Les travaux réalisés portent sur la synthèse de nanoparticules de PVDF à l’aide de la polymérisation radicalaire contrôlée (PRC) par transfert de chaîne réversible par addition-fragmentation (RAFT) en émulsion. Dans un premier temps, un méthoxy poly(éthylène glycol) commercial porteur d’une fonction hydroxyle (PEG-OH) a été employé pour la stabilisation des particules de PVDF. Cette stabilisation est assurée par des réactions de transfert irréversible opérant le long des chaînes de PEG conduisant à la formation in situ d’un stabilisant de type copolymère greffé. Par la suite, un PEG modifié chimiquement à partir du PEG-OH, portant à son extrémité de chaîne une fonction xanthate (macroRAFT, PEG-X), réactive et réactivable, a été utilisé. Les expériences réalisées en présence de ce macroRAFT ont démontré une forte implication de l’extrémité xanthate dans le procédé de polymérisation en émulsion du VDF. En effet, des particules stables de l’ordre de 70 nm de diamètre sont obtenues, alors que l’utilisation de PEG-OH conduit à des tailles beaucoup plus importantes (200 nm). Cette tendance est confirmée lors de l’étude de l’impact de divers paramètres comme la masse molaire de la chaîne PEG ou encore la quantité d’amorceur. Des analyses complémentaires (tension de surface et calorimétrie différentielle à balayage) ont permis de comparer le taux d’ancrage de PEG-X et de PEG-OH. Les quantités en macroRAFT ont ensuite été augmentées dans le but d’obtenir des particules composées de copolymères à blocs. Des analyses RMN approfondies ont été menées pour identifier les espèces créées lors de la polymérisation en émulsion du VDF lorsque PEG-OH et PEG-X sont utilisés en tant que stabilisant. Par comparaison, des PEG portant des fonctions réactives de types (méth)acrylate et thiol ont également été employés comme stabilisant et leurs efficacités comparées à celles de PEG-OH et de PEG-X. Par ailleurs, d’autres architectures à base de PEG ont été évaluées en utilisant un macroRAFT difonctionnel (X-PEG-X) et un polymère greffé (PPEGA-X). Enfin, des latex de PVDF ont été synthétisés en présence de macroRAFT de type poly(acide (méth)acrylique) obtenus par polymérisation RAFT de l’acide acrylique ou méthacrylique en présence d’un trithiocarbonate ou d’un xanthate. Comme précédemment, plusieurs paramètres ont été variés comme la masse molaire des chaînes macromoléculaires, la quantité d’amorceur et la quantité de macroRAFT. Ces études ont encore une fois démontré la forte implication des extrémités RAFT dans la stabilisation des particules de PVDF / This work describes the synthesis of self-stabilized PVDF particles by combining the advantages of emulsion polymerization with those of controlled radical polymerization (CRP) using the RAFT process. First, a commercial methoxy poly(ethylene glycol) carrying a hydroxyl function (PEG-OH) was used for the stabilization of PVDF particles. The stabilization is provided by irreversible transfer reactions occurring along the PEG-OH chains leading to the formation of a grafted copolymer stabilizer in situ. This PEG-OH was then chain-end functionalized to introduce a xanthate group (macroRAFT, PEG-X). The experiments carried out in the presence of this macroRAFT demonstrated a strong implication of the xanthate chain-end in the VDF emulsion polymerization process. Indeed, particle sizes of 200 nm and 70 nm were obtained in the presence of PEG-OH and PEG-X, respectively. This trend was confirmed during the study of the impact of various parameters such as the molar mass of the PEG chain or the initiator amount. Additional analyses (surface tension measurement and differential scanning calorimetry) allowed to compare the anchoring efficiency of PEG-X and PEG-OH. The macroRAFT amount was then increased to form particles composed of block copolymer. In-depth NMR analyses were then conducted to identify the species created during the VDF emulsion polymerization process in the presence of PEG-OH and PEG-X. In comparison, PEGs carrying reactive functions such as (meth)acrylate and thiol were used as stabilizers and their efficiencies compared to those of PEG-OH and PEG-X. The macroRAFT architecture was also varied using a difunctional macroRAFT (X-PEG-X) and a grafted polymer (PPEGA-X). Finally, PVDF latexes were synthesized with poly((meth)acrylic acid) (P(M)AA) functionalized by either a trithiocarbonate or a xanthate. Like previously, several parameters were varied such as the macromolecular chain length, the initiator amount and the macroRAFT amount. Again, these studies demonstrated the strong impact of the RAFT chain-end in the stabilization of PVDF particles

