Orientador: Prof. Dr. Vani Xavier de Oliveira Junior / Dissertação (mestrado) - Universidade Federal do ABC, Programa de Pós-Graduação em Ciência & Tecnologia - Química, 2014. / Peptídeos são biomoléculas formadas pela ligação de dois ou mais aminoácidos através de ligações peptídicas, entre um grupo amina de um aminoácido e o grupo carboxila de outro aminoácido. Atualmente, uma das metodologias de síntese aplicada é a síntese de peptídeos em fase sólida, pela estratégia t-Boc. No presente trabalho foi analisada a eficiência da etapa de clivagem, utilizando o método convencional a 5°C e 30°C e a clivagem assistida por micro-ondas. Nesse sentido, foram utilizadas como suporte sólido as resinas Merrifield, MBHA, BHA e PAM. Os resultados mostram que a etapa de clivagem é influenciada pelo tamanho e sequência peptídica e pela resina empregada. Os melhores rendimentos foram encontrados para as clivagens assistidas por micro-ondas com a resina BHA e entre as clivagens convencionais, os melhores resultados foram obtidos a 5ºC, com as resinas MBHA e BHA. / Peptides are biomolecules formed by connecting two or more amino acids by peptide bonds between an amino group of an amino acid and the carboxyl group of another amino acid. Currently, one of the methodologies applied synthesis is the synthesis of peptides solid phase by t-Boc strategy. The present study examined the efficiency of the cleavage step using the conventional method at 5°C and 30°C and cleavage by microwave assisted. Accordingly were used as solid support the Merrifield, MBHA, BHA and PAM resins. The results show that cleavage step is influenced by size and peptide sequence and the resin employed. The best yields were found for the microwave assisted with the BHA resin and between conventional cleavages, the best results were obtained at 5°C, with the BHA and MBHA resin cleavages.

O presente trabalho trata do estudo, projeto, desenvolvimento, construção e medida de lentes discretas planares (DLAs). Estes dispositivos atuam como sistemas irradiantes, especialmente com características multi-feixes. A construção destas lentes utiliza tecnologias compatíveis com a fabricação de circuitos impressos, com alguns detalhes que são característicos da área de antenas e circuitos planares. O estudo aborda as equações de projeto e considerações gerais relativas ao atendimento de especificações técnicas preliminares. Foram desenvolvidas duas lentes discretas, uma na frequência de 8GHz (banda X) e outra na frequência de 40GHz (banda Ka- faixa de ondas milimétricas). São apresentados os resultados de medidas destas duas lentes, que comprovam a possibilidade de uso em aplicações multi-feixes, bem como seu efeito de foco, análogo ao observado em lentes óticas comuns. / The object of this work is the study, design, development, fabrication and measurement of discrete lens arrays (DLAs). These devices act as radiant systems, especially with multi-beam characteristics. Their construction follows the same procedures and techniques normally found in printed circuit fabrication, with some further details that are pertinent to the antenna and planar circuit field. This study contains the design equations and general remarks as to fulfill preliminary technical specifications. Two real designs were developed, one in the X-band (8GHz) and another in the millimeter range, Ka band (40GHz). Their respective measurement results are presented, which proved their possible application in multi-beam systems, as well as their focusing effect, which is analogous to that observed in common optical lenses.

Ce travail s’inscrit dans le cadre duprojet européen FREEZEWAVE (ERA-NetSUSFOOD) et porte sur l’étude et lamodélisation d’un procédé de congélationassistée par micro-ondes. Il a pour objectif unemeilleure compréhension des phénomènesphysiques associés à ce procédé. Un modèlecouplant thermique, changement de phase etélectromagnétisme a été développé. Une étudenumérique préliminaire a permis d’appréhenderles interactions complexes entre micro-ondes etmatière durant le changement de phase,notamment l’importance de la diminution despropriétés diélectriques sur la modification desphénomènes de résonance entrainant ledéplacement des « points chauds » et sur laquantité de chaleur générée.Un gel modèle a été caractérisé puis utilisé pourvalider le modèle sur un pilote développé pourl’étude. La micro-tomographie à rayon X apermis la mesure de la taille des cristaux et amis en évidence, lors d’une congélationconventionnelle, l’impact du tempscaractéristique de congélation et du gradient detempérature sur la taille des cristaux de glace.Cette étude a permis de constater une nettediminution de la taille des cristaux de glace lorsd’une congélation assistée par micro-ondes parrapport à une congélation conventionnelle. EnfinIl a été montré que la réduction de taille descristaux n’était pas due aux oscillations detempérature provoquées par des créneaux depuissance micro-ondes mais à la quantitéd’énergie apportée / This work was performed in thecontext of the European project FREEZEWAVE(ERA-net SUSFOOD) and focuses on studyingand modelling the microwave assisted freezingprocess. The main objective was to acquire abetter understanding of the correspondingphysical phenomena. A model coupling thermal,phase change and electromagnetism wasdeveloped. A preliminary numerical studypermitted to grasp the complex interactionsbetween microwaves and matter, especially theimportance of the dielectric properties reductionon resonance phenomena, leading to the movingof “hot spots”, and on the generated heat.A methylcellulose gel was characterised andused for the model validation on a prototype pilotspecially designed for this study. A protocolbased on X ray tomography was developed todetermine the ice crystal size. It highlighted, fora conventional freezing process, that thethermal gradient and characteristic freezing timeimpacts the ice crystals sizes.In the case of microwave assisted freezing, thestudy permitted to show a clear decrease in icecrystal size compared to conventional freezing.Finally, it has been shown that the ice crystalsize reduction was not a consequence oftemperature oscillations due to microwavespulses but the consequence of the energyquantity brought to the system by microwaves.

