abstract: Micro-electro-mechanical systems (MEMS) film bulk acoustic resonator (FBAR) demonstrates label-free biosensing capabilities and is considered to be a promising alternative of quartz crystal microbalance (QCM). FBARs achieve great success in vacuum, or in the air, but find limited applications in liquid media because squeeze damping significantly degrades quality factor (Q) and results in poor frequency resolution. A transmission-line model shows that by confining the liquid in a thickness comparable to the acoustic wavelength of the resonator, Q can be considerably improved. The devices exhibit damped oscillatory patterns of Q as the liquid thickness varies. Q assumes its maxima and minima when the channel thickness is an odd and even multiple of the quarter-wavelength of the resonance, respectively. Microfluidic channels are integrated with longitudinal-mode FBARs (L-FBARs) to realize this design; a tenfold improvement of Q over fully-immersed devices is experimentally verified. Microfluidic integrated FBAR sensors have been demonstrated for detecting protein binding in liquid and monitoring the Vroman effect (the competitive protein adsorption behavior), showing their potential as a promising bio-analytical tool. A contour-mode FBAR (C-FBAR) is developed to further improve Q and to alleviate the need for complex integration of microfluidic channels. The C-FBAR consists of a suspended piezoelectric ring made of aluminum nitride and is excited in the fundamental radial-extensional mode. By replacing the squeeze damping with shear damping, high Qs (189 in water and 77 in human whole blood) are obtained in semi-infinite depth liquids. The C-FBAR sensors are characterized by aptamer - thrombin binding pairs and aqueous glycerine solutions for mass and viscosity sensing schemes, respectively. The C-FBAR sensor demonstrates accurate viscosity measurement from 1 to 10 centipoise, and can be deployed to monitor in-vitro blood coagulation processes in real time. Results show that its resonant frequency decreases as the viscosity of the blood increases during the fibrin generation process after the coagulation cascade. The coagulation time and the start/end of the fibrin generation are quantitatively determined, showing the C-FBAR can be a low-cost, portable yet reliable tool for hemostasis diagnostics. / Dissertation/Thesis / Ph.D. Electrical Engineering 2011

Uma vasta gama de sensores são aplicados no mercado atual na busca pela melhoria de processos e produtos. Há um grande crescimento em novos sistemas que possam apresentar recursos que técnicas convencionais não apresentam. A busca por uma nova plataforma de sensoriamento surge a partir do interesse em identificar e controlar parâmetros ambientais isolados. Esta pesquisa em área incipiente no Brasil mostra o desenvolvimento de um sensor a partir de um material inteligente (smart material), que por definição, possui uma ou mais propriedades que podem sofrer mudanças significativas a partir de um estímulo externo. O presente trabalho é baseado na investigação de uma fita de material magnético amorfo, que ao exibir propriedades magnéticas e elásticas pelo efeito da magnetostricção, permite o monitoramento remoto de fenômenos físico-químicos do ambiente em que estiver exposta. O desenvolvimento deste sensor tem finalidade no monitoramento sem fio de solicitação mecânica, e alteração do tipo de fluido presente em um dado ambiente. O estudo e avaliação do sensor contou com técnicas de caracterização experimentais e de simulação. São apresentados sistemas e ensaios capazes verificar as ressonâncias do modo de vibração puro da amostra a partir de medidas ópticas e elétricas, quando submetidos a variação de fenômenos físicos. Os resultados indicam a dependência do efeito direto ao estímulo na ação externa do campo magnético em decorrências das características do material. Os resultados quantificados e qualificados na correlação entre os métodos utilizados, justificam a aplicação do smart material no sensoriamento de viscosidade e carregamento aplicado em ambientes isolados. Em consequência das discussões apresentadas para as curvas comportamentais na variação dos parâmetros físico-químico a plataforma de sensoriamento é validada. / New amorphous magnetic materials have magnetic and elastic properties which allows the identification and control of environmental parameters remotely. This work was based in the investigation of a magnetoelastic thin strip, widely used as anti-theft device. In this study it was discussed the employment of this material as a sensor capable identify an environmental change through magnetoelasticity. In order to characterize the strips it was employed several techniques, namely: finite element modeling of the vibrational modes, electromagnetic impedance and laser interferometry. It was presented an analysis of the displacement of the longitudinal modes. The knowledge of the vibration mode allowed the sensor electric characterization when subjected to environmental changes. According to the sample dimensions under magnetic field, test systems were developed in order to perform optic and electric measurements. A proper parameter adjustment of the power supply allowed the determination of the fundamental and higher order resonance frequencies. The magnetostrictive behaviour of the anti-theft strips is related to the Young modulus where the vibration frequency is inversely proportional to the length of the strip. Studies showed that the strip performance is also related to many other parameters, such as the mechanical and electromagnetic properties and the environment to which it is exposed. The strips here presented are largely employed as sensor for temperature, pressure, density, mas variation, viscosity and flux velocity mainly because their wireless capabilities. The data from the polarization field are a section of the knowledge required to better investigate the best performance of the sensor. The sensor characterization through several techniques applied in viscous media and under pressure raise some issues. However, the construction of some devices allowed the application of different values of viscosity and pressure upon the magnetized strip. This made the results interpretation less complex. The resonances were observed in the experimental data and mathematical modellin. Calibration curves were defined to make the results interpretation easier.Previously applied and studied techniques which cover the characterization and behaviour of the material provide valid justifications for the implementation of remote sensors made of amorphous metallic strips. The results presented here justify the application of the analysed amorphous strip as a viscosity and pressure sensor in isolated enviroments.