Polyunsaturated fatty acids (PUFA) have been used with some success in the treatment of canine atopic dermatitis (CAD). Correspondent in vitro studies revealed that PUFA play a crucial role in the exocytosis of mast cells. n3 PUFA such as α-linolenic acid (LNA), eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), as well as the n6 PUFA linoleic acid (LA) have been shown to arrest the secretion of inflammatory mediators. Contrary, the n-6 PUFA arachidonic acid (AA) has been proven to promote the production of mast cell inflammatory mediators. However, we are still lacking a complete picture of the mode of action. The goal of this work was to further characterize the modulatory effects of PUFA supplementation on the plasma membrane lipid composition of mast cells. Furthermore the consequences of a membrane modulation of mast cells by PUFA on the localization and activity on of the membrane bound enzyme phospholipases D (PLD) were investigated. Canine mastocytoma cells (C2) were supplemented with one of the following PUFA: LNA, EPA, DHA, LA or AA. To investigate the influence of PUFA on the lipid composition of membrane microdomains, lipid rafts were separated from non-raft plasma membranes of mast cells for the first time using a detergent-free isolation technique. Results show that PUFA are significantly increased in rafts as well as in non-rafts microdomains (Publication 1). The incorporation of PUFA into the membrane goes along with an increase of the unsaturation status and the fluidity of the membrane. This rise in membrane fluidity may result in a reorganization of membrane signaling molecules and enzymes such as the PLD. To define the impact of a PUFA supplementation on PLD trafficking, C2 were transfected with green fluorescent protein (GFP) fusion plasmids encoding PLD1 or PLD2. Since the transfection ability of the suspension cell line C2 is limited, a special transfection protocol was established, suitable for non-adherent cell lines. Transfection succeeded using chicken egg white as coating material for the cell culture plates. The transfection efficiency rose to 50% versus 5% in uncoated plates. In addition to the obvious increase in the transfection efficiency, the new technique is simple and economic and might be suitable for a wide range of suspension cell lines (Publication 2). Using this optimized protocol the influence of PUFA on the trafficking of PLD isoforms was studied. LNA, EPA, DHA and LA but not AA prevented the stimulation-induced translocation of PLD1 to the plasma membrane. Since the translocation of PLD1 is important for mast cell exocytosis, LNA, EPA, DHA and LA do have an inhibiting effect on the stimulation-induced release of pro-inflammatory mediators. All PUFA tested boosted the total PLD activity. In order to rule out, which PLD isoform was affected by the PUFA, the mast cells were supplemented with DHA or AA in the presence of specific PLD isoform inhibitors. DHA completely abolished the inhibitiory effect of the PLD1 inhibitor but had no effect on the inhibitory effect of PLD2 inhibitor. On the other hand, AA suppressed the inhibitory effect of both PLD1 and PLD2 inhibitor (Publication 3). Taking together, the studies provide a mechanistic base for the role of PUFA in the exocytosis processes of mast cells. PUFA of the n3 and the n6 families impact the lipid composition of membrane microdomains, which in turn lead to a modulation of the physiochemical properties of the membrane. LNA, EPA, DHA and LA suppress the release of inflammatory mediators through their inhibitory action on the stimulation-induced translocation of the PLD1. Contrariwise, AA permits the stimulation-induced migration of PLD1 to the plasma membrane and increases the activity of both PLD isoforms. Therefore, LNA, EPA, DHA