Le travail présenté dans cette thèse s’inscrit dans le contexte du développement de nouveaux procédés pour la mise en forme de matériaux composites pour répondre aux contraintes industrielles de gain de temps et d’énergie. Le procédé de chauffage par micro-onde reposant sur un principe de chauffage volumique permet de garantir ces avantages. L’inconvénient majeur est que le comportement du champ électrique lors de l’interaction entre matériaux composites et micro-ondes est peu connu. L’objectif de cette thèse est donc de proposer des solutions numériques pour approfondir la connaissance du procédé et la physique associée afin de mettre en avant ses capacités quant à un développement industriel. Pour ce faire, le travail réalisé est axé autour de trois verrous. En premier lieu, une nouvelle méthode numérique est proposée afin de résoudre les équations de Maxwell en 3D dans un stratifié composite. Prendre en compte le comportement 3D est essentiel afin de décrire avec précision l’impact des différentes couches du matériau et de leur épaisseur sur la propagation du champ électrique. Dans un second temps, la simulation électromagnétique est couplée à une résolution thermique afin de simuler le procédé de chauffage d’une pièce composite. Différents paramètres du procédé sont étudiés afin de mettre en avant les plus sensibles pour l’utilisation du chauffage micro-onde pour les matériaux composites. Enfin, l’attention du lecteur est portée sur le développement d’une méthode de simulation pour un contrôle en temps réel du procédé en comparaison avec des essais expérimentaux. / The context of the present work is the development of new processes for the heating and forming of composite materials in order to provide an answer to the industrials needs for less energy and less time-consuming processes. In that sense, microwave heating is perfect match as it relies on volumetric heating. The major drawback is that the behaviour of the electric field while interacting with composite material is poorly known. Therefore, the main objective of this thesis is to provide numerical solutions to go more deeply in the understanding of such process and put forward its capabilities for an industrial development.To fulfil this objective, the work is oriented over three main axes. First, an innovative simulation tool is presented in order to solve the Maxwell’s equations in a thin multi layered domain. Taking into account the 3D behaviour of the electric field is a major issue in order to describe precisely the impact of the different plies of the laminate on the propagation of the electric field.Then, the electromagnetic simulation is coupled with a thermal simulation in order to simulate the full heating process of a composite part. Parameters of the process are investigated to bring forward the most crucialones. Finally, real-time control of the process is tackled using a model order reduction simulation technique. These results are compared to experimental work on two sets of samples.

<p>Catalysis has a profound impact on all living species on the earth. Nature’s catalysts, the enzymes, have the ability to selectively promote a specific bio-chemical transformation, given the required substrate. As well as being highly selective, enzymes enhance the speed of these reactions, helping them to run at temperatures much lower than normally required, i.e. at body temperature. In comparison, reactions used in the production of new materials such as polymers, medicines, fragrances, petrochemicals, etc. are often catalyzed by transition metals. This thesis describes how the selectivity and activity of these catalysts can be influenced via two conceptually different methods: chelation control and microwave heating. The thesis primarily focuses on regio- and stereochemical aspects of the palladium-catalyzed arylation of olefins, i.e. the Heck reaction. Reaction rate enhancement of both palladium and enzyme (polymerase chain reaction [PCR]) catalysis by microwave heating is also discussed. </p><p>Novel chelation-controlled palladium-catalyzed multi- and asymmetric arylations of vinyl ethers were performed, resulting in tetra-substituted olefins as well as chiral quaternary carbon centers with excellent optical purity. In addition, a new synthetic route to diarylated ethanals, relying on a double chelation-controlled regioselective arylation followed by hydrolysis, has been discovered. High temperature conditions, using microwave heating, substantially reduce the reaction time for ligand-controlled asymmetric Heck arylations, while retaining levels of enantioselectivity in most cases. In addition, a potentially useful fast synthetic protocol for the employment of aryl boronic acids in oxidative Heck arylation was developed. Finally, microwave-assisted PCR was described for the first time; this method allows reductions in the run time of 50%.</p>

