Etude de l'oxyde de cuivre CuO, matériau de conversion en film mince pour microbatteries au lithium (caractérisation des processus électrochimiques et chimiques en cyclage)

La miniaturisation des appareils électroniques et la multiplication de leurs fonctionnalités conduisent à développer des microsources d énergie adaptées, parmi lesquelles figurent les microbatteries au lithium. Malgré leurs excellentes performances, ces systèmes de stockage électrochimique tout solide restent toutefois limités en termes de capacité surfacique. Cette caractéristique étant intrinsèquement liée aux matériaux d électrodes, nous avons choisi de nous intéresser à des couches minces de CuO, dont la capacité volumique théorique (426 Ah .cm-2. m-1) est sensiblement plus élevée que celle des matériaux d intercalation utilisés jusqu à présent. Ce matériau réagit avec le lithium selon un mécanisme particulier, dit de conversion, qui induit la formation d un système multiphasé et nanostructuré d une grande complexité. Dans le cadre de ce travail, la compréhension des mécanismes électrochimiques et chimiques mis en jeu au cours du cyclage de couches minces d oxyde de cuivre (CuO) a été l objectif majeur. Celui-ci a nécessité une caractérisation fine du matériau actif d électrode et des interfaces générées (interfaces solide/solide et interface solide/électrolyte). Ces études ont été principalement menées à partir de la Spectroscopie Photoélectronique à Rayonnement X (XPS), de la Microscopie à Force Atomique (AFM) et d une modélisation théorique exploitant les méthodes de la chimie quantique. Les propriétés chimiques et morphologiques des couches minces de CuO cyclées ont été corrélées à leur comportement électrochimique. Une forte influence de leur structure et de leur morphologie initiales a pu être ainsi mise en évidenceThe miniaturization of electronic components and the increasing number of their functionalities lead to the development of suitable energy microsources, among which lithium microbatteries appear. Despite the excellent performances of these all-solid-state electrochemical power sources, one main limitation that remains is their surface capacity. Its value being intrinsically connected to the nature of electrode materials, we chose to focus on CuO thin films which are characterized by a theoretical volumetric capacity (426 Ah .cm-2. m-1) in far larger than the one of conventional intercalation materials used today. Indeed, this material reacts with lithium according to a particular mechanism, referred as conversion reaction, inducing the formation of a multiphase nanostructured system with a high complexity. In the framework of this study, understanding of electrochemical and chemical mechanisms which take place during the cycling of copper oxide thin films (CuO) was the main objective. This one has required a fine characterization of the electrode active material and the generated interfaces (solid/solid interfaces and solid/electrolyte interface). These studies have been mainly carried out with X-ray Photoelectron Spectroscopy (XPS), Atomic Force Microscopy (AFM) and theoretical approaches based on quantum chemistry methods. The chemical and morphological properties of the cycled CuO thin films have been linked to their electrochemical behavior. An important influence of their initial structure and morphology was then evidenced.PAU-BU Sciences (644452103) / SudocSudocFranceF

σ-Phase Formation in Super Austenitic Stainless Steel During Directional Solidification and Subsequent Phase Transformations

The solidification path and the σ-phase precipitation mechanism in the S31254 (UNS designation) steel are investigated thanks to Quenching during Directional Solidification (QDS) experiments accompanied by scanning electron microscopy observations and electron backscattered diffraction (EBSD) analysis. Considering experimental conditions, the γ-austenite is found to be the primary solidifying phase (1430 °C), followed by δ-ferrite (1400 °C, ≈ 87 pct solid fraction). The σ-phase appears in the solid-state through the eutectoid decomposition of the δ-ferrite: δ → σ + γ2 (1210 °C), whereas the σ-phase is predicted to form from the austenite at 1096 °C in equilibrium conditions. The resulting temperatures of solidification path and phase transformation are compared with Gulliver–Scheil model and equilibrium calculations predicted using Thermo-Calc© software. It is shown that the thermodynamics calculations agree with experimental results of solidification path. The EBSD analysis show that the δ-ferrite has δNW2 ORs with the σ-phase

Solidification path and phase transformation in super-austenitic stainless steel UNS S31254