and LA but not AA inhibit the release of mast cell inflammatory mediators upon stimulation. / Mehrfach ungesättigte Fettsäuren (PUFA) können mit einigem Erfolg zur Behandlung der caninen atopischen Dermatitis (CAD) eingesetzt werden. In vitro-Studien zeigten, dass PUFA eine entscheidende Rolle in der Exozytose von Mastzellen spielen. N-3-PUFA wie α-Linolensäure (LNA), Eicosapentaensäure (EPA), Docosahexaensäure (DHA) sowie die n-6-PUFA Linolsäure (LA) können die Sekretion von Entzündungsmediatoren vermindern. Arachidonsäure (AA) als n-6 mehrfach ungesättigte Fettsäure hingegen fördert die Entzündungsmediatoren-Freisetzung aus den Mastzellen. Eine vollständige Aufklärung der Wirkungsweise fehlt aber weiterhin. Das Ziel dieser Arbeit war eine weitergehende Charakterisierung der modulierenden Effekte einer PUFA-Supplementierung auf die Lipidzusammensetzung der Plasmamembran von Mastzellen. Darüber hinaus wurden die Auswirkungen von PUFA auf die Lokalisation und Aktivität des Membran-gebundenen Enzyms Phospholipase D (PLD) untersucht. Canine Mastozytom-Zellen (C2) wurden mit einer der folgenden PUFA kultiviert: LNA, EPA, DHA, LA oder AA. Um den Einfluss von PUFA auf die Lipidzusammensetzung der Membran-Mikrodomänen zu untersuchen, konnten sowohl Lipid Raft als auch Nicht-Raft Plasmamembran-Anteile von Mastzellen zum ersten Mal mittels einer Detergenzien-freien Isolationsmethode getrennt werden. Hervorzuheben ist, dass PUFA signifikant vermehrt in Raft- sowie in Nicht-Raft Membranmikrodomänen eingelagert werden (Publikation 1). Die Integration von PUFA in die Membran geht mit einer Steigerung der Doppelbindungsanzahl und der Fluidität der Membran einher. Diese Erhöhung der Membranfluidität kann zu einer Reorganisation von membranären Signalmolekülen und Enzymen wie der PLD führen. Um die Auswirkungen einer PUFA-Supplementierung auf den intrazellulären Transport der PLD in C2 zu bestimmen, wurden die Zellen mit PLD1- oder PLD2-codierenden grün fluoreszierenden Protein-(GFP-)Fusionsplasmiden transfiziert. Da die Transfektionsfähigkeit der Suspensions-Zelllinie C2 begrenzt ist, wurde ein für nicht-adhärente Zelllinien geeignetes Transfektionsprotokoll etabliert. Mit Hühnereiweiß als Beschichtungsmaterial für die Zellkultur-Platten stieg die Transfektionseffizienz auf 50% im Vergleich zu 5% bei unbeschichteten Platten. Neben der deutlichen Erhöhung der Transfektionseffizienz ist die neu etablierte Technik einfach durchzuführen sowie wirtschaftlich und kann für eine Vielzahl von Suspension-Zelllinien geeignet sein (Publikation 2). Unter Verwendung dieses optimierten Protokolls wurde der Einfluss von PUFA auf die Translokation der PLD-Isoformen untersucht. LNA, EPA, DHA und LA, nicht aber AA verhindern die stimulationsinduzierte Translokation der PLD1 an die Plasmamembran. Die Translokation der PLD1 ist wichtig für die Mastzell-Exozytose. LNA, EPA, DHA und LA haben hier eine hemmende Wirkung auf die stimulationsinduzierte Freisetzung von proinflammatorischen Mediatoren. Alle getesteten PUFA verstärken die Gesamt-PLD-Aktivität. Um zu unterscheiden, welche PLD-Isoform durch PUFA beeinflusst ist, wurden die Mastzellen mit DHA oder AA in Gegenwart von PLD-Isoform-Inhibitoren supplementiert. DHA hebt die inhibitorische Wirkung des PLD1-Inhibitors vollständig auf, zeigte aber keinen Einfluss auf die hemmende Wirkung des PLD2-Inhibitors. Andererseits unterdrückt AA die hemmende Wirkung des PLD1- als auch des PLD2-Inhibitors (Publikation 3). Zusammenfassend bietet die Studie eine mechanistische Basis für die Rolle von PUFA bei Exozytose-Prozessen von Mastzellen. PUFA der n-3- und n-6-Familie beeinflussen die Lipidzusammensetzung von membranären Mikrodomänen, was wiederum zu einer Modulation der physikalisch-chemischen Eigenschaften der Membran führt. LNA, EPA, DHA und LA verhindern die Freisetzung von Entzündungsmediatoren durch ihre hemmende Wirkung auf die stimulationsinduzierte Translokation der PLD1. Umgekehrt erlaubt AA eine stimulationsinduzierte Migration der PLD1 zur Plasmamembran und steigert die Aktivität der beiden Isoformen der PLD. Somit hemmen LNA, EPA, DHA und LA, aber nicht AA die Freisetzung von Mastzell-Entzündungsmediatoren nach Stimulation.

