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A presente pesquisa teve como objetivo a construção de microssensores amperométricos e potenciométricos para mensuração de oxigênio dissolvido (OD), gás sulfídrico (\'H IND.2\'S\'), íons amônio (\'NH IND.4\'POT.+\'), nitrato (\'NO IND.3\'POT.-\'), nitrito (\'NO IND.2\'POT.-\') e hidrogeniônicos (\'H POT.+\') em biofilmes aplicados a nitrificação de água residuária. Os biofilmes analisados por meio do uso dos microssensores construídos foram desenvolvidos sobre superfícies suportes de reatores de bancada do tipo célula de fluxo, as quais foram operadas sob diferentes condições operacionais em cinco experimentos distintos. Substrato sintético com concentrações de nitrogênio total Kjeldahl (NTK) de 40 ± 10 mg/L e demanda química de oxigênio (DQO) de 95 ± 5 mg/L foi utilizado para alimentação das células de fluxo no decorrer de todos os experimentos. Lodo aeróbio proveniente de reator de lodos ativados da Estação de Tratamento de Esgoto das Flores localizada em Rio Claro-SP foi usado como inóculo das células de fluxo. Análises físico-químicas de pH, alcalinidade, DQO, NTK, \'NO IND.3\'POT.-\', \'NO IND.2\'POT.-\' do afluente e do efluente das células de fluxo operadas foram realizadas para o monitoramento das condições de operação das mesmas. Concomitantemente às últimas, a obtenção de perfis de concentrações de oxigênio dissolvido, pH, íons nitrato e amônio foi realizada nos biofilmes formados sobre as superfícies inertes nas células. Os microssensores de OD se mostraram eficientes na mensuração de oxigênio dissolvido no interior de filmes biológicos que continham zonas aeróbias, anóxicas e anaeróbias. Os microeletrodos de pH e de íons amônio permitiram a verificação das variações de pH e das concentrações de \'NH IND.4\'POT.+\' (sentido meio líquido-biofilme) que se deram nas células de fluxo operadas. Os microssensores de íons nitrato construídos não apresentaram seletividade aos seus analitos (\'NO IND.3\'POT.-\') e foi constatado que os mesmos detectavam concentrações de íons nitrato e nitrito no meio, portanto esses passaram a ser denominados de microssensores para detecção de íons \'NO IND.X\'POT.-\'. A construção dos microeletrodos destinados a mensuração de íons nitrito não foi passível de realização visto que a membrana íon seletiva que seria aplicada nos mesmos não se encontrou disponível no mercado. Os microeletrodos de \'H IND.2\'S\' foram calibrados e, mediante as suas curvas de calibração verificou-se que os mesmos foram eficientes na medição da concentração do gás dissolvido em água, entretanto esses microssensores não foram empregados em biofilmes. / The goal of the current research was the construction of amperometric and potentiometric microsensors to measure dissolved oxygen (DO), hydrogen sulfide (\'H IND.2\'S\'), nitrite, nitrate, ammonium and pH in biofilms applied at wastewater treatment. The biofilms that were analyzed with the constructed microsensors were grown at the surface of flat-plate reactors, which were operated in five distinct experiments under different operational conditions. The growth media that had total Kjeldahl nitrogen (TNK) of 40 ± 10 mg/L and carbon oxygen demand (COD) of 90 ± 5 mg/L was used as feed of the flatplate reactors during the experiments. The reactors were inoculated with sludge originating from activated sludge reactor located in Rio Claro (SP). Alkalinity, pH, COD, \'NO IND.3\'POT.-\', \'NO IND.2\'POT.-\' analyses of the affluent and effluent of the reactors were carried out for the accompaniment of the operational conditions of the flat-plate reactors. Concomitantly to the last ones, microprofiles of DO, pH, nitrate and ammonium were obtained in the biofilms. The DO microsensors constructed showed a good performance when they were applied to measure oxygen concentrations in the microenvironments in biofilms. Ammonium and pH microelectrodes allowed the verification of the variations of pH and ammonium concentrations in the direction from the bulk liquid to the biofilm that occurred at the flatplate reactors. The nitrate microsensor has not presented selectivity for its primary ions (\'NO IND.3\'POT.-\') and it was evidenced that the same one detected the concentration of nitrate and nitrite (\'NO IND.X\'POT.-\'). The nitrite microsensor could not be constructed since the membrane that would be used was not available in the market. The \'H IND.2\'S\' microelectrodes had shown efficiency in measuring aqueous solutions with different concentrations of dissolved \'H IND.2\'S\'; however these devices were not applied in biofilms.