Ces travaux de thèse tentent de répondre à un besoin de surveillance fiable et durable de la concentration d’hydrogène dans un environnement radioactif. Dans ces travaux, nous proposons l’étude et le développement d’un capteur physique d’hydrogène à base de micropoutres résonantes en silicium. La particularité de ce type de capteur vient du fait qu’il ne contient pas de couche sensible et est donc moins sujet au vieillissement que les capteurs chimiques à base de couche sensibles. Compte tenu de la faible masse volumique de l’hydrogène par rapport à celle de l’air et de la bonne sensibilité des micropoutres résonantes aux propriétés physiques du gaz environnant (masse volumique et viscosité), l’utilisation de micropoutres résonantes pour le suivi de la concentration de l’hydrogène dans l’air est tout à fait possible. L’objectif de ces travaux de recherche est l’amélioration de la sensibilité et de la limite de détection de ce type de capteur. Tout d’abord, une étude des méthodes de suivi de faibles variations de la fréquence de résonance a été effectuée. Ceci a permis de déterminer la méthode ayant le meilleur rapport signal sur bruit, permettant ainsi d’améliorer la limite de détection en termes de variation de fréquence de résonance. Dans une seconde partie, une étude de l’influence de la géométrie et des dimensions sur la sensibilité vis-à-vis des variations de la masse volumique du gaz environnant a été réalisée. A l’issu de cette étude, des critères géométriques et dimensionnels permettant l’optimisation de la sensibilité ont été dégagés. D’autres aspects visant à améliorer les performances (sensibilité et limite de détection) de ces capteurs ont été étudiés, comme l’influence du courant d’actionnement et des tensions de polarisation (actionnement électromagnétique et détection piézorésistive) et l’utilisation des modes supérieurs de résonance. Par ailleurs, l’étude de l’influence des paramètres environnementaux (température et pression) sur le comportement des micropoutres résonantes a été établie. / These PhD research tries to meet a need for a reliable and a sustainable hydrogen concentration monitoring in a radioactive environment. In this work, we propose the study and development of resonant silicon microcantilever-based physical hydrogen sensors. The special feature of this sensor is that it does not contain any sensitive and consequently the reliability is improved, compared to devices with sensitive coating. In view of the low density of hydrogen compared to that of air, and the good sensitivity of a resonant microcantilever to the physical properties of the surrounding gas (density and viscosity), the use of vibrating uncoated microcantilever for monitoring hydrogen concentration in air is therefore possible. The objective of this research is to improve the sensitivity and the limit of detection of such sensors. First of all, a study of methods for monitoring small changes in resonant frequency has been conducted in order to determine the method having the best signal to noise ratio, thus, allowing improvement of its resolution in terms of resonant frequency variation measurement. In a second part, a study of the influence of microcantilever geometries and dimensions on their sensitivity to the gas density variation has been performed. As a result, geometrical and dimensional criteria for optimizing the sensitivity to the gas density have been identified. Other factors in a view of improving performance (sensitivity and detection limit) of vibrating microbeams have been studied, such as the influence of the actuating current and bias voltages (electromagnetic actuation and piezoresistive detection) and using high resonant modes. Furthermore, the study of the influence of environmental parameters (temperature and pressure) on the sensors behavior has been established.