Ce travail de thèse a visé la préparation de matériaux biohybrides à base de poly (liquide ionique)s (PIL) et de polysaccharide, en l’occurrence la gomme de guar. Les chaînes de poly (1- [2-acryloyl éthyl] -3 bromure-méthylimidazolium (poly (AEMIBr)) ont été synthétisées par polymérisation contrôlée de type RAFT. Des homopolymères de DP élevé (jusqu'à 300) et de faible dispersité (inférieur à 1,19) ont été obtenus seulement en quelques heures dans l'eau. Ces PIL ont par ailleurs été utilisés comme macroagents de transfert pour générer différents copolymères à blocs en milieu homogène et en émulsion dans le but d’accéder à des nano objets autoassemblés. En effet, différentes morphologies ont été obtenues en s’appuyant sur lesconcepts de la PISA. De plus, des copolymères greffés de type guar-g-PIL ont finalement été construits en milieu liquide ionique.en utilisant des dérivés de guar macroagents de transfert Les PIL combinent à la fois les propriétés des IL (non-volatile, stabilité thermique et chimique, haute conductivité...) et celles des polymères en termes de renforcement mécanique, c’est pourquoi ils ont été exploités pour élaborer des matériaux biohybrides de haute performance. La stratégie envisagée dans ce travail réside sur l’exploitation de trois composants: (i) les chaînes de poly (AEMIBr), (ii) le guar et (iii) un liquide ionique: le chlorure de butylméthylimidazolium (BMIMCl). La voie expérimentale permettant l’obtention de tels matériaux est très simple et non dégradante puisqu’elle n’implique que des étapes de solubilisation de polymères en milieu IL. Les propriétés rhéologiques et thermiques de ces matériaux ont été évaluées. En outre, la morphologie interne, par des mesures de WAXS et SAXS, ainsi que le transport ionique ont été étudiés. Il en ressort que de multiples interactions synergiques sont formées entre le guar et les chaînes de PIL, en parallèle des interactions de type PIL/IL et guar/IL. Des ionogels possédant un haut module élastique (jusqu'à 30 000 Pa) et une stabilité thermique élevée (jusqu'à 310 °C) ont ainsi été obtenus. En particulier, la présence de PIL a permis d’améliorer de façon considérable la stabilité dimensionnelle des gels, en limitant complétement les phénomènes d’exudation rencontrés dans les systèmes binaires guar/IL. Il s’avère, de plus, que ces matériaux sont parfaitement homogènes à l’échelle d’observation des analyses SAXS et WAXS. Ces gels ioniques présentent d'excellentes propriétés de transport ionique (10-4 S/cm à 30 °C) grâce notamment à leur structuration interne continue. Cette famille des matériaux multicomposants à base de guar, présente un fort potentiel, notamment pour une utilisation en tant que gel électrolyte dans le domaine de l’énergie. / This Ph.D work focuses on the preparation of biohybrid materials based on poly(ionic liquid)s (PIL) and a polysaccharide, guar gum. Poly(1-[2-acryloylethyl]-3-methylimidazolium bromide (poly(AEMIBr)) chains were synthesized through RAFT polymerization. Homopolymers with DP up to 300 and dispersity below 1.19 were obtained within hours in water. High chain-end fidelity further allowed for PIL chain extension with various monomers and stable PIL-based nanoparticles with various morphologies using the PISA concept were achieved. A series of guar-g-PIL graft copolymers were finally constructed in IL using guar macroRAFT agents. As PILs combine the attributes emanating from IL molecules (non-volatile, thermally stable, conducting…) with the ones of polymers in terms of mechanical reinforcement, the resulting polymers were exploited to elaborate high performance biohybrid materials. The cornerstone of this subsequent work was based on the straightforward formation of three-component blends: (i) poly(AEMIBr), (ii) guar and (ii) ionic liquid: butylmethylimidazolium chloride (BMIMCl). The pathway to obtain such ternary blends is very simple, since it only implies successive polymer solubilisation steps in IL. The rheological and thermal properties of the resulting materials were investigated. Also, the internal morphology by WAXS and SAXS measurements as well as the ionic transport were studied. It appeared that strong synergistic hydrogen bonding are developed between guar and PIL chains in addition to PIL/IL and guar/IL interactions. Ionogels with high elastic modulus (up to 30 000 Pa) and high thermal stability (up to 310°C) were prepared. Importantly, addition of PIL significantly enhanced the dimensional stability of the resulting ionogels and overcame IL exudation encountered in IL/guar binary systems. SAXS and WAXS revealed a homogeneous morphology and the ionogels were proven to exhibit excellent conductive properties (10-4 S/cm at 30°C) thanks to their highly continuous morphology. The resulting sustainable multicomponent materials may find applications as gel electrolyte for biobattery systems or supercapacitors.

