Toward the objective to create or to replace impaired tissues, it is essential to establish a culture process allowing tissue growth in vitro . The Petri dish culture or the traditional 2D culture has only a limited potential, mainly caused by a poor oxygen mass transfer to feed larger tissue constructs. In this project, an autonomous and complete bioprocess has been built to fullfill these needs. The developed reactor is versatile because many cell culture chamber designs can be connected to it. Two proportional-integral algorithms (PI) can control the dissolved oxygen concentration and the pH. The pressure, the temperature and mass flow rate are recorded in real time. An actuator allows mimicking the cardiac output flow. In this mémoire , it will be demonstrated how the reactor has been optimized to reduce the risk of bioburden. Also, the procedures to develop the control tools of the PI algorithm will be detailed. To characterize the reactor, a RTD study will be presented. To characterize the cell culture chamber, a permeability analysis using fluorescent microscopy and magnetic resonance imaging (MRI) will be exposed. Finally, two cell culture chamber designs to orient microvessel formation have been tested and these results will be presented.

This thesis studies a multiple-input single ended primary inductor converter (MI SEPIC) topology. The configuration allows the integration of different low-power distributed generation sources, such as individual photovoltaic modules, fuel cells, and small residential wind generators, into a common dc main bus. The current source interface allows the integration of all types of sources without the addition of filters; sources that require a nearly constant input current, such as fuel cells. In addition to discussing the circuit’s main models and operation, the thesis evaluates the stability under a decentralized PI control scheme through small signal analysis. The analysis is verified with simulations and experiments with prototypes. A derived circuit topology, the isolated MI SEPIC, is also explored here. In addition, a nonlinear control scheme, Lyapunov-based control, is implemented to stabilize an MI SEPIC. / text

The work described in this thesis demonstrates the use of supramolecular chemistry in the template-directed synthesis of porphyrin nanorings and as a tool to control conformation and topology of π-conjugated porphyrin oligomers. Particular emphasis is placed on changes to the electronic structure of these oligomers depending on their conformation. Chapter 1 gives an overview of π-conjugated porphyrin oligomers and conjugated macrocycles in general, followed by an introduction into supramolecular cooperativity and small angle X-ray scattering in solution. Chapter 2 describes advances in the synthesis, solution structure elucidation and optoelectronic properties of a fully conjugated cyclic porphyrin hexamer. The high rigidity and symmetry of this nanoring as well as its bent π-system lead to a significant decrease in its HOMO-LUMO gap. The resulting near-infrared emission was exploited in the fabrication of light emitting diodes, demonstrating the use of a bent topology for minimizing aggregation in thin films. The synthesis of a [12]porphyrin nanoring using a hexadentate template is presented in Chapter 3. The concept of Vernier templating is introduced as a general strategy for the synthesis of large monodisperse macrocycles. The nanoring is characterized and its cooperative binding to two template molecules is studied. In Chapter 4 a bidentate ligand is used in the cooperative formation of a sandwich complex beween two nanorings. Chapter 5 provides an analysis of the rigidity of the butadiyne linked porphyrin oligomers used throughout this thesis. A linear chain is significantly more flexible in solution than on a surface where it is confined within two dimensions. Analysis of the persistence length indicates that a porphyrin nanoring with more than around 20 units would not be significantly strained. The supramolecular binding of linear porphyrin oligomers to carbon nanotubes is analyzed in Chapter 6. The binding strength increases sharply with oligomer length and binding is strongest with (8,6) and (7,5) tubes. The energy level alignment in these porphyrin CNT complexes appears to be favorable for an application in photovoltaics. In Chapter 7 bisamidine-carboxylate salt bridges together with zinc-nitrogen coordination chemistry are used to access a variety of topologies in assemblies based on carboxylic acid functionalized porphyrin dimers.