A presente pesquisa teve como objetivo primordial a verificação da viabilidade técnica de empregar sistema do tipo célula a biocombustível para tratamento de esgoto sanitário com geração de energia elétrica. A célula a biocombustível, em escala de bancada, adotada foi constituída por reator anaeróbio seguido de reator aeróbio, visando à remoção de matéria orgânica carbonácea e à nitrificação Cada reator apresentou área de 0,6275 m2 e volume útil de 24,0 L. A célula a biocombustível foi alimentada com esgoto sanitário com tempo de detenção hidráulica médio de 8 horas (nos dois módulos). Em cada reator instalou-se um eletrodo imerso, de modo que os dois eletrodos foram unidos por fio condutor externo. Foi verificada a potencialidade do sistema em gerar energia elétrica a partir das reações químicas e bioquímicas que se deram junto aos eletrodos e nos biofilmes aderidos aos mesmos. A operação da célula a biocombustível foi dividida em cinco Fases, denominadas de I, II, III, IV e V, sendo que o fator principal que distinguiu essas Fases consistiu no material eletródico. Manta de fibra de carbono e placa de grafite foram adotadas como ânodo da célula (reator anaeróbio). Chapa de aço inoxidável (AISI 316) e malhas de aço inoxidável (AISI 316) foram usadas como cátodo do sistema (reator aeróbio). Para monitoramento do sistema foram realizadas análises físico-químicas do afluente, do efluente do reator anaeróbio e do efluente do reator aeróbio e para o acompanhamento da produção de energia elétrica utilizou-se potenciômetro acoplado a software específico. Microssensores de OD, pH e potencial redox foram empregados como ferramentas auxiliares para o acompanhamento do crescimento e desenvolvimento dos biofilmes aderidos aos eletrodos da célula a biocombustível. Como resultados concernentes ao tratamento do esgoto sanitário foram obtidas eficiências médias de remoção de DQO de (74,4±17,1)% e de nitrificação de (65,8±21,0)%, no decorrer das cinco Fases. O valor da maior densidade de potência média verificada foi de 107,0 mW.m-2, ocorrida quando o ânodo da célula a biocombustível consistiu em placa de grafite e o cátodo em malha de aço inoxidável (AISI 316) do tipo 20, na Fase V. A dosagem de cloreto férrico e a colocação de meio suporte de material plástico no sistema para limpeza automática do cátodo, realizadas na Fase em que se observou a maior densidade de potência média foram consideradas como positivas no aprimoramento da obtenção de energia elétrica. Por meio da combinação dos resultados relacionados à geração de energia elétrica e da aplicação dos microssensores constatou-se que o desenvolvimento de biofilmes espessos sobre os eletrodos da célula a biocombustível consiste em fator negativo da sua eficiência energética. Concluiu-se que a célula a biocombustível é tecnicamente viável para o tratamento de esgoto com geração de energia elétrica, contudo diante do conhecimento que se tem sobre essa tecnologia, a sua adoção em escala real ainda é economicamente inviável. / This research aimed mainly to verify the technical feasibility of employing a system called biofuel cell for treating wastewater and generating electricity at the same time. The biofuel cell, in lab scale, adopted consisted of an anaerobic followed by an aerobic reactor, aiming the removal of carbonaceous organic matter and nitrification. Each reactor had an area of 0.6275 m2 and useful volume of 24.0 L. The biofuel cell was fed with sanitary wastewater with hydraulic retention time of eight hours (in both modules). In each reactor was installed an electrode immersed, and the two electrodes were connected by a wire conductor. The capability of the system to generate electricity from the chemical and biochemical reactions that occurred along the electrodes and in biofilms attached to them was verified. The biofuel cell operation was divided into five Phases, named I, II, III, IV and V, and the main factor that distinguished these Phases consisted of the electrode material. Carbon fiber felt and graphite plate were adopted as the anode of the cell (on anaerobic reactor). Stainless steel plates (AISI 316) and stainless steel meshes (AISI 316) were used as the cathode (on aerobic reactor). Monitoring system were carried out with physicochemical analyzes of the influent, anaerobic effluent and aerobic effluent and for monitoring the