Ce travail est axé sur l’amélioration des propriétés de biospécificité de sondes polymères fluorescentes, d’architectures contrôlées synthétisées par polymérisation RAFT, pour deux applications principales : le ciblage de tumeurs cancéreuses in vivo et le marquage de protéines pour des études in cellulo. Pour une imagerie ciblée de l’angiogénèse tumorale in vivo, des systèmes de ciblage multivalents à deux niveaux ont été élaborés en combinant à la fois i) des polymères bien contrôlés synthétisés par polymérisation RAFT et par le procédé PISA, ii) des clusters peptidiques tétravalents présentant une forte affinité pour les intégrines αvβ3 et iii) des fluorophores émettant dans le rouge lointain/proche-infrarouge pour un suivi in vitro et in vivo par microscopie optique. Deux types de sondes ont été synthétisés, des conjugués linéaires et des nanoparticules chevelues. La présentation multivalente du cluster peptidique permet d’augmenter considérablement l’affinité pour les intégrines αvβ3. Les premières évaluations biologiques indiquent une internalisation cellulaire des sondes polymères médiée par les clusters peptidiques ainsi qu’un marquage sélectif des cellules sur-exprimant les intégrines αVβ3. Pour le marquage de protéines, deux stratégies ont été explorées : le marquage de protéines natives par couplage covalent de sondes ω-fonctionnelles et le marquage de protéines recombinantes par des sondes porteuses d’un ligand spécifique. Pour la première stratégie, une fonction ester activé a été introduite en extrémité ω de sondes polymères par chimie thiol-ène pour marquer les résidus lysines des protéines natives. Cette approche a abouti à un poly-marquage difficile à contrôler mais offrant une brillance élevée. Pour la seconde stratégie, un groupement acide nitrilotriacétique (NTA) a été introduit en extrémité α des sondes polymères afin de marquer spécifiquement les protéines taguées Histidines. Cette approche a permis un marquage efficace de différentes protéines et permet de contrôler précisément le nombre de sondes par protéine ainsi que leur site de fixation sur la protéine. Finalement, suite à ces travaux, une nouvelle stratégie de synthèse de polymères séquencés par addition successive de monomères hétéro-bifonctionnels en utilisant des réactions chimiques très efficaces, sélectives et orthogonales a été proposée et validée. / This work is focused on improving the biospecificity properties of fluorescent polymer probes, with controlled architectures, for two main applications: the in vivo targeting of cancer tumors and the labeling of proteins for in cellulo studies. For a targeted imaging of tumor angiogenesis in vivo, targeting systems presenting two levels of multivalency were developed by combining both i) well-controlled polymers synthesized by RAFT polymerization and the PISA process, ii) peptide tetravalent clusters exhibiting a high affinity for the αvβ3 integrins and iii) fluorophores emitting in the far red / near-infrared for a monitoring in vitro and in vivo by optical microscopy. Two types of probes were synthesized, linear conjugates and hairy nanoparticles. Multivalent presentation of the peptide cluster induced a significant increase of the affinity for αvβ3 integrins. The first biological evaluations also indicated an efficient cellular internalization of polymer probes mediated by the peptide clusters and a selective labeling of cells over-expressing αvβ3 integrins. For protein labeling, two strategies were explored: the labeling of native proteins by covalent coupling of ω-functional polymer probes and the labeling of recombinant proteins by probes bearing a specific ligand at one chain-end. For the first strategy, an activated ester function was introduced at the ω-end of polymer probes by thiol-ene chemistry to label the lysine residues of native proteins. This approach resulted in a poly-labeling, difficult to control but providing highly bright bioconjugates. For the second strategy, a nitrilotriacetic acid group (NTA) was introduced at the α-end of polymers probes to specifically label Histidine tagged proteins. This approach enabled an efficient labeling of different proteins with a more precise control of the number of probes per protein and of the binding site. Finally, following this work, a new synthetic strategy of sequenced polymers by successive addition of hetero-bifunctional monomers using highly efficient, selective and orthogonal chemical reactions was proposed and validated.

