Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This study aims to investigate chemical, physical, mechanical and surface properties of Eucalyptus grandis and Eucalyptus cloeziana wood subjected to different treatments of freezing and heat. To achieve this, six trees for each specie were used to prepare sample for each mechanical test. The samples were subjected to six thermal treatments. Freezing treatment was performed in a horizontal freezer at -22 ± 2°C for 72 hours, while heat treatment was performed using an oven with force air circulation at 180 and 200 ± 1°C for 3.5 hours. Sampling to perform chemical, physical and surface tests were obtained from samples used in mechanical characterization of wood. Chemical changes were evaluated quantitatively through wet process and qualitatively through infrared spectroscopy (ATR-IR). Physical properties evaluated were: weight loss, specific gravity, equilibrium moisture content, dimensional stability and hygroscopicity of wood. Mechanical evaluation was performed through static bending, impact strength, compression parallel to fibers and Janka hardness. Color and wettability of wood were evaluated using colorimetry and contact angle techniques, respectively. The main findings showed that freezing slightly affected the chemical properties of wood, in which the main changes were found in heat treatments, mainly at 200°C. Freezing improve in weight and equilibrium moisture content of wood, while heat treatment caused weight loss and decrease of equilibrium moisture content of wood. Both heat treatments improved dimensional stability of wood, however when freezing and heat was performed in a combination, they did not showed the best results. Regarding the hygroscopicity of wood, results obtained in heat treatment at 200°C should be highlighted. On the other hand, freezing treatment increased absorption of water. In general, freezing reduced mechanical properties of wood. Heat treatments increased stiffness at static bending and strength at compression parallel to fibers of wood however was responsible for reduction in other mechanical properties. Color of wood was affected mainly for heat treatments, in which a darkening of surface was observed and quantified by decrease of parameter L*. Wettability of wood slightly decreased after heat treatments. Influence of freezing on wettability of wood was related to the natural characteristic of wood from species studied because they did not showed a defined tendency. Therefore, it is believed that treatments performed in this study changed significantly the technological properties of wood. / O presente estudo teve como objetivos investigar as propriedades químicas, físicas, mecânicas e superficiais da madeira de Eucalyptus grandis e Eucalyptus cloeziana submetida a diferentes tratamentos de congelamento e termorretificação. Para tanto, foram confeccionados, a partir de seis árvores de cada espécie, corpos de prova para cada ensaio mecânico. Os corpos de prova foram submetidos a seis tratamentos térmicos. O congelamento foi realizado em um freezer horizontal sob condições de temperatura e tempo de -22 ± 2°C durante 72 horas, enquanto que a termorretificação foi realizada em uma estufa laboratorial com circulação de ar forçada, à 180 e 200 ± 1°C durante 3,5 horas. A amostragem para realização dos ensaios químicos, físicos e superficiais foram provenientes dos corpos de prova utilizados na caracterização mecânica da madeira. As modificações químicas foram avaliadas quantitativamente em ensaios via úmida e qualitativamente por espectroscopia no infravermelho (ATR-IR). As propriedades físicas avaliadas foram a perda de massa e massa específica, teor de umidade de equilíbrio, estabilidade dimensional e higroscopicidade da madeira. Para avaliação das propriedades mecânicas foram realizados ensaios de flexão estática, flexão dinâmica, compressão paralela e dureza Janka. Também foram avaliadas a colorimetria e molhabilidade da madeira, por meio das técnicas de colorimetria e ângulo de contato. Os principais resultados encontrados mostraram que o congelamento pouco afetou as propriedades químicas da madeira, sendo as principais alterações oriundas do processo de termorretificação, principalmente a 200°C. O congelamento causou acréscimos na massa e no teor de umidade de equilíbrio da madeira, enquanto que a termorretificação ocasionou a perda de massa e redução do teor de umidade de equilíbrio. Os dois tratamentos térmicos causaram melhoria na estabilidade dimensional, entretanto, quando combinados, não apresentaram os melhores resultados. Para a higroscopicidade destacam-se os resultados obtidos na termorretificação a 200°C, por outro lado, o congelamento aumentou a absorção de água. De maneira geral, o congelamento causou redução nas propriedades mecânicas da madeira. A termorretificação causou aumento na rigidez a flexão estática e resistência a compressão paralela e redução nas demais propriedades mecânicas. A coloração da madeira foi afetada principalmente pela termorretificação, em que ocorreu um escurecimento superficial, quantificado pelo decréscimo do parâmetro de claridade L*. A molhabilidade da madeira diminuiu sensivelmente após a realização dos tratamentos de termorretificação. A influência do congelamento sobre a molhabilidade foi atribuída a características naturais da madeira das espécies estudadas, sem apresentar tendência definida. Dessa forma, verificou-se que os tratamentos realizados alteraram significativamente as propriedades tecnológicas da madeira.