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

Cette thèse se situe dans le cadre de l'analyse symbolique des protocoles Les contributions sont représentées par l'obtention de résultats de décidabilité et de transfert dans les directions suivantes qui sont des thèmes majeurs en vérification des protocoles : - traitement des primitives cryptographiques : chiffrement CBC, signatures en aveugle; - propriétés de sécurité : secret fort, existence de cycles de clefs; - approches pour la sécurité : construction de protocoles sûrs. Ainsi, nous avons montré la décidabilité (d'une part) de l'existence de cycles de clefs et (d'autre part) du secret pour des protocoles utilisant le mode de chiffrement CBC ou des signatures en aveugle. Nous avons aussi transféré la sécurité des protocoles d'un cadre faible vers un cadre plus fort dans les sens suivants. D'une part, nous avons montré qu'une propriété de secret faible implique sous certaines hypothèses une propriété de secret plus forte. D'une autre part, nous avons construit des protocoles sûrs à partir de protocoles ayant des propriétés plus faibles. / This thesis is developed in the framework of the symbolic analysis of security protocols. The contributions are represented by decidability and transfer results in the following directions which are major topics in protocol verification: - treatment of the cryptographic primitives: CBC encryption, blind signatures; - security properties: strong secrecy, existence of key cycles; - approaches for protocol security: construction of the secure protocols. Thus, we showed the decidability (on the one hand) of the existence of key cycles for a bounded number of sessions using a generalized constraint system approach, and (on the other hand) of secrecy for protocols using the CBC encryption or blind signatures for an unbounded number of sessions by using a refined resolution strategy on a new fragment of Horn clauses. We also transferred protocol security from a weak framework towards a stronger framework in the following directions. On the one hand, we showed that a weak property of secrecy (i.e. reachability-based secrecy) implies under certain well-motivated assumptions a stronger secrecy property (i.e. equivalence-based secrecy). On the other hand, we built protocols secure against active adversaries considering an unbounded number of sessions, by transforming protocols which are secure in a non-adversarial setting.

A device for identifying forest fires in an early stage has been developed during the course of this project. Attached to a drone, this prototype will provide a live-stream to a web server displaying a blended frame, made of a thermographic image showing thermal radiation and a regular photography with the visible light. The platform consists of a small single-boarded computer, a thermal camera sensor and a regular camera module. All powered by a power bank and fitted into a custom made 3D printed plastic case. At startup the computer automatically executes scripts written in Python, initializing its sensor components and processes the captured images which finally gets transmitted to a live-stream via a web server connection. Everything described above worked well, but originally the intent was for the web interface to provide a map with the current location coordinates of the drone. Since a module for mobile communication with support for GPS was not acquired, any implementation of such kind was impossible. However, several drone models already possess the feature to obtain such coordinates.

Orientador: Enéas Rente Ferreira / Banca: Darlene Aparecida Oliveira Ferreira / Banca: Marcos Antônio de Castro Marques Teixeira / Banca: Alexandre Carvalho de Andrade / Banca: Silvio Carlos Bray / Resumo: As características da sociedade se refletem diretamente no arranjo espacial da cidade, na forma como as pessoas habitam, trabalham e se deslocam em seu cotidiano. Na cidade moderna, produto da economia de mercado, é comum a tentativa de aglutinação da população segundo estratos econômicos, com as pessoas buscando a proximidade com seus assemelhados. Nesse contexto, atuam diferentes agentes sociais, cada um centrado principalmente em estratégias e práticas espaciais de valorização espacial, expandindo-se em todo o território, inclusive em Áreas de Preservação Permanente - APP. Em consonância com os objetivos propostos, buscou-se, inicialmente, na literatura, o aporte teórico para a temática a ser desenvolvida, bem como os procedimentos a serem adotados no tratamento dos dados estatísticos quantitativos apresentados em forma de mapas temáticos. Conceituaremos termos que julgamos necessários, os seus respectivos, entendimentos na analise dessa pesquisa. Nas considerações finais, apontamos uma análise teórica metodológica pertinente a um novo redirecionamento urbano, baseado em uma Geografia Critica de construção espacial para uma qualidade de vida em Teresina, onde prevaleça a construção e reconstrução do espaço e sua continua análise / Abstract: Society's characteristics are reflected directly in the spatial arrangement of the city, in the way people live, work and travel in their daily lives. In the modern city, a product of the market economy, it is common to attempt to agglutination of the population according to economic strata, with people seeking proximity to their counterparts. Where different actors, each centered mainly on spatial strategies and practices of spatial enhancement, however, expanding throughout the country, including in Permanent Preservation Areas - APP. In line with the goals we sought initially in the literature, the theoretical basis for the theme to be developed, and the procedures to be adopted in the treatment of quantitative statistical data presented in the form of thematic maps. We conceptualize terms which we believe are necessary, their respective, understandings in the analysis of this research. In the final considerations, we point out a methodological theoretical analysis relevant to a new urban redirection based on a Critical Geography spatial construction for a quality of life in Teresina. Where prevails the construction and reconstruction of space and continues its analysis / Doutor

