Les aptamères correspondent à de courtes séquences d'oligonucléotides possédant une forte affinité et spécificité envers un ligand (petites molécules organiques, peptides, acides nucléiques, protéines, cellules). Du fait de leurs remarquables propriétés, ils sont utilisés comme alternative aux anticorps dans les dispositifs de type biocapteur/biopuce, notamment pour la détection de petites molécules (PM < 2000 Da). L'imagerie de résonance des plasmons de surface (SPRi) est une technique de détection optique qui a gagné une attention croissante ces dernières années. Elle est basée sur un principe de variation de l'indice de réfraction d'une surface sélective lors de l'interaction sonde/cible. Sa sensibilité est néanmoins limitée aux molécules de poids moléculaire supérieur à 2000 Da. Dans le cadre de ces travaux, nous avons développé une biopuce à aptamères pour à la détection d'une petite molécule, l'adénosine, au moyen de la technique de résonance des plasmons de surface (SPR). Pour cela, deux différentes stratégies ont été développées. La première combine l'utilisation de nanoparticules d'or (AuNPs) pour l'amplification du signal SPRi avec l'ingénierie des séquences d'aptamères. La seconde stratégie est basée sur l'exploitation de la stabilité thermodynamique apportée par l'interaction de la cible (adénosine) avec les séquences d'aptamères. Le dispositif SPR est alors couplé à un système de régulation de température, permettant ainsi d'assurer la dissociation des complexes et d'établir des profils de dénaturation caractéristiques. Nos résultats initient ainsi une nouvelle approche dans la détection de petites molécules par SPRi et ouvrent de nouvelles perspectives de développement des biocapteurs à aptamères. / Aptamers are single-stranded DNA (ssDNA) or RNA molecules capable of binding to target molecules, including proteins, metal ions and drugs. Because of their specific binding abilities and many advantages over antibodies (higher stability, lower cost, easy chemical modification…), they provide a great opportunity to produce sensing surfaces for effective and selective detection of small molecules. Surface Plasmon Resonance imaging (SPRi) has become one of the most widely used label-free method for the study of biorecognition events on sensor surfaces. This technique provides a rapid approach, however, limited by low refractive index changes occurring when small molecules (<2000 Da) are captured on the sensor. Whereas significant reflectivity variation is observed upon the interaction of large molecules like proteins with the sensing interface, for small molecules targets such adenosine, the reflectivity variation is often too small to be detected by SPRi. Thereby, only few studies have been reported so far on SPRi-based biosensor for small molecules detection using aptamers. In this work, we developed two bioassay strategies for the detection of a model small molecule, adenosine, using Surface Plasmon Resonance imaging. The first one combines the SPRi signal enhancement effect induced by gold nanoparticles (AuNPs) with the advantage of using engineered DNA aptamers. The experimental results have demonstrated that the presence of gold nanoparticles and adenosine, which works as a molecular linker between engineered aptamer fragments, can significantly increase the SPRi response. The second strategy is based on the thermodynamics of binding between adenosine and its aptamer. To that end, SPRi technique was coupled with rigorous temperature control and aptamer duplex stability was monitored (affected by target binding) by quantification of melting transitions. Our results initiate a new approach for small molecule detection using SPRi with the aim to validate future prospects for integration in parallelized platform.