The purpose of this thesis was to capture the development of legal regulation of the Czech water law and of water-law relationships, and to point out that miller's law, fisheries law and navigation law are naturally related to the water law. Water transport and handling were not regulated in any manner in the most ancient times. The Czech water law was built on the heritage of the Roman legal culture. From the end of the 10th century, the first mentions of water-law relationships can be found, particularly in monarch's charters. The first important legal regulations related to water included the Mining Code (Ius Regale Montanorum) by king Wenceslas II of 1300-1305 and the Code Maiestas Carolina by king Charles IV, which was not implemented in practice, though. The so called lawbooks are another significant resource for understanding legal regulations related to water. Elements of a complex legal regulation with statewide legal force started to be applied from the end of the 15th and in the course of the 16th century - a number of municipal establishments and the code of municipal law created by Pavel Kristián of Koldín. A considerable boom of legal regulations with respect to all aspects of water-law relationships was seen during the reign of Maria Theresia and Joseph II (the navigation patent,...

Les édifices médiévaux du Midi rhodanien apparaissent souvent comme dépourvus de charpente ou simplement couverts de structures en bois sans grand intérêt technique. Cette idée s’appuie sur un constat indubitable : le paysage architectural de la région est essentiellement minéral. Très tôt, l’art du maçon a été favorisé par un sous-sol inépuisable en pierre à bâtir et des forêts relativement limitées dans la production de bois d’œuvre de qualité. Longtemps passés sous silence, les ouvrages charpentés existent et dénotent une singularité méconnue. L’objectif de ce travail est donc de mettre en lumière les charpentes de toit et de plancher réalisées dans ce territoire peu propice à leur réalisation. Il vise à apporter des éléments nouveaux permettant de nuancer l’idée d’une architecture sans bois. Il cherche à mettre en évidence une autre manière de concevoir les charpentes, sans doute moins monumentales que celles des régions riches en forêts mais tout aussi innovantes. La démonstration s’appuie sur des vestiges appartenant principalement aux XIVe et XVe siècles, dont la réalisation indique l’existence d’un secteur du bâtiment particulièrement actif et révélant des savoir-faire particuliers. Les charpentiers ont ainsi su pallier certaines difficultés d’approvisionnement en mettant en œuvre des formes et des techniques originales. / Most of the medievial buildings on the south side of the Rhone Valley turn out to be without roof frameworks or simply covered by wooden structures showing little technical interest. This idea is supported by an unmistakable observation: the architectural landscape of the region is mostly mineral. From early times, masonry work developed thanks to an unlimited building-stone reserve in the subsoil, and furthermore forests produced little high-quality lumber. Even though they have long been ignored, timber roof structures exist and (they) bring out remarkable singularities. The purpose of this study is to bring to light roof frameworks and floor frameworks which were built in an area little suited to their construction. It aims to bring new evidence that allows to moderate the notion of a wooden- free architecture. The study seeks to point out another way of designing of roof frames, undoubtedly less monumental than the ones built in areas with extensive forests, and yet equally innovative. The theory is based on remains dating back from the 14th to 15th centuries, the study of which proves the existence of a particularly active building sector, and reveals specific skills. Carpenters thus managed to overcome wood supply difficulties by implementing original shapes and techniques.