A análise química de solo fornece suporte para o manejo de sua fertilidade, por meio de extratores que visam determinar o grau de suficiência ou deficiência de nutrientes no solo. As metodologias que avaliam a disponibilidade de fósforo (P) certamente são as que apresentam as maiores controvérsias devido, principalmente, à complexidade do comportamento do nutriente no solo. No Brasil, os métodos mais utilizados para avaliar a disponibilidade de P em solos agricultáveis são Mehlich e resina de troca iônica. O método que emprega tiras de papel de filtro impregnadas com óxido de ferro (Papel-Pi) possui princípio semelhante ao da resina, no entanto é pouco utilizado no Brasil. Devido à deficiência generalizada de nutrientes nos solos brasileiros o gesso agrícola constitui-se um insumo adequado para minimizar condições adversas. Porém, foram relatados problemas na avaliação da disponibilidade de P em solos com elevados teores de gesso (gipsíferos) devido à reação deste com o íon bicarbonato (HCO3 -), presente na solução Olsen ou na resina de troca iônica, formando carbonato de cálcio que precipita e/ou adsorve o P disponível. Nestas situações os teores de P tendem a ser subestimados. Em solos ácidos, onde o gesso é amplamente utilizado, não há relatos sobre este problema. Assim, objetivou-se com o presente trabalho estudar a interferência do gesso na disponibilidade de P em solos ácidos, sendo conduzidos quatro experimentos. Em três experimentos de incubação aplicaram-se tratamentos com doses variando de 0 até 75 g kg-1 de fosfogesso, gipsita ou gesso puro, além de doses de P na forma de superfosfato triplo (SFT) ou fosfato natural reativo (FNR). Foram utilizadas amostras de cinco solos com características químicas e físicas variadas. Foi conduzido um experimento com doses de fosfogesso em casa de vegetação cultivando-se milho. Avaliaram-se os teores de P nas amostras de solo pelos métodos da resina de troca iônica (saturada com NaHCO3), Mehlich e Papel-Pi, e no experimento de casa de vegetação, estes teores foram correlacionados com a produção de massa seca e com o P acumulado pelo milho. Em todas as situações estudadas o gesso interferiu na avaliação dos teores de P-resina, fato não observado para os teores de PMehlich e P-Papel-Pi. Confirmou-se a hipótese de que métodos que empregam HCO3 - podem subestimar os teores de P devido à interferência do gesso, naturalmente dos solos ou adicionado com a finalidade de corrigi-los. Houve boa correlação entre os teores de P-Papel-Pi e P-Mehlich, exceto quando utilizou-se FNR, pois a solução Mehlich superestimou estes valores devido à sua ação ácida. De forma geral, não houve boa correlação entre os teores de P no solo e a produção de massa seca e o P acumulado pelo milho, devido ao desenvolvimento irregular das plantas em função das maiores doses de fosfogesso. Portanto, confirmou-se que os problemas da interação do bicarbonato com o gesso, relatados até então para solos gipsíferos ou calcareos, podem ocorrer também em solos ácidos com aplicação de gesso. No entanto, notou-se claramente que a quantidade de gesso necessária para causar esta interferência supera as doses normalmente aplicadas. / The soil chemical analysis provides technical support for soil fertility management through methodologies aiming to evaluate the level of sufficiency or deficiency of nutrients. The methods used to evaluate the phosphorus (P) bioavailability are certainly the most controversial which is due, mainly, to the complex interactions of this nutrient in the soil. In Brazil, the most common methodologies to evaluate soil P bioavailability in agricultural soils are the Mehlich and the ion exchange resin. The method that uses filter paper strips impregnated with iron oxide (Pi paper) is very similar in principle to the ion exchange resin, but has not been adequately studied in Brazil. Due to general soil fertility problems, gypsum has been applied acting as a soil subsurface ameliorant and also to decrease high soil sodium contents. Although, problems have been detected when evaluating P bioavailability in soils with high contents of gypsum due to the reaction of bicarbonate (HCO3 -), contained in the Olsen solution or in the ion exchange resin, because of the precipitation of calcium carbonate. In these situations the levels of P tend to be underestimated. In acid soils, where gypsum is widely applied, there is no investigation and reports on this problem, which was the objective of this study. Four experiments were carried out. In three incubation experiments different combinations were tested of P rates varying from 0 to 75 g kg-1 of phosphogypsuym, gipsite or reagent grade gypsum and the P sources triple superphosphates and Arad phosphate rock (APR). Five soil samples with different chemical and physical properties were used. Also, a greenhouse experiment was carried out with two short corn crops submitted to rates of gypsum applied to the soil. The soil samples were analyzed by three different methodologies, i.e., the ion exchange resin with NaHCO3 -, Mehlich and Pi paper, and in the greenhouse experiment the soil contents by these different procedures were correlated with dry-matter yield and P uptake by the corn plants. In all situations the presence of gypsum did interfere in the P bioavailability by the resin method, with a clear trend to decrease the P contents. The hypothesis that methods that utilize the HCO3 - can underestimate the amounts of soil P due to the presence of gypsum, natural or added to soils, was once again confirmed. An adequate correlation was found between the amounts of P evaluated by the Pi Paper and the Mehlich procedure, except when the APR was used, once the Mehlich tended to overestimate the values due to its acidic condition. In general, there was no adequate relation between the soil P and corn dry-matter yield or P uptake, which was probably due to irregular development of plants in treatments where high rates of gypsum was applied. It was shown that the interaction of HCO3 - with gypsum, before only reported for soils high in gypsum, can also occur in acid soils but it was noticed that the amount of gypsum to cause the interference is generally higher than the rates normally used at field conditions.