O objetivo desse trabalho foi o de obter-se fios de cobre em três composições químicas distintas da liga Cu-Mg a partir de cobre eletrolítico e de magnésio. Foram avaliadas as etapas envolvidas, começando com a fusão de botões em forno a arco na composição do eutético Cu-Mg, diluição destes botões em forno resistivo, vazamento em lingoteira de cobre, seguido de tratamento térmico de homogeneização em forno resistivo a 910 ºC por 2 h. Os tarugos foram posteriormente trabalhados mecanicamente por forjamento rotativo seguido de um passe final de acabamento por trefilação, para obtenção do fio. As análises químicas realizadas nos lingotes indicaram que a rota de preparação dos fios mostrou-se adequada aos estudos em escala de laboratório, suficiente para a confecção de fios com área de seção transversal de 4 mm2 por 10 m de comprimento, para cada composição de liga. Os fios foram caracterizados mecanicamente por ensaio de tração e de dureza após tratamento térmico de recristalização a 510 ºC por 1 h. Os fios também tiveram as condutividades elétricas medidas na condição recristalizada e os resultados foram comparados com dados experimentais da literatura. Os materiais obtidos mostraram-se adequados à utilização como fio condutor de energia elétrica. Os limites de escoamento e de resistência a tração tiveram seus valores melhorados com o aumento do teor de magnésio na liga, 11 % e 24 %, respectivamente, enquanto houve queda nos valores de condutividade elétrica para cerca de 60 % IACS (International Annealed Copper Standard). / The aim of this work was to obtain copper wires in three different chemical compositions starting from electrolytic copper and magnesium. The mains steps were evaluated, starting from the melting of small eutectic cooper-magnesium specimens in an electric arc furnace, followed by further dilution of this buttons in a resistive furnace and casting it in a copper mould. The as cast billets were homogenized in a resistive furnace at 910 ºC for 2 h. The billets were mechanically cold worked by swaging and a final drawing step to attain a round shape and a reasonable surface quality. The cast ingots chemical analysis indicated that the processing route showed to be adequate, in laboratory scale, to obtain wires with cross sectional area of 4 mm2 and 10 m in length. The wires in both conditions as cold worked and after a recovering heat treatment at 510 ºC for 1 h, were mechanically characterized by tensile testing and hardness. The wires had also the electric conductivity assessed in the recovered heat-treated state and the results were compared to the literature data. The obtained material showed to be adequate to be used as electric conductor. The yield strain and ultimate tensile strength were improved with the increasing amount of Mg in the alloy, 11 % and 24 %, respectively, while the electric conductivity decreased to 60 % IACS (International Annealed Copper Standard).

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Orientador: Eloi da Silva Feitosa / Banca: Pietro Ciancaglini / Banca: Rosangela Itri / Banca: João Ruggiero Neto / Banca: Vera Aparecida de Oliveira Tiera / Resumo: Estudos de calorimetria diferencial de varredura (DSC) e fluorescência de estado estacionário da sonda Vermelho do Nilo indicam a formação de vesículas de DODAX (X = Cl- ou Br-) em concentrações de surfactantes tão baixas quanto 10 µM. Estas vesículas foram denominadas microvesículas (µV), cuja Tm diminui monotonicamente com a concentração de DODAX até valores de Tm das vesículas tradicionais preparadas em 1.0 mM do surfactante. O efeito do contra-íon (Br- e Cl-) no comportamento termotrópico de fase das vesículas mistas de DODAB-DODAC foi investigado por DSC, condutimetria e espalhamento dinâmico de luz (DLS). Observou-se que a Tm aumenta sigmoidalmente de 45.8 a 48.9 oC com a fração molar de DODAC (xDODAC), com um ponto de inflexão no ponto eqüimolar. A condutividade e o diâmetro hidrodinâmico das vesículas variam muito pouco com xDODAB, indicando que a densidade superficial de carga das vesículas de DODAX é semelhante entre si, e o efeito do contra íon na Tm de DODAX se deve a interações específicas desses contra-íons na interface das vesículas. Medidas de DSC, fluorescência e turbidez de misturas de DODAB-DDAB indicam que as vesículas de DODAB têm maior afinidade por DDAB do que o oposto, resultando na formação de duas populações de vesículas mistas de DDAB-DODAB, com propriedades distintas. Além disso, medidas de fluorescência mostraram que a presença de pequena quantia de DODAB incorporado nas vesículas de DDAB causa um efeito significante na emissão da sonda devido ao aumento do tamanho das vesículas, sugerido por medidas de turbidez. O estudo dos sistemas DODAB/CnTAB/água na concentração total de surfactante igual a 1,0 e 5,0 mM, variando a concentração de CnTAB, e também mantendo a concentração de DODAB fixa em 1,0 mM, revelou uma forte dependência do comprimento da cadeia de hidrocarbonetos... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Differential scanning calorimetry (DSC) and fluorescence of the probe Nile Red studies reveal the formation of DODAX vesicles (X = Br- and Cl-) at surfactant concentrations as low as 10 µM. These vesicles were referred to as microvesicles (mV), whose Tm decreases monotonically with increasing DODAX concentration to the value for the ordinary vesicles at 1 mM. The effect of counterion (Br- and Cl-) on the thermotropic phase behavior of mixed DODAB-DODAC vesicles were investigated by differential scanning calorimetry (DSC), conductimetry and dynamic light scattering (DLS). Tm increases sigmoidally from 45.8 to 48.9 oC with DODAC molar fraction (xDODAC), with an inflection point at the equimolarity. The conductivity and the apparent hydrodynamic diameter vary little with xDODAB, indicating that the surface charge density is similar for DODAX, evidencing that the effect of counterion on Tm is due to the counterion specific interactions. DSC, fluorescence and turbidity measurements indicate a higher affinity of DDAB for DODAB vesicles than the reverse, resulting in two populations of mixed DDAB-DODAB vesicles with different properties. Besides, fluorescence measurements show that the presence of a small amount of DODAB in DDAB vesicles causes a pronounced effect on the Nile Red emission, due to the increase in vesicle size, as suggested from turbidity results. The study of DODAB/CnTAB/água systems at 1.0 and 5.0 total surfactant concentration, and varying CnTAB concentrations with constant 1.0 mM DODAB revealed a strong dependence of the chain length n and relative concentration of the surfactante in the properties of mixed DODAB-CnTAB vesicles. This study allowed analyzing the thermotropic phase behavior containing different amount of DODAB, and the mechanism of vesicle-micelle transition with increasing CnTAB concentration, below and above CMC... (Complete abstract click electronic access below) / Doutor

Ce travail de thèse se propose d’analyser la question identitaire dans un corpus de films d’Afrique des années 2000. Echappant à la définition monolithique du "cinéma africain" comme genre à part, ces récits de fiction transnationaux reflètent la pluralité des appartenances culturelles des cinéastes. À partir de la notion de paraphrase, théorisée par Jean-Pierre Esquenazi dans son livre La vérité de la fiction. Comment peut-on croire que les récits de fiction nous parlent sérieusement de la réalité? nous étudions de quelle manière les fictions choisies exemplifient certains aspects des réalités complexes et des parcours de leurs auteurs. Il s’agit de parcours – personnels et collectifs – marqués par l’histoire de la colonisation, par des représentations initiales déformées des Africains et par l’expérience et les déchirures de la migration, celle-ci plaçant les cinéastes en position de minorité dans leur pays de résidence. Nous montrons que ce statut en marge, qui oblige à une redéfinition de soi, peut devenir source de créativité artistique et générer un style cinématographique original. Les fictions étudiées, tout en partant de contextes socioculturels spécifiques, touchent à des problématiques humaines universelles. Elles produisent des énonciations collectives qui prennent aussi une valeur politique. Grâce à des formes narratives et à des esthétiques sobres la plupart du temps, mais capables d’exprimer l’hybridité culturelle et la pluralité, ce sont des personnages complexes, aux identités composites, qui sont mis en scène dans leur devenir. Les notions de cinéma accentué d’Hamid Naficy et de mineur développée par Deleuze et Guattari nous aident à explorer comment le regard décentré, interstitiel et multifocal des cinéastes transnationaux offre des points de vue différents et novateurs. / The aim of this thesis is to analyze the identity issues in a corpus of African films made in the 2000's. These transnational films escape from the monolithic definition of "African cinema" as a genre, and translate the plural belongings of filmmakers. Using the concept of paraphrase theorized by Jean-Pierre Esquenazi in his book La vérité de la fiction. Comment peut-on croire que les récits de fiction nous parlent sérieusement de la réalité?, we study how these fictions illustrate some aspects of their authors' complexe realities and paths. Their personal and collective experiences are marked by initial misrepresentations, by colonization, by migration and cultural ruptures, which place the filmmakers in a marginal position within their countries of residence. It will illustrate how the exilic condition, requiring a redefinition of oneself, could also become a source of artistic creativity, and could encourage one to invent an adequate cinematographic style. These fictions, even starting from specific socio-cultural contexts, expand to some larger human issues. Expressing collective statements, they become political movies. Through often sober narrative forms and aesthetics, but able to express cultural hybridity and plurality, complex characters, with shifting identities, are shown in their becoming process. The ideas of accented cinema by Hamid Naficy and of minor by Deleuze and Guattari help us to explore how the "off-centered", interstitial and multifocal perspective of the transnational filmmakers offer us different and innovatory points of view.