As análises estruturais têm como procedimento usual considerar apoios rígidos nas fundações e aplicar as ações de maneira instantânea. Essas duas simplificações podem induzir a uma configuração de esforços não condizentes com a estrutura real. Este trabalho investiga a interação solo-estrutura (ISE) em edifícios de paredes de concreto apoiados em fundação do tipo radier. O presente estudo considera a sequência construtiva da edificação, denominada por ações evolutivas, objetivando obter resultados mais condizentes com a estrutura real. A investigação é realizada mediante simulação numérica utilizando o Método dos Elementos Finitos (MEF) por meio do pacote computacional DIANA®. A tipologia do modelo numérico é baseada em um conjunto de edifícios já construídos. São utilizados dados de monitoramento de recalques geotécnicos ao longo da construção dos edifícios para aferir as propriedades constitutivas do solo no modelo numérico. São analisados os efeitos da deformação da fundação na redistribuição de esforços e tensões das paredes da superestrutura, a contribuição da rigidez da estrutura na uniformização dos recalques e demais parâmetros que envolvem a ISE na estrutura e na fundação. A NBR-16055 (ABNT, 2012) obriga que seja incorporado a interação solo-estrutura nas análises de edifícios de paredes de concreto acima de 5 pavimentos. O presente estudo indica que os efeitos da ISE na estrutura têm uma maior dependência da rigidez relativa estrutura-solo. Deste modo, é proposto um coeficiente específico de rigidez relativa estrutura-solo para edifícios de paredes de concreto. São realizados estudos paramétricos que indicam que o coeficiente proposto pode ser utilizado como um parâmetro para análise da ISE em edifícios de paredes de concreto. / The usual procedure in structural analysis neglects the deformation of the foundations and the load sequence of the building. These simplifications can provide inaccurate results. This work deals with the structural analysis of concrete wall buildings settled on raft foundations taking into account the soil-structure interaction (SSI) and the progressive vertical loading. The numerical simulation was performed using the finite element method (FEM) in the DIANA® software. The numerical model is based on a set of buildings already constructed. During the construction process, the settlement of many points were measured and are used here to evaluate the constitutive soil parameters to feed the numerical models. The obtained results show a redistribution of the walls internal forces and the loss of uniformity of their vertical normal stress. The progressive vertical loading during the construction reduces the influences of the soil-structure interaction. The Brazilian code for concrete wall buildings (NBR-16055, 2012) requires that the soil/structure interaction be incorporated into the structural model in the buildings with more than 5 stories. A specific relative stiffness structural-soil factor is proposed for concrete wall buildings. The present study indicates that the SSI results are not related to the number of floors of the building. The SII have a larger dependence on soil stiffness and relative stiffness structure-soil.

Analisam-se problemas de interação solo-estrutura através de uma formulação tridimensional obtida da combinação entre o Método dos Elementos de Contorno (MEC) e o Método dos Elementos Finitos (MEF). Os elementos estruturais que interagem com o solo são modelados pelo Método dos Elementos Finitos. E o solo, considerado como um meio semi-infinito, homogêneo, elástico linear e isotrópico, é modelado pelo Método dos Elementos de Contorno, empregando a solução fundamental de Mindlin. A solução fundamental de Mindlin é particularmente adequada para o tipo de problemas em análise, ou seja, problemas envolvendo sólidos tridimensionais semi-infinitos, já que é necessário discretizar apenas a superfície carregada do solo e/ou a linha de carga, e não todo o sólido tridimensional. A discretização da estaca em vários elementos finitos de viga tridimensional, permitindo a consideração de estacas de qualquer tamanho e submetidas a qualquer tipo de carregamento é uma das principais contribuições do trabalho. Outra contribuição diz respeito à consideração da ação horizontal no sistema placa-estaca-solo, diretamente aplicada na placa, e não redistribuída no topo das estacas. Por isso, os elementos estruturais laminares (radiers, sapatas e blocos de fundação) são modelados por elementos finitos de casca plana, possibilitando a consideração dos efeitos de flexão e de membrana. Essa abordagem permite a análise tanto de um grupo de estacas com bloco de capeamento rígido quanto de um radier estaqueado de qualquer rigidez. O acoplamento entre o MEC e o MEF é feito através de uma formulação mista em que a matriz dos coeficientes de influência do solo obtida pelo MEC é adicionada à matriz de rigidez dos elementos estruturais obtida pelo MEF, resultando em uma matriz de rigidez equivalente. Exemplos numéricos de interação estaca-solo, placa-solo e casca plana-estaca-solo são resolvidos para verificar, validar e demonstrar a eficiência das formulações desenvolvidas e implementadas. / Soil-structure interaction problems are analyzed by a tridimensional formulation obtained combining the Boundary Element Method (BEM) and the Finite Element Method (FEM). Structural elements that interact with the soil are modeled by the Finite Element Method. And the soil, considered as a semi-infinite, homogeneous, linear elastic and isotropic medium, is modeled by the Boundary Element Method, using Mindlin\'s fundamental solution. Mindlin\'s fundamental solution is particularly suitable for the type of problems under analysis, viz. problems involving semi-infinite three-dimensional solids, since it is necessary to discretize only the loaded surface of the soil and/or the line-load, and not all the three-dimensional solid. The discretization of the pile in several three-dimensional beam finite elements, allowing the consideration of piles of any size and subjected to any type of loading, is one of the main contributions of this work. Another contribution is about the consideration of the horizontal load in the plate-pile-soil system, directly applied to the plate, and not redistributed on the top of the piles. Therefore, the laminar structural elements (rafts, footings, and foundation blocks) are modeled by flat shell finite elements, making possible the consideration of the effects of flexion and membrane. This approach allows the analysis of both a capped pile group and a piled raft of any stiffness. The coupling between the BEM and the FEM is performed through a mixed formulation in which the matrix of the soil\'s influence coefficients obtained by the BEM is added to the stiffness matrix of the structural elements obtained by the FEM, resulting in an equivalent stiffness matrix. Numerical examples of pile-soil, plate-soil and flat shell-pile-soil interaction are solved to verify, validate and demonstrate the efficiency of the developed and implemented formulations.