electricity production it was used a potentiometer coupled with a specific software. DO, pH and redox potential microsensors were employed as auxiliary tools for monitoring the growth and development of biofilms attached to the electrodes of the biofuel cell. The results concerning the treatment of wastewater were COD efficiencies removal of (74.4 ± 17.1)% and nitrification of (65.8 ± 21.0)%, throughout the five Phases. The amount of the higher power density observed was 107.0 mW.m-2 occurred when the anode of the biofuel cell consisted of graphite plate and cathode of stainless steel mesh (AISI 316) type 20, on Phase V . The dosage of ferric chloride and the placement of plastic midia on the aerobic module of the system for automatic cleaning of the cathode, conducted on Phase V, were considered positive for the improvement in obtaining electricity. By combining the results related to power generation and application of microsensors it was concluded that the development of thick biofilms on the electrodes of a biofuel cell is a negative factor in their energy efficiency. It was also concluded that the biofuel cell is technically feasible to treat sanitary wastewater and to generate electricity, but actually, based on the knowledge we have about this technology, its adoption in large scale is still not economically feasible.

O pós-tratamento de efluentes de reatores anaeróbios, tais como o Upflow Anaerobic Sludge Blanket (UASB), na maior parte de suas aplicações, faz-se necessário, já que esse tipo de tratamento biológico promove remoção de DBO na faixa de 60 a 75% e tem baixa eficiência na remoção de nitrogênio e fósforo. A remoção de nitrogênio geralmente é feita de forma convencional pela nitrificação, seguida da desnitrificação. Tanto a nitrificação, como a desnitrificação podem ser efetuadas em reatores com crescimento suspenso ou crescimento aderido, contudo é conhecido que sistemas baseados em biofilmes exercem influência direta na taxa da degradação de substrato e facilitam a retenção de bactérias nitrificantes em reatores. O principal objetivo deste trabalho é o de acompanhar o desenvolvimento de biofilmes aeróbios em reatores do tipo célula de fluxo para a nitrificação de substrato sintético simulando efluente de UASB, submetidos a diferentes velocidades superficiais (1, 4 e 8 m/h) e taxas de carregamento (0,25; 0,5 e 1,0 g N/\'M POT.2\' biofilme.dia). O desenvolvimento dos biofilmes nitrificantes foi acompanhado mediante perfis de microssensores e estimativa do número mais provável de bactérias nitrificantes (NMP). Nas células de fluxo operadas com taxa de carregamento mais baixa (0,25 g N/\'M POT.2\' biofilme.dia), foram obtidas as melhores eficiências de remoção de NTK, a qual representa valor menor que as taxas de carregamento empregadas na literatura para reatores de crescimento aderido usados na nitrificação. Considerando as células de fluxo com taxa de carregamento mais baixa, a célula que apresentou remoção de NTK próxima a 100% foi a de menor velocidade superficial de (1 m/h). Porém, esses sistemas apresentaram baixa eficiência para a nitrificação completa, obtendo maior produção de nitrito do que de nitrato; poderiam ser usados então na remoção de nitrogênio pela via curta. Os microssensores de OD foram eficientes para as análises de perfis de OD no interior dos biofilmes nitrificantes, mostrando grandes variações, à medida que o biofilme se desenvolvia, nas concentrações de OD do líquido circundante e do fundo do biofilme. / The post-treatment of anaerobic reactor effluents, such as the Upflow Anaerobic Sludge Blanket (UASB), in most applications, is necessary, since this kind of biological treatment promotes BOD removal ranging from 60 to 75% and it has low efficiency in nitrogen and phosphorous removal. Nitrogen removal is usually carried out in a conventional way through nitrification, followed by denitrification. Nitrification, as well as denitrification, can be achieved in suspended growth reactors, or in adhered growth reactors, however it is known that systems based on biofilms exert direct influence in substrate degradation rates and ease the retention of nitrifying bacteria in reactors. The main objective of this work is to follow the development of aerobic biofilms in flow cell type reactors for the nitrification of synthetic substrate simulating an UASB