Uma vasta gama de sensores são aplicados no mercado atual na busca pela melhoria de processos e produtos. Há um grande crescimento em novos sistemas que possam apresentar recursos que técnicas convencionais não apresentam. A busca por uma nova plataforma de sensoriamento surge a partir do interesse em identificar e controlar parâmetros ambientais isolados. Esta pesquisa em área incipiente no Brasil mostra o desenvolvimento de um sensor a partir de um material inteligente (smart material), que por definição, possui uma ou mais propriedades que podem sofrer mudanças significativas a partir de um estímulo externo. O presente trabalho é baseado na investigação de uma fita de material magnético amorfo, que ao exibir propriedades magnéticas e elásticas pelo efeito da magnetostricção, permite o monitoramento remoto de fenômenos físico-químicos do ambiente em que estiver exposta. O desenvolvimento deste sensor tem finalidade no monitoramento sem fio de solicitação mecânica, e alteração do tipo de fluido presente em um dado ambiente. O estudo e avaliação do sensor contou com técnicas de caracterização experimentais e de simulação. São apresentados sistemas e ensaios capazes verificar as ressonâncias do modo de vibração puro da amostra a partir de medidas ópticas e elétricas, quando submetidos a variação de fenômenos físicos. Os resultados indicam a dependência do efeito direto ao estímulo na ação externa do campo magnético em decorrências das características do material. Os resultados quantificados e qualificados na correlação entre os métodos utilizados, justificam a aplicação do smart material no sensoriamento de viscosidade e carregamento aplicado em ambientes isolados. Em consequência das discussões apresentadas para as curvas comportamentais na variação dos parâmetros físico-químico a plataforma de sensoriamento é validada. / New amorphous magnetic materials have magnetic and elastic properties which allows the identification and control of environmental parameters remotely. This work was based in the investigation of a magnetoelastic thin strip, widely used as anti-theft device. In this study it was discussed the employment of this material as a sensor capable identify an environmental change through magnetoelasticity. In order to characterize the strips it was employed several techniques, namely: finite element modeling of the vibrational modes, electromagnetic impedance and laser interferometry. It was presented an analysis of the displacement of the longitudinal modes. The knowledge of the vibration mode allowed the sensor electric characterization when subjected to environmental changes. According to the sample dimensions under magnetic field, test systems were developed in order to perform optic and electric measurements. A proper parameter adjustment of the power supply allowed the determination of the fundamental and higher order resonance frequencies. The magnetostrictive behaviour of the anti-theft strips is related to the Young modulus where the vibration frequency is inversely proportional to the length of the strip. Studies showed that the strip performance is also related to many other parameters, such as the mechanical and electromagnetic properties and the environment to which it is exposed. The strips here presented are largely employed as sensor for temperature, pressure, density, mas variation, viscosity and flux velocity mainly because their wireless capabilities. The data from the polarization field are a section of the knowledge required to better investigate the best performance of the sensor. The sensor characterization through several techniques applied in viscous media and under pressure raise some issues. However, the construction of some devices allowed the application of different values of viscosity and pressure upon the magnetized strip. This made the results interpretation less complex. The resonances were observed in the experimental data and mathematical modellin. Calibration curves were defined to make the results interpretation easier.Previously applied and studied techniques which cover the characterization and behaviour of the material provide valid justifications for the implementation of remote sensors made of amorphous metallic strips. The results presented here justify the application of the analysed amorphous strip as a viscosity and pressure sensor in isolated enviroments.