Au cours des dernières décennies, les avancées en termes de technologies robotiques sous-marines ont permis de réaliser des levés sur les fonds marins à l'aide de véhicules sous-marins autonomes (AUV). Ainsi, équiper un AUV avec un sonar latéral permet de scanner une vaste zone de manière rapide. Naturellement, les forces armées se sont intéressées à de tels dispositifs pour effectuer des missions de chasses aux mines rapides et sécurisées pour le facteur humain. Néanmoins, analyser des images sonar par un ordinateur plutôt que par un opérateur reste très complexe. En effet, les chaînes de reconnaissance automatique de cibles (ATR) doivent faire face à la variabilité de l'environnement marin et il a été démontré qu'une forte relation existe entre la texture d'une image et la difficulté d'y détecter des mines. Effectivement, sur des fonds fortement texturés, voire encombrés, les performances d'une chaîne ATR peuvent être très dégradées. Ainsi, intégrer des informations environnementales dans le processus apparaît comme une piste crédible pour améliorer ses performances. Ces travaux de thèse proposent d'étudier la manière de décrire cet environnement marin et comment l'intégrer dans un processus ATR. Pour répondre à ces défis, nous proposons tout d'abord une nouvelle représentation des images sonar basée sur l'utilisation du signal monogène. Ce dernier permet d'extraire des informations énergétiques, géométriques et structurelles sur la texture locale d'une image. La nature multi-échelle de cet outil permet de tenir compte de la variabilité en taille des structures sous-marines. Ensuite, le concept de dimension intrinsèque est introduit pour décrire une image sonar en termes d'homogénéité, d'anisotropie et de complexité. Ces trois descripteurs sont directement reliés à la difficulté de détection des mines sous-marines dans un fond texturé et permettent de réaliser une classification très précise des images sonar en fonds homogènes, anisotropes et complexes. De notre point de vue, la chasse aux mines sous-marines ne peut pas être réalisée de la même manière sur ces trois types de fond. En effet, leurs natures et caractéristiques propres mènent à des challenges variés pour le processus ATR. Pour le démontrer, nous proposons de réaliser un premier algorithme de détection spécifique, appliqué aux zones anisotropes, qui prend en considération les caractéristiques environnementales de ces régions. / In the last decades, advances in marine robot technology allowed to perform accurate seafloor surveys by means of autonomous underwater vehicles (AUVs). Thanks to a sidescan sonar carried by an AUV, a wide area can be scanned quickly. Navies are really interested in using such vehicles for underwater mine countermeasures (MCM) purposes, in order to perform mine hunting missions rapidly and safely for human operators. Nevertheless, on-board intelligence, which intends to replace human operator for sonar image analysis, remains challenging. Current automatic target recognition (ATR) processes have to cope with the variability of the seafloor. Indeed, there is a strong relationship between the seafloor appearance on sidescan sonar images and the underwater target detection rates. Thus, embed some environmental information in the ATR process seems to be a way for achieving more effective automatic target recognition. In this thesis, we address the problem of improving the ATR process by taking into account the local environment. To this end, a new representation of sonar images is considered by use of the theory of monogenic signal. It provides a pixelwise energetic, geometric and structural information into a multi-scale framework. Then a seafloor characterization is carried out by estimating the intrinsic dimensionality of the underwater structures so as to describe sonar images in terms of homogeneity, anisotropy and complexity. These three features are directly linked to the difficulty of detecting underwater mines and enable an accurate classification of sonar images into benign, rippled or complex areas. From our point of view, underwater mine hunting cannot be performed in the same way on these three seafloor types with various challenges from an ATR point of view. To proceed with this idea, we propose to design a first specific detection algorithm for sand rippled areas. This algorithm takes into consideration an environmental description of ripples which allow to outperform classic approaches in this type of seafloor.

Le domaine de la bioénérgétique traîte de la circulation et de la transformation de l’énergie dans et entre des organismes et leur environnement. Dans ce manuscrit de thèse, la respiration cellulaire et plus particulièrement la première enzyme de la chaîne respiratoire, la NADH:ubiquinone oxidoreductase (Complexe I) ont été étudiées, dans l’objectif de clarifier sa fonction et son implication dans certaines maladies. Dans une première partie, la création d’une sonde impliquant l’enzyme immobilisée de façon biomimétique est décrite. La caractérisation de ce système est effectuée via spectroscopie infrarouge par exaltation de surface (SEIRAS) couplée à de l’électrochimie. Sa réponse à l’ajout de substrats et d’inhibiteurs est ensuite présentée. Dans une seconde partie, l’interaction du Complexe I avec des lipides et des inhibiteurs (Zn2+ et NADH-OH) ainsi que le rôle d’une Tyrosine située au site de fixation du NADH ont été étudiés par spectroscopies IR et UV-Vis différentielles induites par électrochimie. L’exploration des résultats obtenus sous un angle structural a finalement permis de proposer un modèle pour le mécanisme de couplage entre la réduction d’ubiquinone et le pompage de protons par le Complexe I. / The field of bioenergetics deals with the flow and transformation of energy within and between living organisms and their environment. The work presented in this thesis report focuses on cellular respiration and more specifically on the first enzyme of the respiratory chain, NADH:ubiquinone oxidoreductase (Complex I). This was done to clarify details about its function and its implication in disease. First, the creation of a sensor involving the biomimetically immobilized enzyme is presented and probed through a combination of surface enhanced infrared absorption spectroscopy (SEIRAS) and electrochemistry. This sensor is then tested against different substrates and inhibitors. In a second part, the interaction of Complex I with lipids, inhibitors (Zn2+ and NADH-OH) and the role of a Tyrosine residue situated in the NADH binding pocket are investigated through electrochemically induced UV-Vis and FTIR difference spectroscopies. The results gathered through these experiments are then explored under a structural perspective and a coupling mechanism between quinone reduction and proton translocation by Complex I is proposed.