This thesis explores the use of discourse markers (DMs) in the speech of Chinese non-native speakers (NNSs) of English and native speakers (NSs), using corpus methodologies, the 'Linear Unit Grammar' analysis (Sinclair and Mauranen 2006) and text-based analyses. It reports that the DMs for analysis, 'like', 'oh', 'well', 'you know', 'I mean', 'you see', 'I think' and 'now', occur more frequently in the dialogic genres than in the monologic genres extracted from the three corpora, SECCL, MICASE and ICE-GB. The co-occurrence of DMs is taken as evidence to determine the categories for discussion with the suggested functions being secondary interpretations. Surprisingly, there are similarities in the use of DMs between Chinese NNSs and NSs. For the differences, some require NSs to become more tolerant and inclusive of the versions of English and some require pedagogical interventions for the Chinese NNSs. This thesis demonstrates that the use of DMs correlates with the genre, context, type of activity and identity of the speaker. All such factors affect the speakers' choice of a DM to use when giving priority to discourse organisation, fluency, the engagement of the listeners, the construction of the speaker‟s persona and the creation of solidarity.

The UN predicts that by 2050 there will water shortages throughout the globe. Current sources for safe, clean drinking water are being over mined and exhausted. Seawater provides an alternative water source, but a high salt content makes it unsuitable for the majority of applications. However, reverse osmosis lowers the salt content producing water that is safe for human consumption. Reverse osmosis uses a semi-permeable membrane to prevent the transport of salt but allows for the transport of water. Currently these membranes are susceptible to fouling and contamination, which reduces their efficiency. Graphene-oxide membranes offer a new material for reserves osmosis membranes. Sheets of graphene-oxide are stacked in a layered structure. The separation between the sheets can be controlled using physical confinement, resulting in limited ion permeation of abundant cations in seawater, like Na+ and K+. This is believed to be due to the separation of 0.76 nm between the graphene sheets, forcing the ions to lose its surrounding water molecules, making it unfavourable for the ion to travel through the membrane. Molecular dynamics simulations can give an atomic level insight into the molecular processes within GO membranes. Recent simulations have shown that charged species are attracted to graphene surfaces due to polarisation of the pi-electron system. This work has managed to incorporate these ion-pi interactions into molecular dynamics simulations. Including ion-pi interactions caused some ions, like Na+ and K+, to prefer to lose water molecules and reside at a graphene surface. This work observed the same phenomena when ions were confined to graphene channel ranging from 1.3 nm - 0.7 nm. This observation could have a large impact on whether dehydration is limiting the permeation of these two ions, or if there are additional processes that limit their molecular transport.