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Não consta resumo na publicação. / Abstract not available.

Geometries of sills intruded into the lava pile of the Faroe Island Basalt Group (FIBG), which were targeted in this study, were mostly recorded by conventional mapping methods where measured distances and positions were plotted onto accurate topographic maps aided by the use of high-quality photos of relevant outcrops. These data were subsequently used to manually plot 2D profiles along selected tracks and to produce electronic 3D maps using ArcGIS software. The general geometries of the investigated sills, measured at lateral scales ranging from a few metres to a few kilometres and at vertical scales ranging from a few metres to a few hundred metres, differ somewhat from typical sill geometries reported previously for sills intruded into sedimentary successions. The ubiquitous saucer-shapes of the sills from this study, which generally curve upwards in a gradual manner from inner sub-horizontal sections to steeper outer margins, contrast with the common angular transitions from inner sub-horizontal to outer steeper sections of sills reported from sedimentary host-rocks. In this thesis we explore possible alternatives to already existing theories on sill emplacement in sedimentary successions. Major and trace element compositions for samples representing most of the sills exposed in the Faroe Islands have been determined by means of XRF and ICP-MS analyses. Geochemically most of these sills can be grouped into two main categories characterised either by high or by low TiO2 contents. Different sorts/types of metasomatism of source rocks to high-TiO2 versus low-TiO2 sills are indicated by different Nb and Ta anomalies. Modelling by means of REE and other trace elements suggest that much of the compositional differences between these two main categories can be explained by various degrees of partial melting of broadly similar mantle sources. Additional fractionation and accumulation of plagioclase modified some of the melts that gave rise to the actual sills. The initial partial melting event probably occurred at depths slightly shallower than the lower limit of the garnet stability field at ~85 km while plagioclase crystallisation/accumulation most likely occurred at depths shallower than ~18 km. Isotopic compositions may point to very slight contamination of some sills with crustal material.

Die Arbeit analysiert das Lasermikrosintern von Metallen in seiner Gesamtheit durch kalkulierbare Modelle und Formulierungen. Hierfür wird der Sintervorgang in relevante Prozessschritte untergliedert. Die darauf aufbauenden Berechnungen der Prozessparameter werden in Form analytischer Ansätze und durch numerische Simulation analysiert. Anfänglich werden die Modelle der Einzelschritte und deren Resultate werden auf Übereinstimmung mit den experimentellen Daten und Beobachtungen geprüft. Hierbei dienen die Modelle, Algorithmen und analytischen Beziehungen als nachhaltiges Instrumentarium für Analysen und Beschreibungen dieses und ähnlicher Prozesse. Mithilfe der entwickelten Algorithmen werden die bisherigen Vorstellungen zum Prozessmechanismus verifiziert, korrigiert, ergänzt und offene Fragen zur Prozessmechanik beantwortet. Abschließend werden die mechanistischen Modelle der Einzelschritte zur Diskussion experimenteller Ergebnisse und beobachteter Prozessphänomene in Form einer Gesamtinterpretation der betreffenden Lasermikrosinterregime zusammengeführt. Zunächst werden die Prozessbedingungen und Prozessbeschreibungen sowie die Modelle zur Strahlungsabsorption in Pulvern in Arbeiten fremder Autoren vorgestellt. Zur Beschreibung der Ursache und Wirkung laserinduzierter Plasmen, ein besonders beim Lasermikrosintern bedeutsames Phänomen, wird auf eigene frühere Arbeiten zurückgegriffen. Aus den besonderen Bedingungen des Lasermikrosinterns wird die formale Gliederung des Prozessverlaufs in drei separate Dissipationsphasen abgeleitet. Die drei relevanten Reaktionsphasen sind hierbei, die Absorption der Strahlung, die Wärmeausbreitung und Schmelzerzeugung sowie die Wärmeleitung im Pulverbett. Die ablaufenden Einzelmechanismen als Folge der gepulsten Laserstrahlung werden durch geeignete Näherungen beschrieben und berechnet. Die Resultate werden mit grundlegender Aussage mit experimentellen Beispielen verglichen und verifiziert. Die Betrachtung unterschiedlicher Regime des Lasermikrosinterns erfolgt, gestützt auf die Ergebnisse der Kalkulationen der energetisch-thermodynamischen Synthese. Es werden Aussagen zu den regimespezifischen Prozessmerkmalen getroffen und mit den Beobachtungen verglichen. Oder, es werden regimespezifische Beobachtungen mit Hilfe der im vorhergehenden Abschnitt entwickelten prozessanalytischen Werkzeuge interpretiert. Auswirkungen von Parametervariationen auf den Gesamtprozess werden im Hinblick auf das Optimierungspotential diskutiert.

