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Biodegradable, pH-responsive hydrogel networks composed of poly(methacrylic acid) crosslinked with varying mol percentages of polycaprolactone diacrylate were synthesized. These materials were characterized using NMR and FTIR. The equilibrium and dynamic swelling properties of these pH-responsive materials were studied. Also, the materials’ degradation was characterized using swelling studies and gel permeation chromatography. Methods were developed to incorporate these novel hydrogels as sensing components in silicon-based microsensors. Extremely thin layers of hydrogels were prepared by photopolymerizion atop silicon microcantilever arrays that served to transduce the pH-responsive volume change of the material into an optical signal. Organosilane chemistry allowed covalent adhesion of the hydrogel to the silicon beam. As the hydrogel swelled, the stress generated at the surface between the hydrogel and the silicon caused a beam deflection downward. The resulting sensor demonstrated a maximum sensitivity of 1nm/4.5E-5 pH unit. Sensors were tested in protein-rich solutions to mimic biological conditions and found to retain their high sensitivity. The existing theory was evaluated and developed to predict deflection of these composite cantilever beams. Another type of hydrogel-based microsensor was fabricated utilizing porous silicon rugate filters as transducers. Porous silicon rugate filters are garnering increased attention as components of in vivo biosensors due to their ability for remote readout through tissue. Here, the biodegradable, pH-responsive hydrogel was polymerized within the pores of a porous silicon rugate filter to generate a novel, completely degradable sensor. Silicon was electrochemically etched in hydrofluoric acid to generate the porous silicon rugate filter with its reflectance peak in the near infrared region. Poly(methacrylic acid) crosslinked with polycaprolactone diacrylate was polymerized within the pores using UV free radical photopolymerization. The reflectance peak of this sensor varied linearly with pH in the region pH 2.2 to 8.8. This work shows promise towards utilizing porous silicon rugate filters as transducers for environmentally responsive hydrogels for biosensing applications. / text

The ultimate goal of this research is to provide a low cost, efficient, reproducible, quantitative, non-invasive screening method to diagnose diseases at an early stage through identification of volatile biomarkers of disease. Progress has been made in the areas towards development of an analytical system that can provide a rapid and specific assay for above mentioned Volatile Organic Compounds (VOCs). (i) Methods have been designed for the collection, concentration, identification and quantification of volatile biomarkers. (ii) Advanced signal processing evaluation of data has tentatively identified key VOCs patterns with breath and body odor. (iii) Novel absorbent coatings have been studied for use with miniature chemical sensors that one day may be part of a portable analytical system. Both breath and body odor contain a complex mixture of chemicals, which are influenced by many internal and external factors. Breath and skin odor samples were collected with minimum external contaminations using traditional SPME and active SPME GCMS techniques. Body odor from 65 human subjects was tested with and without selected scent removal products. Breath samples were collected from 21 canine subjects. The VOCs profiles of these samples were determined and then statistically treated with principal component analysis, discriminant analysis, and tree regression techniques to simplify and interpret the complex mixtures. While much of our work has utilized large bench-top equipment, our over-arching goal is to provide a portable device that can diagnose diseases at an early stage. Concurrent work was done to enhance the performance of a miniaturized detector for the detection of potential biomarkers. Two organic polymers mixed with conductive carbon nanoparticles were deposited between the microcapacitor plates of microsensors using ink-jet technology. Microsensors were also fabricated using conducting ionic liquids. The performances of the individual chemicapacitive sensors were characterized through exposure to different concentrations of varied volatile organic compounds with different functional groups in a climate-controlled vapor delivery system.

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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.

The development of environmental continuous monitoring of physicochemical parameters via portable small and inexpensive instrumentation is an active field of research as it presents distinct challenges. The development of a PCB MEMS-based inexpensive CTD system intended for the measurement of environmental parameters in natural waters, is presented in this work. Novel PCB MEMS fabrication techniques have also been developed to construct the conductivity and temperature transducers. The design and fabrication processes are based on PCB MEMS technology that combines Cu-clad liquid crystal polymer (LCP) thin-film material with a direct write photolithography tool, chemical etching and metallization of layers of electroless nickel, gold, and platinum. The basic principles of a planar four-electrode conductivity cell and the resistive temperature device are described here as well as the integration and the packaging of the microfabricated sensors for the underwater environment. Measurement results and successful field evaluation data show that the performance of the LCP thin-film microsensors can compete with that of conventional in-situ instruments.