présenter deux éditions d’un atelier interdisciplinaire et créatif à destination d’étudiantes et étudiants du bassin lausannois (Suisse) s’étant tenues sur deux années successives (2017 et 2018). En plus d’en décrire les origines, les buts et l’organisation, nous profiterons du recueil d’un certain nombre de données lors et après leur déroulement, pour en proposer une analyse critique au regard des modifications apportées suite aux limites attribuées à la première édition, et des perspectives pour la suite à donner à ces initiatives au sein des institutions impliquées

Hematopoietic IKBKE limits the chronicity of inflammasome priming and metaflammation

Obesity increases the risk of developing life-threatening metabolic diseases including cardiovascular disease, fatty liver disease, diabetes, and cancer. Efforts to curb the global obesity epidemic and its impact have proven unsuccessful in part by a limited understanding of these chronic progressive diseases. It is clear that low-grade chronic inflammation, or metaflammation, underlies the pathogenesis of obesity-associated type 2 diabetes and atherosclerosis. However, the mechanisms that maintain chronicity and prevent inflammatory resolution are poorly understood. Here, we show that inhibitor of κB kinase epsilon (IKBKE) is a novel regulator that limits chronic inflammation during metabolic disease and atherosclerosis. The pathogenic relevance of IKBKE was indicated by the colocalization with macrophages in human and murine tissues and in atherosclerotic plaques. Genetic ablation of IKBKE resulted in enhanced and prolonged priming of the NLRP3 inflammasome in cultured macrophages, in hypertrophic adipose tissue, and in livers of hypercholesterolemic mice. This altered profile associated with enhanced acute phase response, deregulated cholesterol metabolism, and steatoheptatitis. Restoring IKBKE only in hematopoietic cells was sufficient to reverse elevated inflammasome priming and these metabolic features. In advanced atherosclerotic plaques, loss of IKBKE and hematopoietic cell restoration altered plaque composition. These studies reveal a new role for hematopoietic IKBKE: to limit inflammasome priming and metaflammation