Les Rotavirus appartiennent à la famille des Reoviridae, famille du groupe III des virus à ARN double brin. Identifiés en 1973 par Ruth Bishop, ces virus non enveloppés sont la première cause de diarrhée aiguë sévère du jeune enfant dans le monde. La capside virale icosaédrique est constituée de 3 couches protéiques de structure : la couche externe formée par la glycoprotéine VP7 d’où émergent les spicules de protéine VP4, la couche intermédiaire constituée par la protéine VP6 représentant près de 50 % du poids du virus et enfin, la couche interne appelée core, résultant de l’assemblage des protéines VP2, d’où émergent vers l’intérieur les protéines VP1 et VP3. Cette capside renferme un génome divisé en 11 segments d’ARN bicaténaires. A ces 6 protéines structurales s’ajoutent les protéines non structurales qui interviennent lors de la réplication du virus. Les deux protéines structurales, VP4 et VP7 sont essentielles pour la fixation de la particule triple couche (TLP) aux membranes des cellules hôtes, par interaction aux récepteurs intégrines, elle sont également impliqués dans la déstabilisation des membranes endosomales, indispensable à la libération de la particule double couche (DLP) infectieuse dans le cytoplasme. Actuellement, contrairement au mécanisme d’action de la protéine VP5*, celui de la glycoprotéine VP7 est inconnu. L’objectif de cette thèse, a été de comprendre le mécanisme moléculaire de déstabilisation des membranes par les peptides dérivés de VP7. Dans un premier temps nous avons montré, par des études in silico, l’existence d’un domaine prédit en hélice membranaire bordé de résidus arginine et lysine hautement conservés, situé à l’extrémité C-terminale de la glycoprotéine VP7. Ces résultats ont conduit à la synthèse de quatre peptides avec lesquels des tests de perméabilisation de membranes modèles de larges vésicules unilamellaires (LUVs) ont été menés. Ceux-ci ont permis d’identifier le domaine minimum le plus actif, VP723, parmi les peptides sélectionnés. Dans un second temps nous avons déterminé la structure de ces peptides par RMN, dans des conditions mimant l’environnement hydrophobe de la membrane. Le peptide minimal VP723 s’organise en hélice α-amphipathique, structure souvent impliquée dans la déstabilisation des membranes cellulaires. La comparaison de sa structure obtenue par RMN à celle du domaine correspondant dans la structure cristallographique de la protéine native montre le réarrangement conformationnel de ce segment après maturation par la trypsine. Ces résultats ont été confirmés par deux mutants de synthèse, dont l’un est inactif pour la perméabilisation des membranes modèles. Ces travaux ont été complétés par des expériences de Résonance Plasmonique aux Ondes guidée (PWR). Des études par RMN du solide sont en cours afin de déterminer l’orientation du peptide dans les membranes modèles. En conclusion, nos résultats mettent en évidence l’importance du domaine C-terminal VP723 de la protéine VP7 dans la déstabilisation des membranes, permettant d’assurer la translocation de la particule virale infectieuse (DLP) de l’endosome vers le cytoplasme. Un modèle du mécanisme d’entrée du virus, médié par les peptides dérivés de la maturation par la trypsine de la glycoprotéine VP7 est proposé. / Rotaviruses belong to the Reoviridae family, belonging to the group III of dsRNA viruses. Identified in 1973 by Ruth Bishop, these non-enveloped viruses are the leading cause of severe diarrhea in young children worldwide. The icosahedral capsid is composed of three structural protein layers: the outer one, formed by the glycoprotein VP7, emerges spicules protein VP4, the intermediate one consists of VP6 protein representing nearly 50% of the weight of the virus and finally, the inner one called core, results from the assembly of proteins VP2, emerges towards the inside of proteins VP1 and VP3. The capsid contains a genome divided into 11 segments of dsRNA. To these six structural proteins are added nonstructural proteins involved in virus replication. The two structural proteins, VP4 and VP7, are involved in the interaction of the triple layer particle (TLP) to integrin receptors, necessary for the release of the infectious double layer particle (DLP) into the cytoplasm following the permeabilization of the membrane of the endosome compartments. Currently, unlike the mechanism of action of the protein VP5*, the glycoprotein VP7 remains unknown. The objective of this work was to understand the molecular mechanism involved in the destabilization of membranes by peptides derived from VP7. In a first step, we have shown, by in silico studies, the existence of a helical trans-membrane domain predicted containing a highly conserved arginine and lysine residues, located at the C-terminus of the VP7 glycoprotein. These results led to the synthesis of four peptides with which permeabilizing tests of model membranes were conducted. We have identified the minimum of the most active domain, named VP723, among the selected peptides. In a second step, we determined the structure of these peptides by NMR under conditions mimicking the hydrophobic environment of the membrane. The VP723 peptide is organized like an α-helical amphipathic structure often involved in the destabilization of cell membranes. The comparison of the structure obtained by NMR to that of the corresponding domain in the crystallographic structure of the native protein shows a conformational rearrangement of the segment after trypsin maturation. These results were confirmed by two synthetic mutants, one of which is inactive for the permeabilization of model membranes. These studies were complemented by experiments Plasmon Resonance guided the Waves (PWR). Studies by solid state NMR are in progress to determine the orientation of the peptide in model of membranes. In conclusion, our results highlight the importance of the C-terminal domain of the VP7 protein, named VP723, in the destabilization of membranes, to ensure the translocation of the infectious viral particle (DLP) from the endosome into the cytoplasm compartments. A mechanism of virus entry mediated by peptides derived from trypsin maturation of the VP7 glycoprotein is proposed in this study.