As análises estruturais têm como procedimento usual considerar apoios rígidos nas fundações e aplicar as ações de maneira instantânea. Essas duas simplificações podem induzir a uma configuração de esforços não condizentes com a estrutura real. Este trabalho investiga a interação solo-estrutura (ISE) em edifícios de paredes de concreto apoiados em fundação do tipo radier. O presente estudo considera a sequência construtiva da edificação, denominada por ações evolutivas, objetivando obter resultados mais condizentes com a estrutura real. A investigação é realizada mediante simulação numérica utilizando o Método dos Elementos Finitos (MEF) por meio do pacote computacional DIANA®. A tipologia do modelo numérico é baseada em um conjunto de edifícios já construídos. São utilizados dados de monitoramento de recalques geotécnicos ao longo da construção dos edifícios para aferir as propriedades constitutivas do solo no modelo numérico. São analisados os efeitos da deformação da fundação na redistribuição de esforços e tensões das paredes da superestrutura, a contribuição da rigidez da estrutura na uniformização dos recalques e demais parâmetros que envolvem a ISE na estrutura e na fundação. A NBR-16055 (ABNT, 2012) obriga que seja incorporado a interação solo-estrutura nas análises de edifícios de paredes de concreto acima de 5 pavimentos. O presente estudo indica que os efeitos da ISE na estrutura têm uma maior dependência da rigidez relativa estrutura-solo. Deste modo, é proposto um coeficiente específico de rigidez relativa estrutura-solo para edifícios de paredes de concreto. São realizados estudos paramétricos que indicam que o coeficiente proposto pode ser utilizado como um parâmetro para análise da ISE em edifícios de paredes de concreto. / The usual procedure in structural analysis neglects the deformation of the foundations and the load sequence of the building. These simplifications can provide inaccurate results. This work deals with the structural analysis of concrete wall buildings settled on raft foundations taking into account the soil-structure interaction (SSI) and the progressive vertical loading. The numerical simulation was performed using the finite element method (FEM) in the DIANA® software. The numerical model is based on a set of buildings already constructed. During the construction process, the settlement of many points were measured and are used here to evaluate the constitutive soil parameters to feed the numerical models. The obtained results show a redistribution of the walls internal forces and the loss of uniformity of their vertical normal stress. The progressive vertical loading during the construction reduces the influences of the soil-structure interaction. The Brazilian code for concrete wall buildings (NBR-16055, 2012) requires that the soil/structure interaction be incorporated into the structural model in the buildings with more than 5 stories. A specific relative stiffness structural-soil factor is proposed for concrete wall buildings. The present study indicates that the SSI results are not related to the number of floors of the building. The SII have a larger dependence on soil stiffness and relative stiffness structure-soil.

Gegenstand dieser Arbeit war die Synthese von thermisch schaltbaren Kammcopolymeren auf Basis von N-(Isopropylacrylamid) (NiPAAm) und Polyethylenglykolmakromonomeren (PEGMA). Die intensive Charakterisierung der aus diesen Copolymeren hergestellten Schichten und deren Anwendung als Zellkultursubstrate war ein weiteres Forschungsziel dieser Arbeit. Die mit Hilfe der neuartigen Schichten erhaltenen Zellkultursubstrate wurden anhand verschiedener adhärenter Zelllinien erfolgreich getestet. Alle getesten Zelltypen (Mausfibroblasten, humane Endothelzellen der Nabelschnurvene und humane korneale Endothelzellen) proliferierten auf den angebotenen Zellkultursubstraten bei 37°C und konnten durch senken der Temperatur geerntet werden.