Climate change is no longer imminent but eminent. To combat climate change, effective, efficient and smart energy use is imperative. Thermal energy storage (TES) with phase change materials (PCMs) is one attractive choice to realize this. Besides suitable phase change temperatures and enthalpies, the PCMs should also be robust, non-toxic, environmental-friendly and cost-effective. Cost-effective PCMs can be realized in bulk blends. Blends however do not have robust phase change unless chosen articulately. This thesis links bulk blends and robust, cost-effective PCMs via the systematic design of blends as PCMs involving phase equilibrium evaluations. The key fundamental phase equilibrium knowledge vital to accurately select robust PCMs within blends is established here. A congruent melting composition is the most PCM-ideal among blends. Eutectics are nearly ideal if supercooling is absent. Any incongruent melting composition, including peritectics, are unsuitable as PCMs. A comprehensive state-of-the-art evaluation of the phase equilibrium-based PCM design exposed the underinvestigated categories: congruent melting compositions, metal alloys, polyols and fats. Here the methods and conditions essential for a comprehensive and transparent phase equilibrium assessment for designing PCMs in blends are specified. The phase diagrams of the systems erythritol-xylitol and dodecane-tridecane with PCM potential are comprehensively evaluated. The erythritol-xylitol system contains a eutectic in a partially isomorphous system unlike in a non-isomorphous system as previous literature proposed. The dodecane-tridecane system forms a probable congruent minimum-melting solid solution, but not a maximum-melting liquidus or a eutectic as was previously proposed. The sustainability aspects of a PCM-based TES system are also investigated. Erythritol becomes cost-effective if produced using glycerol from bio-diesel production. Olive oil is cost-effective and has potential PCM compositions for cold storage. A critical need exists in the standardization of methods and transparent results reporting of the phase equilibrium investigations in the PCM-context. This can be achieved e.g. through international TES collaboration platforms. / Energi är en integrerad del av samhället men energiprocesser leder till miljöbelastning, och klimatförändringar. Därför är effektiv energianvändning, ökad energieffektivitet och smart energihantering nödvändigt. Värmeenergilagring (TES) är ett attraktivt val för att bemöta detta behov, där ett lagringsalternativ med hög densitet är s.k. fasomvandlingsmaterial (PCM). Ett exempel på ett billigt, vanligt förekommande PCM är systemet vatten-is, vilket har använts av människor i tusentals år. För att tillgodose de många värme- och kylbehov som idag uppstår inom ett brett temperaturintervall, är det viktigt med innovativ design av PCM. Förutom lämplig fasförändringstemperaturer, entalpi och andra termofysikaliska egenskaper, bör PCM också ha robust fasändring, vara miljövänlig och kostnadseffektiv. För att förverkliga storskaliga TES system med PCM, är måste kostnadseffektivitet och robust funktion under många cykler bland de viktigaste utmaningarna. Kostnadseffektiva PCM kan bäst erhållas från naturliga eller industriella material i bulkskala, vilket i huvudsak leder till materialblandningar, snarare än rena ämnen. Blandningar uppvisar dock komplexa fasförändringsförlopp, underkylning och/eller inkongruent smältprocess som leder till fasseparation. Denna doktorsavhandling ger ny kunskap som möjliggör att bulkblandningar kan bli kostnadseffektiva och robusta PCM-material, med hjälp av den systematiskutvärdering av fasjämvikt och fasdiagram. Arbetet visar att detta kräver förståelse av relevanta grundläggande fasjämviktsteorier, omfattande termiska och fysikalisk-kemiska karakteriseringar, och allmänt tillämpliga teoretiska utvärderingar. Denna avhandling specificerar befintlig fasjämviktsteori för PCM-sammanhang, men