The solidification path and the σ-phase precipitation mechanism of UNS S31254 alloy were studied on the basis of directional solidified experiments accompanied by scanning electron microscopy observations and energy dispersive X-ray a nalysis. The resulting temperatures of solidification paths and phase transformation were compared with Gulliver-Scheil and equilibrium calculations predicted using ThermoCalc© software. It was confirmed that the experimental solidification path was in agreement with the thermodynamic calculations. The complementarity of the results have made it possible to propose a solidification path and a σ-phase precipitation mechanism for the UNS31254 steel

A gene-expression profiling score for prediction of outcome in patients with follicular lymphoma: a retrospective training and validation analysis in three international cohorts

Patients with follicular lymphoma (FL) have heterogeneous outcomes. Predictor models able to distinguish, at diagnosis, patients at high versus low risk of progression are still needed. A training set of fresh-frozen tumour biopsies was prospectively obtained from 160 untreated patients with high-tumour-burden follicular lymphoma enrolled in the phase 3 randomised PRIMA trial, in which rituximab maintenance was evaluated after rituximab plus chemotherapy induction (median follow-up 6·6 years [IQR 6·0-7·0]). RNA of sufficient quality was obtained for 149 of 160 cases, and Affymetrix U133 Plus 2.0 microarrays were used for gene-expression profiling. We did a multivariate Cox regression analysis to identify genes with expression levels associated with progression-free survival independently of maintenance treatment in a subgroup of 134 randomised patients. Expression levels from 95 curated genes were then determined by digital expression profiling (NanoString technology) in 53 formalin-fixed paraffin-embedded samples of the training set to compare the technical reproducibility of expression levels for each gene between technologies. Genes with high correlation (>0·75) were included in an L2-penalised Cox model adjusted on rituximab maintenance to build a predictive score for progression-free survival. The model was validated using NanoString technology to digitally quantify gene expression in 488 formalin-fixed, paraffin-embedded samples from three independent international patient cohorts from the PRIMA trial (n=178; distinct from the training cohort), the University of Iowa/Mayo Clinic Lymphoma SPORE project (n=201), and the Barcelona Hospital Clinic (n=109). All tissue samples consisted of pretreatment diagnostic biopsies and were confirmed as follicular lymphoma grade 1-3a. The patients were all treated with regimens containing rituximab and chemotherapy, possibly followed by either rituximab maintenance or ibritumomab-tiuxetan consolidation. We determined an optimum threshold on the score to predict patients at low risk and high risk of progression. The model, including the multigene score and the threshold, was initially evaluated in the three validation cohorts separately. The sensitivity and specificity of the score for the prediction of the risk of lymphoma progression at 2 years were assessed on the combined validation cohorts. FINDINGS: In the training cohort, the expression levels of 395 genes were associated with a risk of progression. 23 genes reflecting both B-cell biology and tumour microenvironment with correlation coefficients greater than 0·75 between the two technologies and sample types were retained to build a predictive model that identified a population at an increased risk of progression (p<0·0001). In a multivariate Cox model for progression-free survival adjusted on rituximab maintenance treatment and Follicular Lymphoma International Prognostic Index 1 (FLIPI-1) score, this predictor independently predicted progression (adjusted hazard ratio [aHR] of the high-risk group compared with the low-risk group 3·68, 95% CI 2·19-6·17 [p<0·0001]). The 5-year progression-free survival was 26% (95% CI 16-43) in the high-risk group and 73% (64-83) in the low-risk group. The predictor performances were confirmed in each of the individual validation cohorts (aHR comparing high-risk to low-risk groups 2·57 [95% CI 1·65-4·01] in cohort 1; 2·12 [1·32-3·39] in cohort 2; and 2·11 [1·01-4·41] in cohort 3). In the combined validation cohort, the median progression-free survival was 3·1 years (95% CI 2·4-4·8) in the high-risk group and 10·8 years (10·1-not reached) in the low-risk group (p<0·0001). The risk of lymphoma progression at 2 years was 38% (95% CI 29-46) in the high-risk group and 19% (15-24) in the low-risk group. In a multivariate analysis, the score predicted progression-free survival independently of anti-CD20 maintenance treatment and of the FLIPI score (aHR for the combined cohort 2·30, 95% CI 1·72-3·07). INTERPRETATION: We developed and validated a robust 23-gene expression-based predictor of progression-free survival that is applicable to routinely available formalin-fixed, paraffin-embedded tumour biopsies from patients with follicular lymphoma at time of diagnosis. Applying this score could allow individualised therapy for patients according to their risk category

Extracorporeal Membrane Oxygenation for Severe Acute Respiratory Distress Syndrome associated with COVID-19: An Emulated Target Trial Analysis.