Over the last decades organic light-emitting diodes (OLEDs) and organic solar cells (OSCs) have gained considerable attention as efficient, flexible, lightweight, and potentially low-cost technology for lighting and display applications or as a renewable energy source, respectively. However, achieving long-term stability remains challenging. Revealing and understanding aging processes is therefore of great interest. This work presents fundamental investigations to understand and circumvent organic device degradation. In the first part, single materials used in organic devices were investigated. By tailoring an attenuated total reflection infrared (ATR-IR) spectrometer to the specific needs and subsequent measurements, it is shown that the tris(8-hydroxyquinoline)aluminum (Alq3) molecule, a well known fluorescent green emitter, degrades during air exposure by the formation of carbonyl groups. By using a laser desorption/ionization time of flight mass spectrometer (LDI-TOF-MS) it was shown that a,w-bis-(dicyanovinylen)-sexithiophen (DCV6T-Bu4), a well known small-molecule material which is used as part of the active layer, reacts with oxygen during ultraviolet (UV) irradiation. By using climate boxes and a sun simulator the impact of dry and humid air as well as sunlight on C60, a widely-used acceptor molecule in organic solar cells, was investigated. The breaking of the C60 cage to C58 and C56 and the further reaction of these components with oxygen as well as the dimerization of C58 and C56 molecules were found. The degradation products such as C58O increase with air exposure time but they are independent of the humidity level of the ambient air as well as sunlight irradiation. Subsequent annealing leads to a decrease of the C58O concentration. Many efficient n-dopants are prone to degradation in air, due to the low ionization potentials, thereby limiting the processing conditions. It was found that the air exposure of the highly efficient n-dopant tetrakis(1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinato)ditungsten(II) (W2(hpp)4) leads to oxidation reactions of the molecule to [W(hpp)2 + O] and other degradation products. The decay constant of W2(hpp)4 and the matching mean growth time of the [W(hpp)2 + O] degradation as well as a second very quick degradation of the dopant could be determined. The two decay constants can be explained by the assumption that W2(hpp)4 molecules, which are involved in the charge transfer, do degrade slower due to the fact that the charge transfer leads to a downshift of the energy levels of the W2(hpp)4 molecule. Apart from the properties of the organic materials, other effects such as the impact of different purification systems on the material purity as well as the dependence of material purity on the OLED lifetime has been investigated. No correlations between the purification grade and the amount of impurities were found. OLEDs which contain N,N\'-di(naphthalen-1-yl)-N,N\'-diphenyl-benzidine (alpha-NPD) purified in a vertically interlaced stainless steel sublimation systems shows slightly higher external quantum efficiencies compared to tube-based vacuum sublimation systems. The devices which contain alpha-NPD purified by a sublimation system have an extended lifetime. Finally, the impact of residual gases during device fabrication on OLED lifetime and electrical characteristics was investigated. It was found that water vapor introduces an additional series resistance to the OLED, while the other gases do not influence the electric characteristics. The presence of nitrogen or oxygen impacts the lifetime of the OLEDs by the same amount. Nitrogen is non-reactive, this leads to the conclusion that the influence of nitrogen and oxygen on the OLED lifetime is of non-chemical nature, such as changes in the morphology of the organic layers. Water vapor introduces an additional, even faster degradation process within the first hours of OLED operation. As major sources of device degradation, the dimerization of 4,7-diphenyl-1,10-phenanthroline (BPhen) as well as the complexation reaction of alpha-NPD with a bis(1-phenylisoquinoline)iridium(III) (Ir(piq)2) fragment was identified.

Die Zellmembran dient der Zelle nicht nur als äußere Hülle, sondern ist auch an einer Vielzahl von lebenswichtigen Prozessen wie Signaltransduktion oder Zelladhäsion beteiligt. Wasser als integraler Bestandteil von Zellen und der extrazellulären Matrix hat sowohl einen großen Einfluss auf die Struktur von Biomolekülen, als auch selbst besondere Merkmale in eingschränkter Geometrie. Im Rahmen dieser Arbeit wurden zwei Effekte an Modellmembranen untersucht: Erstens der Einfluss des Gegenions an kationischen Lipiden (DODAX, X = F, Cl, Br, I) auf die Eigenschaften des Grenzflächenwassers und zweitens das Vermögen durch Viskositätsänderungen das Wachstum von Nervenzellen anzuregen sowie die einzelnen Stadien der Bildung von neuronalen Netzwerken und deren Optimierung zu charakterisieren. Lipidmultischichten und darin adsorbiertes Grenzflächenwasser wurden mittels Infrarotspektroskopie mit abgeschwächter Totalreflexion untersucht. Nach Charakterisierung von Phasenverhalten und Wasserkapazität der Lipide wurden die Eigenschaften des Wassers durch kontrollierte Hydratisierung bei einem Wassergehalt von einem Wassermolekül pro Lipid verglichen. Durch die geringe Wasserkapazität können in diesem besonderen System direkte Wechselwirkungen zwischen Lipiden und Wasser aus der ersten Hydratationsschale beobachtet werden. Bemerkenswert strukturierte OH-Streckschwingungsbanden in Abhängigkeit des Anions und niedrige IR-Ordnungsparameter zeigen, dass stark geordnete, in ihrer Mobilität eingeschränkte Wassermoleküle an DODAX in verschiedenen Populationen mit unterschiedlich starken Wasserstoffbrückenbindungen existieren und sich vermutlich in kleinen Clustern anordnen. Die zweite Fragestellung hatte zum Ziel, das Wachstum von Nervenzellen auf Membranen zu beleuchten. Auf der Ebene einzelner Zellen wurde untersucht, ob sich in Analogie zu den bisher verwendeten elastischen Substraten, die Viskosität von Membranen als neuartiger physikalischer Stimulus dafür eignet, das mechanosensitive Verhalten von Neuronen zu modulieren. Das Wachstum der Neuronen wurde auf substrat- und polymergestützten Lipiddoppelschichten mittels Phasenkontrastmikroskopie beobachtet. Die Quantifizierung der Neuritenlängen, -auswuchsgeschwindigkeiten und -verzweigungen zeigten kaum signifikante Unterschiede. Diffusionsmessungen (FRAP) ergaben, dass entgegen der Erwartungen, die Substrate sehr ähnliche Fluiditäten aufweisen. Die Betrachtung der zeitlichen Entwicklung des kollektiven Neuronenwachstums, also der Bildung von komplexen Netzwerken, offenbarte robuste „Kleine-Welt“-Eigenschaften und darüber hinaus unterschiedliche Stadien. Diese wurden durch graphentheoretische Analyse beschrieben, um anhand typischer Größen wie dem Clusterkoeffizienten und der kürzesten Pfadlänge zu zeigen, wie sich die Neuronen in einem frühen Stadium vernetzen, im Verlauf eine maximale Komplexität erreichen und letztlich das Netzwerk durch effiziente Umstrukturierung hinsichtlich kurzer Pfadlängen optimiert wird.