effluent, submitted to different superficial velocities (1, 4 and 8 m/h) and loading rates (0.25; 0.5 and 1.0 g N/\'M POT.2\' biofilm.day). The development of nitrifying biofilms was followed by microsensors profiles and an estimative of the most probable number of nitrifying bacteria (MPN). The best NTK removal efficiencies were obtained in flow cells operated with a lower loading rate (0.25 g N/\'M POT.2\' biofilm.day), which represents a lower level than the levels applied in literature for adhered growth reactors used for nitrification. Considering the flow cells with a lower loading rate, the cell that presented NTK removal close to 100% was the one with the lowest superficial velocity (1 m/h). However, these systems present low efficiency for complete nitrification, obtaining higher nitrite than nitrate production; they could then be used in nitrogen removal by short way. The DO microsensors were efficient for analyses of DO profiles inside nitrifying biofilms, showing great variations, while the biofilm developed itself, in the DO concentrations in the contiguous liquid and at the bottom of the biofilm.

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Ce travail de recherche porte sur la réalisation de dispositifs électroniques spécifiques et originaux (Transistors à effet de champ à microcanaux) dédiés à la détection des espèces chimiques et biochimiques en milieu liquide. Ce dispositif s'appuie sur la technologie des transistors à grille suspendue (SGFET) déjà réalisés à l'IETR, en y apportant une amélioration majeure qui consiste en l'intégration au sein de la structure d'un canal microfluidique. Cette structure, nommée transistor à canal microfluidique intégré, doit permettre de conserver la forte sensibilité de détection du SGFET mais aussi de garantir le passage du liquide testé sous la grille. Cette architecture permet aussi d'augmenter sa robustesse et sa fiabilité tout en ne nécessitant que de très petits volumes de solutions. Des microcanaux avec un bon maintien mécanique ont été réalisés par micro-usinage de surface en utilisant différents matériaux comme couche sacrificielle. Ces canaux ont été intégré dans un FET et leurs accès microfluidiques ont été assurés en réalisant des ouvertures (inlet/outlet) par la face avant. Les tests électriques ont montré un bon fonctionnement de ces capteurs avec une grande sensibilité de mesure du pH mais le passage du liquide est alors majoritairement dû aux phénomènes de capillarité. Une amélioration sur l'architecture de la structure a été faite, en réalisant des ouvertures par la face arrière. Un bon fonctionnement avec une grande sensibilité de mesure de pH ont été présentés. Finalement, une structure hybride contenant une ouverture sur la face avant et une autre sur la face arrière, a été élaborée et les tests d'injection de la solution ont été un succès. / This work presents the achievement of specific and original electronic devices (Field effect transistor with microfluidic channel), dedicated to the detection of chemical and biochemical species in liquid. This device relies on the technologies of suspended gate transistor, developed in IETR, with a major improvement in the structure by adjunction of a microfluidic channel integrated in the structure. This structure named transistor with integrated microfluidic channel must enable to guarantee the flow of liquid under the gate, while keeping the high sensitivity of the SGFET. This architecture also allows increasing its robustness and reliability while requiring only a very small amount of chemicals solutions. Microchannels with good mechanical properties were fabricated by surface micromachining using different materials as a sacrificial layer. These channels have been integrated into a FET and microfluidic accesses (inlet / outlet) were provided by making openings via the front face. Electrical tests showed good functioning of these sensors with high sensitivity of pH measurement. However in this case, liquid flow is mainly achieved by capillarity. An improvement on the architecture of the structure was made with opening on the rear face. A good behaviour with high sensitivity of pH measurement was presented. Finally, a hybrid structure containing one opening access in the front face and one on the rear face was elaborated and the injection of the solution was successful.