sikte på att kunna välja robusta PCM blandningar med specifika egenskaper, beroende på tillämpning. Analysen visar att blandningar med en sammansättning som leder till kongruent smältande, där faser i jämvikt har samma sammansättning, är ideala bland PCM-blandningar. Kongruent smältande fasta faser som utgör föreningar eller fasta lösningar av ingående komponenter är därför ideala. Eutektiska blandningar är nästan lika bra som PCM, så länge underkylning inte förekommer. Därmed finns en stor potential för att finna och karakterisera PCM-ideala blandningar som bildar kongruent smältande föreningar eller fasta lösningar. Därigenom kan blandningar med en skarp, reversibel fasändring och utan fasseparation erhållas – egenskaper som liknar rena materialens fasändringsprocess. Vidare kan man, via fasdiagram, påvisa de blandningar som är inkongruent smältande, inklusive peritektiska blandningar, som är direkt olämpliga som PCM. Denna avhandling ger grundläggande kunskap som är en förutsättning för att designa PCM i blandningar. Genom en omfattande state-of-the-art utvärdering av fas-jämviktsbaserad PCM-design lyfter arbetet de PCM-idealiska blandningarna som hittills inte fått någon uppmärksamhet, såsom kongruenta smältande blandningar, och materialkategorierna metallegeringar, polyoler och fetter. Resultatet av arbetet visar dessutom att vissa PCM-material som ibland föreslås är direkt olämpliga då fasdiagram undersöks, bl a pga underkylning och även peritektiska system med fasseparation och degradering av kapaciteten (t ex Glauber-salt och natriumacetat-trihydrat). Denna avhandling specificerar och upprättar grundläggande teori samt tekniker, tillvägagångssätt och förhållanden som är nödvändiga för en omfattande och genomsynlig fasjämviktsbedömning, för utformning av PCM från blandningar för energilagering. Med detta som bas har följande fasdiagramtagits fram fullständigt: för erytritol-xylitol och för dodekan-tridekan, med PCM-potential för låg temperaturuppvärmning (60-120 °C) respektive frysning (-10 °C till -20 °C) utvärderas fullständigt. Erytritol-xylitol systemet har funnits vara eutektiskt i ett delvis isomorft system, snarare än ett icke-isomorft system vilket har föreslagits tidigare litteratur. Dodekan-tridekan systemet bildar ett system med kongruent smältande fast lösning (idealisk som en PCM) vid en minimumtemperatur, till skillnad från tidigare litteratur som föreslagt en maximumtemperatur, eller ett eutektiskt system. Teoretisk modellering av fasjämvikt har också genomförts för att komplettera det experimentella fasdiagrammet för systemet erytritol-xylitol. Efter granskning av de metoder som använts tidigare i PCM-litteraturen har här valts ett generiskt tillvägagångssätt (CALPHAD-metoden). Denna generiska metod kan bedöma vilken typ av material och fasändring som helst, till skillnad från en tidigare använda metoder som är specifika för materialtyper eller kemiska egenskaper. Denna teoretiska studie bekräftar termodynamiskt solvus, solidus, eutektisk punkt och erytritol-xylitol fasdiagrammet i sin helhet. Vad gäller hållbarhetsaspekter med PCM-baserad TES, lyfter denna avhandling fokus på förnybara och kostnadseffektiva material (t.ex. polyoler och fetter) som PCM. Som exempel har här undersökts erytritol och olivolja, med förnybart ursprung. Erytritol skulle kunna bli ett kostnadseffektivt PCM (163 USD/kWh), om det produceras av glycerol vilket är en biprodukt från biodiesel/bioetanolframställning. Olivolja är ännu ett kostnadseffektivt material (144 USD/kWh), och som här har påvisats innehålla potentiella PCM sammansättningar med lämpliga fasändringsegenskaper för kylatillämpningar. En övergripande slutsats från denna avhandling är att det finns ett behov av att standardisera tekniker, metoder och transparent resultatrapportering när det gäller undersökningar av fasjämvikt och fasdiagram i PCM-sammanhang. Internationella samarbetsplattformar för TES är en väg att koordinera arbetet. / <p>QC 20170830</p>