Le sujet de cette thèse concerne les applications hautes températures, où les moteurs doivent être capables de fonctionner à 400°C pendant 2 heures, selon la norme en vigueur. Il convient dans ce type d’applications de disposer de matériaux assez stables pour que leurs propriétés isolantes restent inchangées, ce qui est le cas du fil émaillé PolyImide (PI). Ce fil émaillé pose néanmoins des problèmes économiques et de fournisseurs, d’où la nécessité de trouver d’autres alternatives. Ce travail de thèse a eu pour but de mettre au point et valider des techniques d’analyses (ATG / ATM / ATR-FTIR / DRS) adaptées au fil émaillé, et ce jusqu’à 400°C. Le PEI présente des propriétés insuffisantes pour ce type d’application car il se dégrade avant 350°C et perd ses propriétés d’isolation électrique. Le PAI est un matériau qui ne se dégrade que peu avant 400°C, et présente des caractéristiques électriques (propriétés diélectriques et de conduction) déjà plus proche du PolyImide. Nous avons pu établir la comparaison de deux PAI dont l’un est conventionnel et l’autre est un nanocomposite à base d’alumine. Ce dernier PAI est plus stable en température mais ne semble pas avoir de propriétés électriques très supérieures. Pour confronter les résultats expérimentaux obtenus dans des conditions particulières aux conditions réelles d’utilisation, des moteurs avec ces fils émaillés ont été fabriqués. Les moteurs équipés des fils PEI/PAI (fil standard) et PAI sont défaillants après 40 minutes au lieu de 2h, contrairement aux moteurs équipés de fil PI. La dégradation du PEI et le fluage du PAI, caractérisé au-delà de sa Tg (280°C), peuvent être la cause des dysfonctionnements de ces moteurs / This work is related to the high temperature application where motors have to withstand severe conditions - 400°C during 2 hours - according to the standard. Electrical insulation becomes a serious challenge for such application where materials have to remain stable, which is the case of PolyImide enameled wire. Other alternatives have to be found because this is a very expensive material with a small number of suppliers. The thermal, structural, mechanical and electrical properties of these systems have been investigated in-situ until 400°C by thermogravimetric analysis, ATR-FTIR microscopy, thermomechanical analysis, dielectric spectroscopy and DC voltage experiments. Dielectric spectroscopy has indicated a loss of insulating properties during the thermal cycle especially for PEI-containing enamels that degrades before 350°C. PAI enameled wires degrade just before 400°C, and electrical properties (dielectric properties and conductivity) are closer to PI‘s in this temperature range. A comparison between a conventional PAI and a PAI filled with nanoparticules of aluminium oxide has been made. The nanocomposite is thermally more stable but does not show better electrical behavior. To correlate all these results to the real test conditions (combined thermal, electrical and mechanical stresses), electrical motors have been fabricated using the enameled wires said before. They all breakdown after 40 minutes running, except motors made with PI enameled wires. The degradation of PEI ad the creeping of PAI up to its Tg (280°C) can explain the breakdown of these motors

The migration behavior of actinides and other radioactive contaminants in the environment is controlled by prominent molecular phenomena such as hydrolysis and complexation reactions in aqueous solutions as well as the diffusion and sorption onto minerals present along groundwater flow paths. These reactions significantly influence the mobility and bioavailability of the metal ions in the environment, in particular at liquid-solid interfaces. Hence, for the assessment of migration processes the knowledge of the mechanisms occurring at interfaces is crucial. The required structural information can be obtained using various spectroscopic techniques. In the present study, the speciation of uranium(VI) and neptunium(V) at environmentally relevant mineral – water interfaces of oxides of titania, alumina, silica, zinc, and alumosilicates has been investigated by the application of attenuated total reflection Fourier-transform infrared (ATR FT-IR) spectroscopy. Moreover, the distribution of the hydrolysis products in micromolar aqueous solutions of U(VI) and Np(V/VI) at ambient atmosphere has been characterized for the first time, by a combination of ATR FT-IR spectroscopy, near infrared (NIR) absorption spectroscopy, and speciation modeling applying updated thermodynamic databases. From the infrared spectra, a significant change of the U(VI) speciation is derived upon lowering the U(VI) concentration from the milli- to the micromolar range, strongly suggesting the dominance of monomeric U(VI) hydrolysis products in the micromolar solutions. In contradiction to the predicted speciation, monomeric hydroxo species are already