Uma vasta gama de sensores são aplicados no mercado atual na busca pela melhoria de processos e produtos. Há um grande crescimento em novos sistemas que possam apresentar recursos que técnicas convencionais não apresentam. A busca por uma nova plataforma de sensoriamento surge a partir do interesse em identificar e controlar parâmetros ambientais isolados. Esta pesquisa em área incipiente no Brasil mostra o desenvolvimento de um sensor a partir de um material inteligente (smart material), que por definição, possui uma ou mais propriedades que podem sofrer mudanças significativas a partir de um estímulo externo. O presente trabalho é baseado na investigação de uma fita de material magnético amorfo, que ao exibir propriedades magnéticas e elásticas pelo efeito da magnetostricção, permite o monitoramento remoto de fenômenos físico-químicos do ambiente em que estiver exposta. O desenvolvimento deste sensor tem finalidade no monitoramento sem fio de solicitação mecânica, e alteração do tipo de fluido presente em um dado ambiente. O estudo e avaliação do sensor contou com técnicas de caracterização experimentais e de simulação. São apresentados sistemas e ensaios capazes verificar as ressonâncias do modo de vibração puro da amostra a partir de medidas ópticas e elétricas, quando submetidos a variação de fenômenos físicos. Os resultados indicam a dependência do efeito direto ao estímulo na ação externa do campo magnético em decorrências das características do material. Os resultados quantificados e qualificados na correlação entre os métodos utilizados, justificam a aplicação do smart material no sensoriamento de viscosidade e carregamento aplicado em ambientes isolados. Em consequência das discussões apresentadas para as curvas comportamentais na variação dos parâmetros físico-químico a plataforma de sensoriamento é validada. / New amorphous magnetic materials have magnetic and elastic properties which allows the identification and control of environmental parameters remotely. This work was based in the investigation of a magnetoelastic thin strip, widely used as anti-theft device. In this study it was discussed the employment of this material as a sensor capable identify an environmental change through magnetoelasticity. In order to characterize the strips it was employed several techniques, namely: finite element modeling of the vibrational modes, electromagnetic impedance and laser interferometry. It was presented an analysis of the displacement of the longitudinal modes. The knowledge of the vibration mode allowed the sensor electric characterization when subjected to environmental changes. According to the sample dimensions under magnetic field, test systems were developed in order to perform optic and electric measurements. A proper parameter adjustment of the power supply allowed the determination of the fundamental and higher order resonance frequencies. The magnetostrictive behaviour of the anti-theft strips is related to the Young modulus where the vibration frequency is inversely proportional to the length of the strip. Studies showed that the strip performance is also related to many other parameters, such as the mechanical and electromagnetic properties and the environment to which it is exposed. The strips here presented are largely employed as sensor for temperature, pressure, density, mas variation, viscosity and flux velocity mainly because their wireless capabilities. The data from the polarization field are a section of the knowledge required to better investigate the best performance of the sensor. The sensor characterization through several techniques applied in viscous media and under pressure raise some issues. However, the construction of some devices allowed the application of different values of viscosity and pressure upon the magnetized strip. This made the results interpretation less complex. The resonances were observed in the experimental data and mathematical modellin. Calibration curves were defined to make the results interpretation easier.Previously applied and studied techniques which cover the characterization and behaviour of the material provide valid justifications for the implementation of remote sensors made of amorphous metallic strips. The results presented here justify the application of the analysed amorphous strip as a viscosity and pressure sensor in isolated enviroments.

The primary focus of this dissertation is the development of novel fluorescent near-infrared molecules for various applications. In Chapter 1, a compound dU-BZ synthesized via Sonogashira coupling reaction methodology is described. A deoxyuridine building block was introduced to enhance hydrophilic properties and reduce toxicity, while an alkynylated benzothiazolium dye was incorporated for near-IR emission and reduce photodamage and phototoxicity that is characteristic of common fluorphores that are excited by UV or visible light. A 30-fold enhancement of fluorescence intensity of dU-BZ was achieved in a viscous environment. Values of fluorescence quantum yields in 99% glycerol/1% methanol (v/v) of varying temperature from 293 K to 343 K, together with fluorescence quantum yields, radiative and nonradiative rate constants and fluorescence lifetimes in glycerol/methanol solutions of varying viscosities from 4.8 to 950 cP were determined. It was found that both fluorescence quantum yields and fluorescence lifetimes increased with increasing viscosity, which is consistent with results predicted by theory. This suggests that the newly designed compound dU-BZ is capable of functioning as a probe of local microviscosity, and was later confirmed by in vitro bioimaging experiments. In Chapter 2, a new BAPTA (O,O*-bis(2-aminophenyl)ethyleneglycol-N,N,N*,N*-tetra acetic acid) and BODIPY (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene)-based calcium indicator, BAPBO-3, is reported. A new synthetic route was employed to simplify both synthesis and purification, which tend to be low yielding and cumbersome for BAPTA derivatives. Upon excitation, a 1.5-fold increase in fluorescence intensity in buffer containing 39 ?? Ca2+ and a 3-fold increase in fluorescence intensity in buffer containing 1 M Ca2+ was observed; modest but promising fluorescence turn-on enhancements. In Chapter 3, a newly-designed unsymmetrical squaraine dye, SQ3, was synthesized. A one-pot synthesis was employed resulting in a 10% yield, a result that is generally quite favorable for the creation of unsymmetrical squaraines Photophysical and photochemical characterization was conducted in various solvents, and a 678 nm absorption maximum and a 692 nm emission maximum were recorded in DMSO solution with a fluorescence quantum yield of 0.32. In vitro cell studies demonstrated that SQ3 can be used as a near-IR probe for bioimaging.