Hydrogen peroxide and chlorine detection is critical for many biological and environmental applications. Hydrogen peroxide plays important roles in a variety of fields including plant physiology, medical, environmental and biochemical applications. Its role in plant defense and signal transduction, diseases such as Parkinson's and Alzhemier's, industrial processes such as disinfection and wastewater treatment and biochemical enzymatic reactions is critical. Given the gamut of areas that hydrogen peroxide is a key component of; its detection assumes great importance. Similarly chlorine has long been used as a disinfectant for making drinking water safe, but excessive chlorination is an environmental and health hazard in itself. In this work, micromachining techniques have been used to design, fabricate and test electrochemical sensors and microneedle structure that can be integrated for detection of hydrogen peroxide and free chlorine. A novel nanomaterial has been integrated with the hydrogen peroxide microsensor, which greatly increases the sensor lifetime and robustness. Miniaturization, low detection limits, high sensitivity and selectivity, as well as ease of fabrication are some of the other advantages of this work.

Recent interest has emerged in microsensor platforms that are capable of supporting reconnaissance, surveillance and target acquisition operations. These devices typically consist of one or more sensors, signal conditioning and processing subsystems, a radio link and a power source. Sensors employed can range from acoustic, to seismic, to magnetic, to visible/infrared imagers. A notable shortcoming of these systems is the fact that they are battery powered. The use of a finite power source places an upper limit on the lifespan of such a system. Thus, a major thrust in the development and usage of these microsensor platforms lies in the conservation of their limited energy resources. In attempt to reduce power consumption and hence extend the system's lifespan, communication bandwidths are often limited. In order to reduce the required bandwidth, much of the signal processing necessary to achieve a desired functionality must be performed within the microsensor platform itself. This thesis effort provides this crucial bandwidth reduction by implementing in hardware an algorithm developed by the University of Maryland, which limits transmissions to the best view Regions-of-Interest (ROI) data, on the CAuS platform by BAE Systems. The hardware implementation was verified with a Matlab script that compared its results with those of the original algorithm. It was shown that these implementations were consistent for all of the data sets tested. Moreover, a subjective analysis, in which the detected ROIs were visually inspected, was performed to corroborate the former quantitative results. / Master of Science

Nous proposons dans le cadre de ce travail de thèse, une nouvelle approche de la détection non invasive de l’alcoolémie sanguine à l’aide de microcapteurs d’éthanol à base de SnO2. Cette méthodologie se base sur une détection indirecte de l’alcoolémie sanguine par une mesure des vapeurs d’éthanol émises par la perspiration cutanée suite à une consommation d’alcool. Afin de valider cette approche, il a fallu dans un premier temps démontrer la pertinence et la faisabilité de cette méthodologie de détection par la réalisation d’essais cliniques pilotes en collaboration avec une équipe médicale d’étude pharmacologique du CPCET Marseille. Les différentes mesures du taux d’éthanol réalisées dans les fluides biologiques tels que le sang et l’air expiré ont pu être précisément corrélées avec les mesures de vapeurs d’éthanol réalisées à travers la perspiration à l’aide de trois microcapteurs de gaz commerciaux à base d’oxydes métalliques intégrés à un bracelet. Ces dispositifs ont l’avantage d’être sensibles mais pas sélectifs à la nature du gaz détecté. Durant ces travaux, des couches sensibles de SnO2 ont été déposées par pulvérisation cathodique RF magnétron réactive sur un transducteur breveté par notre équipe, intégrant trois capteurs sur une même puce. L’optimisation des paramètres de dépôt et les analyses structurales des couches de SnO2, nous ont permis de réaliser un multicapteur d’éthanol démontrant des performances sous éthanol ; en termes de sensibilité sous atmosphère humide, de répétabilité et de temps de réponses et de recouvrement ainsi que du point de vue sélectivité / A new approach of a noninvasive detection of blood alcohol concentration using ethanol microsensors based on SnO2 Is developed in this work. The methodology is based on an indirect detection of blood alcohol concentration by measuring the ethanol vapor emitted through the skin perspiration after alcohol consumption. In order to validate this approach, first we demonstrated the relevance and the feasibility of this detection method by carrying out pilot clinical trials in collaboration with a medical