present at pH ≥ 2.5 and become dominant at pH 3. At higher pH levels (> 6), a complex speciation is evidenced including carbonate containing complexes. For the first time, spectroscopic results of Np(VI) hydrolysis reactions are provided in the submillimolar concentration range and at pH values up to 5.3, and they are comparatively discussed with U(VI). For both actinides, the formation of similar species is suggested at pH ≤ 4, whereas at higher pH, the infrared spectra evidence structurally different species. At pH 5, the formation of a carbonate-containing dimeric complex, that is (NpO2)2CO3(OH)3−, is strongly suggested, whereas carbonate complexation occurs only under more alkaline conditions in the U(VI) system. The results from the experiments of the sorption processes clearly demonstrate the formation of stable U(VI) surface complexes at all investigated mineral phases. This includes several metal oxides, namely TiO2, Al2O3, and SiO2, serving as model systems for the elucidation of more complex mineral systems, and several alumosilicates, such as kaolinite, muscovite and biotite. From a multiplicity of in situ experiments, the impact of sorbent characteristics and variations in the aqueous U(VI) system on the sorption processes was considered. A preferential formation of an inner-sphere complex is derived from the spectra of the TiO2 and SiO2 phases. In addition, since the in situ FT-IR experiments provide an online monitoring of the absorption changes of the sorption processes, the course of the formation of the U(VI) surface complexes can be observed spectroscopically. It is shown that after prolonged sorption time on TiO2, resulting in a highly covered surface, outer-sphere complexation predominates the sorption processes. The prevailing crystallographic modification, namely anatase and rutile, does not significantly contribute to the spectra, whereas surface specific parameters, e.g. surface area or porosity are important. A significant different surface complexation is observed for Al2O3. The formation of inner-spheric species is assumed at low U(VI) surface coverage which is fostered at low pH, high ionic strength and short contact times. At proceeded sorption the surface complexation changes. From the spectra, an outer-spheric coordination followed by surface precipitation or polymerization is deduced. Moreover, in contrast to TiO2, the appearance of ternary U(VI) carbonate complexes on the γ-Al2O3 surface is suggested. The first results of the surface reactions on more complex, naturally occurring minerals (kaolinite, muscovite and biotite) show the formation of U(VI) inner-sphere sorption complexes. These findings are supported by the spectral information of the metal oxide surfaces. In this work, first spectroscopic results from sorption of aqueous Np(V) on solid mineral phases are provided. It is shown that stable inner-sphere surface species of NpO2+ are formed on TiO2. Outer-sphere complexation is found to play a minor role due to the pH independence of the sorption species throughout the pH range 4 – 7.6. The comparative spectroscopic experiments of Np(V) sorption onto TiO2, SiO2, and ZnO indicate structurally similar bidentate surface complexes. The multiplicity of IR spectroscopic experiments carried out within this study yields a profound collection of spectroscopic data which will be used as references for future investigations of more complex sorption systems in aqueous solution. Furthermore, from a methodological point of view, this study comprehensively extends the application of ATR FT-IR spectroscopic experiments to a wide range in the field of radioecology. The results obtained in this work contribute to a better understanding of the geochemical interactions of actinides, in particular U(VI) and Np(V/VI), in the environment. Consequently, more reliable predictions of actinides migration which are essential for the safety assessment of nuclear waste repositories can be performed. / Das Migrationsverhalten von Aktiniden und anderen radioaktiven Schadstoffen in der Umwelt wird von wichtigen molekularen Prozessen entlang der Grundwasserfließwege reguliert. Dazu gehören sowohl die Hydrolyse und Komplexierung in wässrigen Lösungen als auch Diffusion und Sorption der Schwermetalle an Mineralen. Diese Reaktionen beeinflussen entscheidend die Mobilität und Bioverfügbarkeit der Metallionen in der Umwelt, insbesondere an den fest-flüssig Grenzflächen. Genaue Kenntnisse über die an diesen Grenzflächen stattfindenden Mechanismen sind somit entscheidend, um Migrationsprozesse verlässlich abschätzen zu können. Die benötigten strukturellen Informationen können mit verschiedenen spektroskopischen Techniken ermittelt werden. Das Ziel der vorliegenden Arbeit war die Untersuchung der Speziation von Uran(VI) und Neptunium(V) an umweltrelevanten Grenzflächen von Oxiden des Titans, Aluminiums, Siliziums und Zinks und von Alumosilikaten