RATIONALE: Whether COVID patients may benefit from extracorporeal membrane oxygenation (ECMO) compared with conventional invasive mechanical ventilation (IMV) remains unknown. OBJECTIVES: To estimate the effect of ECMO on 90-Day mortality vs IMV only Methods: Among 4,244 critically ill adult patients with COVID-19 included in a multicenter cohort study, we emulated a target trial comparing the treatment strategies of initiating ECMO vs. no ECMO within 7 days of IMV in patients with severe acute respiratory distress syndrome (PaO2/FiO2 <80 or PaCO2 ≥60 mmHg). We controlled for confounding using a multivariable Cox model based on predefined variables. MAIN RESULTS: 1,235 patients met the full eligibility criteria for the emulated trial, among whom 164 patients initiated ECMO. The ECMO strategy had a higher survival probability at Day-7 from the onset of eligibility criteria (87% vs 83%, risk difference: 4%, 95% CI 0;9%) which decreased during follow-up (survival at Day-90: 63% vs 65%, risk difference: -2%, 95% CI -10;5%). However, ECMO was associated with higher survival when performed in high-volume ECMO centers or in regions where a specific ECMO network organization was set up to handle high demand, and when initiated within the first 4 days of MV and in profoundly hypoxemic patients. CONCLUSIONS: In an emulated trial based on a nationwide COVID-19 cohort, we found differential survival over time of an ECMO compared with a no-ECMO strategy. However, ECMO was consistently associated with better outcomes when performed in high-volume centers and in regions with ECMO capacities specifically organized to handle high demand. This article is open access and distributed under the terms of the Creative Commons Attribution Non-Commercial No Derivatives License 4.0 (http://creativecommons.org/licenses/by-nc-nd/4.0/)

Centrality evolution of the charged-particle pseudorapidity density over a broad pseudorapidity range in Pb-Pb collisions at root s(NN)=2.76TeV

Peer reviewe

The exfoliation process : regulatory mechanisms, role in regulating the number of cells in the mammary gland and in milk yield variations.

Le lait est produit par les cellules épithéliales mammaires (CEM). La quantité de lait produit est déterminée par le nombre de CEM et leur activité métabolique. Le nombre de CEM dépend de l’équilibre entre la prolifération cellulaire et l’apoptose. Le processus d’exfoliation, défini comme le décrochage des CEM de l’épithélium mammaire et leur évacuation dans le lait, a été proposé comme participant aussi à la régulation du nombre de CEM. Les objectifs de cette thèse étaient d’identifier les mécanismes biologiques impliqués dans la régulation de ce processus et d’étudier son rôle dans la régulation du nombre de CEM et son influence sur la production laitière. Nos résultats montrent qu’une partie des CEM est exfoliée entre deux traites consécutives.Cependant, la majorité des CEM sont exfoliées au moment de la traite suite à la contraction des cellules myoépithéliales et à la perte d’intégrité de l’épithélium induites par la décharge d’ocytocine. Le cortisol, au contraire, participerait à la restauration de l’intégrité de l’épithélium mammaire après la fin de la traite et limiterait l’exfoliation. Nous avons montré que les variations du taux d’exfoliation étaient opposées aux variations de production laitière dans le cas d’une restriction alimentaire et après la fin d’un traitement à l’hormone de croissance mais pas dans le cas d’un changement de fourrage, de l’inhibition de la prolactine et pendant un traitement à l’hormone de croissance. Le processus d’exfoliation des CEM participe donc à la régulation de la production laitière mais pas de façon systématique.Milk is synthesized by mammary epithelial cells (MEC). Milk yield is determined by the number of MEC in the mammary gland and the metabolic activity of these cells. It is well known that MEC number depends on the balance between cell proliferation and apoptosis. The MEC exfoliation process, defined as the shedding of MEC from the mammary epithelium into milk, is another process that might participate in the regulation of MEC number in the udder and thus in milk yield variations. The aims of this thesis were to identify the mechanisms that regulate the exfoliation process and to study the potential role of this process in regulating the number of MEC and milk yield.Our results showed that some MEC are exfoliated between milkings. Most of the MEC are, however, exfoliated during milking as a consequence of the myoepithelial cell contraction and the disruption of mammary epithelium integrity, both of which are caused by milking-induced oxytocin release. Cortisol may play a role in limiting MEC exfoliation by restoring mammary epithelium integrity after milking. We showed that the exfoliation process participates in regulating milk yield during feed restriction and after a treatment with bovine growth hormone but did not participate in regulating milk yield when forage in the ration was changed, when prolactin secretion was inhibited, or during a treatment with bovine growth hormone. These results suggest that the MEC exfoliation process likely participates in regulating milk yield but not systematically