team of pharmacological study of CPCET Marseille. The different measurements of the ethanol concentration carried out in biological fluids such as blood and exhaled air could be precisely correlated with the measurements of ethanol vapors performed through the perspiration using three commercial gas microsensors based on metal oxides integrated into a bracelet. . These devices have the advantage of being sensitive but not selective to the nature of the gas detected. During this thesis work, sensitive layers of SnO2 were deposited by reactive magnetron RF sputtering on a transducer patented by our team, integrating three sensors on the same chip. The optimization of the deposition parameters and the structural analyzes of the SnO2 layers, allowed us to develop an ethanol multi-sensor demonstrating performances under ethanol; in terms of sensitivity on humidity, repeatability and response and recovery times as well as from the point of selectivity

La mise au point de nouveaux systèmes biocompatibles de suivi des phénomènes de polymérisation de protéines est un enjeu majeur pour la compréhension des mécanismes moléculaires en vue d’une détection et d’un traitement précoce des pathologies dites conformationnelles telles que la maladie d’Alzheimer ou les maladies à prions. Dans ces pathologies, des protéines ou des fragments de celles-ci perdent leur structure, puis s’assemblent en fibres ordonnées au sein d’agrégats. Les mécanismes moléculaires du changement de conformation d'une protéine et sa polymérisation en fibres amyloïdes sont encore largement inconnus. La compréhension de ces mécanismes et le diagnostic sont étroitement liés à la disponibilité d’un concept analytique performant pour le suivi ex vivo de ces phénomènes.Pour répondre à cette problématique, un microsystème a été mis au point pour la détection et le suivi de polymérisation de la protéine tau et du peptide Aß, principaux biomarqueurs de la maladie d’Alzheimer. Le microcapteur est basé sur la propagation d’ondes acoustiques hautes fréquences qui permettent d’extraire les propriétés rhéologiques du milieu cible. En mesurant l’impédance complexe du biocapteur, un traitement du signal dédié permet l’extraction des paramètres viscoélastiques (module élastique et module visqueux). L’étude et le développement de ce microsystème impliquent un savoir-faire pluridisciplinaire en instrumentation : élaboration et conception et modélisation de biocapteurs, conditionnement des signaux et résolution des problèmes inverses associés.Tout d’abord, le capteur a été optimisé pour améliorer sa sensibilité et permettre le suivi de polymérisation. Un travail sur la faisabilité du système a montré la possibilité de discriminer des solutions de protéines de différentes concentrations. La finalité du système de détection étant la détection simultanée des différents biomarqueurs à l’origine de la maladie d’Alzheimer, un capteur multi-électrodes permettant la détection de ces différents analytes a été développé. / The development of new biocompatible systems for monitoring protein polymerization processes is a key issue for understanding the molecular mechanisms of detection and for early treatment of so-called conformational diseases such as Alzheimer's disease or prion diseases. In these pathologies, proteins or fragments lose their structure and then assemble themselves into ordered fibers within aggregates. The molecular mechanisms of the conformational changes of a protein and its polymerization into amyloid fibers are still largely unknown. Understanding these mechanisms and diagnosis are closely related to the availability of an efficient analytical concept for the ex vivo monitoring of these phenomena.To address this problem, a microsystem has been developed for the detection and monitoring of polymerization of tau and Aß peptide, the main biomarkers of Alzheimer's disease. The microsensor is based on the propagation of acoustic high frequency waves that extract the rheological properties of the target environment. By measuring complex impedance of the biosensor, a dedicated signal processing allows the extraction of viscoelastic parameters (viscosity and elasticity). The study and development of this microsystem involve multidisciplinary expertise in instrumentation: development and design and modeling of biosensors, signal conditioning and solving associated inverse problems.First, the sensor has been optimized to improve its sensitivity and allow tracking of polymerization. Work on the feasibility of the system showed the ability to discriminate protein solutions of different concentrations. Since the purpose of the detection system is the simultaneous detection of different biomarkers responsible for Alzheimer's disease, a multi-electrode sensor for the detection of these different analytes has been developed. The optimization of the sensor, the microfabrication processes and chemical surface treatments are also developed in this work.