mittels ATR FT-IR Spektroskopie. Des Weiteren wurde die Verteilung aquatischer Spezies in mikromolaren Lösungen des U(VI) und Np(V/VI) unter Normalbedingungen charakterisiert. Diese erstmalige Untersuchung wurde mit einer Kombination aus Speziationsmodellierung unter Anwendung aktueller thermodynamischer Daten und ATR FT-IR und NIR Absorptionsspektroskopie realisiert. Die Infrarotspektren zeigen eine deutliche Änderung der Speziesverteilung im Konzentrationsverlauf vom millimolaren zum mikromolaren Bereich. Dies verweist auf die Bildung monomerer U(VI) Hydrolyseprodukte. Im Gegensatz zu berechneten Speziationen werden diese monomeren Komplexe schon bei pH ≥ 2,5 gebildet und dominieren die Speziation bei pH 3. Bei höheren pH-Werten (> 6) konnte eine komplexe Speziesverteilung mit Anteilen von Karbonatkomplexen nachgewiesen werden. Erstmals konnten im Rahmen dieser Arbeit spektroskopische Befunde der Hydrolysereaktionen des Np(VI) im submillimolaren Konzentrationsbereich bis pH 5,3 erhalten werden. Diese wurden im Vergleich mit der U(VI) Speziation diskutiert. Obwohl im sauren Bereich (pH ≤ 4) die Bildung ähnlicher Komplexe nachgewiesen wurde, zeigen die bei höheren pH-Werten erhaltenen Spektren eine unterschiedliche Speziesverteilung. Im Gegensatz zum U(VI) bildet das Np(VI) schon bei pH 5 karbonathaltige aquatische Spezies wie (NpO2)2CO3(OH)3−. Die Ergebnisse der Sorptionsexperimente von U(VI) zeigen die Bildung stabiler Oberflächenkomplexe an allen untersuchten Mineralphasen. Dies umfasst mehrere als Modellsystem dienende Metalloxide wie TiO2, Al2O3 und SiO2, als auch komplexere Alumosilikate wie Kaolinit, Muskovit und Biotit. Für eine detaillierte Charakterisierung der Oberflächenkomplexe wurde eine Vielzahl von in situ Sorptionsexperimenten durchgeführt, die den Einfluss unterschiedlicher Parameter der mineralischen Phase als auch des wässrigen U(VI) Systems berücksichtigen. Die bevorzugte Bildung von innersphärischen Komplexen an TiO2 und SiO2 wird aus den spektroskopischen Daten abgeleitet. Da die in situ FT-IR Spektroskopie eine kontinuierliche Registrierung der Absorptionsänderungen während der ablaufenden Sorptionsprozesse erlaubt, kann somit der Verlauf dieser Prozesse quasi in Echtzeit spektroskopisch verfolgt werden. Es konnte gezeigt werden, dass mit fortschreitender Sorptionsdauer, d.h. bei hohen Beladungsdichten, die Bildung einer weiteren außersphärischen Spezies die Sorption dominert. Die vorliegende kristallographische Modifikation, Anatas und Rutil, ist nicht maßgeblich für das Auftreten unterschiedlicher Sorptionsprozesse verantwortlich, obwohl Parameter wie die spezifische Oberfläche und die Porosität für den Sorptionsprozess von Bedeutung sind. Deutlich verschiedene Oberflächenreaktionen werden für Al2O3 beobachtet. Aus den Spektren kann die Ausbildung einer innersphärischen Spezies bei sehr niedrigen U(VI) Beladungen, niedrigen pH-Werten, hohen Ionenstärken und kurzen Kontaktzeiten abgeleitet werden. Bei fortschreitender Sorption ändert sich die Art der Oberflächenkomplexe. Zunächst bilden sich außersphärische Spezies, während im weiteren Verlauf die Spektren auf eine beginnende Oberflächenausfällung bzw. Polymerisation hinweisen. Weiterhin wird das Auftreten von ternären U(VI) Karbonatkomplexen an γ-Al2O3 aus den spektroskopischen Daten abgeleitet. Die ersten Ergebnisse der Sorptionsexperimente an komplexeren, natürlich auftretenden Mineralphasen (Kaolinit, Muskovit und Biotit) zeigen eine bevorzugte Ausbildung von innersphärischen U(VI) Komplexen. Diese Resultate werden durch die spektralen Befunde der Experimente der Metalloxide gestützt. Erstmalig werden in dieser Arbeit spektroskopische Ergebnisse der Sorptionsprozesse von wässrigen Np(V) an verschiedenen Mineralphasen präsentiert. Wie U(VI) bildet Np(V) stabile innersphärische Oberflächenkomplexe an TiO2. Die Speziesverteilung an der TiO2 Oberfläche ist im pH Bereich 4 – 7,6 konstant. Daher ist zu erwarten, dass eine außersphärische Komplexierung hier nur eine untergeordnete Rolle spielt. Der Vergleich von Spektren der Np(V) Sorptionskomplexe an TiO2, SiO2 und ZnO weist auf die Bildung strukturell ähnlicher bidentater Komplexe hin. Die Vielzahl der hier vorgestellten infrarotspektroskopischen Experimente bietet eine fundierte Sammlung spektroskopischer Daten, die für zukünftige Untersuchungen komplexer aquatischer und mineralischer Systeme unerlässlich ist. Gleichzeitig wurde der Anwendungsbereich der ATR FT-IR Technik auf dem Gebiet der Radioökologie umfassend erweitert. Die im Rahmen dieser Arbeit gewonnenen Ergebnisse tragen zu einem besseren Verständnis der geochemischen Wechselwirkungen von Aktiniden, im Speziellen von U(VI) und Np(V) in der Umwelt bei. Damit unterstützen sie den Aufklärungsprozess der Migration von radioaktiven Kontaminationen und dienen als Grundlage für zuverlässige Prognosen für die Sicherheitsbewertung von Endlagern für nukleare Abfälle.