Détection des mastocytes dans les adénomes de Conn (rôle potentiel dans la physiopatholgie de l'hyperaldostéronisme primaire)

L'hyperaldostéronisme primaire (HAP) est une cause classique d'hypertension artérielle. Les mécanismes physiopathologiques de l'adénome de Conn sont mal connus. Dans la surrénale humaine normale (SHN), la sérotonine (5-HT), produite par les mastocytes, stimule la sécrétion d'aldostérone via son récepteur de type 5-HT4. Par ailleurs, les mastocytes sont impliqués dans le développement tumoral de nombreux tissus. L'objectif de mon travail était de préciser le rôle des mastocytes et de la 5-HT dans le contrôle de la production d'aldostérone par les adénomes de Conn. Matériels et Méthodes : Nous avons étudié par immunohistochimie 21 tissus provenant de patients atteints d'adénome de Conn, 16 étaient suivis à Paris (HEGP) et 5 à Rouen, et 8 tissus contrôles provenant de pièces de néphrectomie élargie. Ces résultats ont été comparés rétrospectivement aux données cliniques et paracliniques des patients. Enfin, des cultures de cellules de lignées mastocytaires humaines (LAD 2 et HMC-1) et de cellules de la lignée corticosurrénalienne humaine H295R ont été réalisées. Résultats : Les tissus surrénaliens de patients atteints d'adénome de Conn contiennent des mastocytes de type MCt significativement plus nombreux que dans la SHN. Deux types de répartition mastocytaire sont observés : majoritairement péri-adénomateuse (= groupe A) et intra-adénomateuse (= groupe B). La taille des adénomes du groupe A est significativement supérieure à celle du groupe B et on observe une corrélation significative entre la densité des mastocytes et la taille de l'adénome. D'autre part, le récepteur de type 5-HT4est détecté au sein des adénomes et dans le tissu péri-tumoral. Les fibres nerveuses semblent établir des contacts avec les mastocytes en périphérie des adénomes pouvant ainsi contrôler leur activité. Enfin, les surnageants de culture des cellules HMC-1 et LAD 2 stimulent la production d'aldostérone par les cellules H295R et la 5-HT augmente la libération d'aldostérone par les cellules H295R via son récepteur 5-HT4. Conclusion : Les adénomes de Conn sont associés à une prolifération des mastocytes intra-sun-énaliens susceptibles de jouer un rôle dans le développement des lésions et l'hypersécrétion d'aldostérone via la 5-HT et son récepteur de type 4. Les mastocytes et le récepteur 5-HT4 représentent par conséquent des cibles potentiellement intéressantes pour le développement de traitements pharmacologiques de I' hyperaldostéronisme.ROUEN-BU Médecine-Pharmacie (765402102) / SudocSudocFranceF

Les préférences écologiques (paléorégimes alimentaires, paléohabitats) des grands mammifères herbivores des sites à Hominidés du miocène supérieur du Nord Tchad (reconstitution au moyen de l'analyse isotopique en carbone et oxygène du carbonate de l'émail dentaire)

POITIERS-BU Sciences (861942102) / SudocSudocFranceF