Bakgrund: En akut akillesseneruptur (ATR) resulterar i begränsning av funktion som kan kvarstå under lång tid. I litteraturen finns ett flertal reliabla och valida utvärderingsinstrument som används vid funktionsbedömningar efter ATR. Då osäkerhet angående lämpligt val av tester inför återgång i aktivitet/idrott föreligger finns ett behov av tydliga riktlinjer i fråga om kliniskt relevanta utvärderingsinstrument. Syfte: Syftet med studien var att identifiera kliniskt relevanta fysioterapeutiska utvärderingsinstrument för bedömning av funktion hos personer med akillesseneruptur samt kartlägga dessa utifrån ett validitets och reliabilitetperspektiv. Metod: En kartläggande litteraturstudie. Litteratursökningen genomfördes i databaserna PubMed, Cinahl och PEDro mellan 2023-02-07 – 2023-02-15 utifrån inklusionskriterierna: vuxna individer med akut ATR, artiklar publicerade 2013-2023, observations- och randomiserade kontrollerade studier. Av identifierade utvärderingsinstrument valdes 15 ut, baserat på kriterierna: frekvens, klinisk användbarhet samt kategorisering enligt ramverket International Classification of Functioning, Disability and Health (ICF). Valda utvärderingsinstrument kategoriserades enligt ICF samt granskades avseende reliabilitet och validitet om denna data fanns tillgänglig. Resultat: Totalt inkluderades 15 olika utvärderingsinstrument, såväl objektiva som subjektiva, för granskning utifrån reliabilitet och validitet. Fem av dessa visade både god reliabilitet och validitet samt klinisk användbarhet. Inga diagnosspecifika utvärderingsinstrument inom ICF-kategorierna personlighetsfaktorer och omgivningsfaktorer identifierades. Slutsats: Achilles Tendon Resting Angle (ATRA), Achilles Tendon Total Rupture Score (ATRS), Foot and Ankle Outcomes Score (FAOS), Heel-Rise Endurence och Heel-Rise Height är fem tillförlitliga utvärderingsinstrumnet att använda i klinik. Inför återgång till aktivitet/idrott är det nödvändigt att komplettera med idrottsspecifika utvärderingsinstrument samt instrument som utvärderar psykologiska faktorer. / Background: An acute achilles tendon rupture (ATR) results in limitations of function that remains for a long time. There are several reliabel and valid outcome measures used in functional evaluation after ATR presented in the litterature. Due to uncertainties regarding which appropriate outcome measures to use for return to activities/sports there is a need for clinical guidelines. Purpose: The purpose was to identify physiotherapeutic outcome measures for the evaluation of function in people with achilles tendon ruptures and to chart these from a perspecive of reliability and validity. Method: A scoping review. A litterature search were performed in the databases PubMed, Cinahl and PEDro between 2023-02-07 – 2023-02-15 based on the inclusion criteria: adults with acute ATR, articles published between 2013-2023, clinical trials and randomized controlled trials. From identified outcome measures 15 were selected based on the criteria frequency, clinical usability and categorized by the theoretical framework International Classification of Functioning, Disability and Health (ICF). Selected outcome measures were categorized according to ICF and reviewed for republicity of results, if this data was available. Results: 15 outcome measures, both objective and subjective, were included for evaluation regarding reliability and validity. Five of these proved good reliability, validity and clinical usability. In the ICF categories, personal factors and environmental factors, no diagnose specific outcome measures were identified. Conclusion: Achilles Tendon Resting Angle (ATRA), Achilles Tendon Total Rupture Score (ATRS), Foot and Ankle Outcomes Score (FAOS), Heel-Rise Endurence och Heel-Rise Height are five reliable outcome measures to use in clinical practice. Before return to activities/sports it is necessary to add sportspecific outcome measures and evaluation of psychological factors.

In the UK there has been growing concern about the relationship between levels of alcohol consumption and offending behaviour. The Alcohol Treatment Requirement (ATR) was introduced to the UK in 2007 and was piloted in a District in the north of England in July 2007. The ATR is a coercive form of treatment delivered jointly by the probation service and the National Health Service (NHS) and was funded by the NHS. The ATR centres on supporting offenders to cease their offending behaviour and reduce or end their alcohol misuse. Two female alcohol treatment workers have been appointed to specifically deliver the ATR. Therefore this study aimed to investigate the delivery of the ATR, and more specifically, aimed to explore what impact the ATR might have in relation to positive behaviour change and rehabilitation for offenders with alcohol problems. In order to meet the expectations of producing 'outcome' data for the NHS funders, and indepth theoretical data worthy of an academic PhD, this research took a pragmatic methodological approach which enabled different social realities of the ATR to be explored. To this end, a mixed methods design was employed involving quantitative and qualitative data collection methods. The data for this research was generated in three phases with Phase One aiming to explore quantitatively the characteristics, impacts and outcomes of those sentenced to the ATR. This phase revealed that the ATR is being delivered to predominantly young, male, alcohol dependent, violent, persistent offenders. This analysis further revealed that the ATR was effective in bringing about positive treatment outcomes and in reducing reoffending. In order to explore further how this positive change was occurring, Phase Two consisted of qualitative participant observations of the treatment interaction involving the female alcohol treatment workers and the male offenders. By drawing on positioning theory, the analysis considered the complexity of the gendered interactions that occurred during these encounters. It was found that the two female alcohol treatment workers resisted positions of 'feminine carer' offered up by these young men in order to occupy positions of control. Indeed this analysis provided great insight into the constant flow of negotiations and manoeuvring of positions that occurred between the alcohol treatment worker and the offender, argued to be vitally important in working towards positive behaviour change. During Phase Three ten offenders were interviewed in order to explore through a dialogical lens (Bakhtin, 1982) how they constructed and experienced treatment on the ATR. In exploring the offenders' stories dialogically, the analysis highlighted how the ATR was enabling, in that it offered a 'space' for these offenders to engage and internalise a dialogue that draws on the authoritative voice of therapy. Therefore it was revealed that through dialogue with the 'other', offenders were able to re-author a more 'moral' and 'worthy' self. Moreover, the ATR has been found to be successful in enabling the offenders' hegemonic masculine identities to be both challenged and protected as a result of the multilayered interactions that occurred during these treatment encounters. This research therefore concludes that coercive treatment, rather than being a concern, should be embraced as a way of enabling change for offenders with alcohol problems. Furthermore, this research has highlighted the value of the relational aspect of treatment in bringing about positive behaviour changes. Finally this research has shown that community sentences offer a more constructive way of engaging with offenders than those who receive a custodial sentence.