This thesis compiles results of research in two mutuallydependent parts: 1) development of ferromagnetic resonance(FMR) spectrometer to study microwave properties offerromagnetic materials, and 2) characterization of new irongarnets: pulsed laser deposited Y3Fe5O12and Bi3Fe5O12films and Ce:Y3Fe5O12single crystal. First part describes a novelBroadbandFMRSpectrometerdesigned to characterize thin ferromagneticfilms. The spectrometer uses two probeheads: one is the X-bandmicrowave reflection cavity for room temperature measurementsand the in-cryostat microstrip line probe to perform FMRexperiments in the frequency range from 50 MHz to 40 GHz. Veryuniform and stable magnetic field up to 2.4 T, temperatures 4 Kto 420 K, and continuous frequency scan performed byHP8722Dvector network analyzer provide various modes ofoperation. Both probeheads are equipped with two-circlegoniometers to ensure accurate study of magneticanisotropy. The spectrometer was used to make express-analysis ofquality thus to optimize processing parameters of epitaxialiron garnet films grown by pulsed laser deposition (PLD).Comprehensive study of uniaxial and cubic magnetocrystallineanisotropy has been performed for Ce:Y3Fe5O12bulk crystal as well as for Y3Fe5O12and Bi3Fe5O12films grown on different substrates by PLD andreactive ion beam sputtering techniques. BroadbandFMR-spectroscopy revealed difference in spectra of domain wallresonances: instead of“soft”spin modes in filmsgrown by liquid phase epitaxy, PLD-made films show“diffuse”transformation of domains near thesaturation field. This effect indicates non-uniformity ofsaturation magnetization and field of uniaxial anisotropy inPLD-iron garnets. Spin wave resonances in comparison withuniform FMR have been studied to evaluate“localquality”of ferromagnetic films. The resonance field andFMR linewidth behavior were studied at various crystallographicdirections determined by X-ray diffraction. FMR was used to choose PLD-made YIG films with low losses atmicrowave frequencies and to build magnetostatic surface wavesmicrowave bandpass filter. The filter was designed as a planarfilm structure with a microstrip line for transducers. It is afirst demonstration of feasibility to introduce PLD processingtechnique to magnetostatic wave technology. Magneto-optical study of Ce:Y3Fe5O12single crystal complements results ofFMR-spectroscopy of new garnets. <b>Keywords:</b>ferrites, thin films, ferromagnetic resonance,microwaves, FMR spectrometer, magnetic anisotropy,magnetostatic waves.

Catalysis has a profound impact on all living species on the earth. Nature’s catalysts, the enzymes, have the ability to selectively promote a specific bio-chemical transformation, given the required substrate. As well as being highly selective, enzymes enhance the speed of these reactions, helping them to run at temperatures much lower than normally required, i.e. at body temperature. In comparison, reactions used in the production of new materials such as polymers, medicines, fragrances, petrochemicals, etc. are often catalyzed by transition metals. This thesis describes how the selectivity and activity of these catalysts can be influenced via two conceptually different methods: chelation control and microwave heating. The thesis primarily focuses on regio- and stereochemical aspects of the palladium-catalyzed arylation of olefins, i.e. the Heck reaction. Reaction rate enhancement of both palladium and enzyme (polymerase chain reaction [PCR]) catalysis by microwave heating is also discussed. Novel chelation-controlled palladium-catalyzed multi- and asymmetric arylations of vinyl ethers were performed, resulting in tetra-substituted olefins as well as chiral quaternary carbon centers with excellent optical purity. In addition, a new synthetic route to diarylated ethanals, relying on a double chelation-controlled regioselective arylation followed by hydrolysis, has been discovered. High temperature conditions, using microwave heating, substantially reduce the reaction time for ligand-controlled asymmetric Heck arylations, while retaining levels of enantioselectivity in most cases. In addition, a potentially useful fast synthetic protocol for the employment of aryl boronic acids in oxidative Heck arylation was developed. Finally, microwave-assisted PCR was described for the first time; this method allows reductions in the run time of 50%.

The main objective of the study was to determine the effects of enzymes on quality of breads baked in halogen lamp-microwave combination, microwave and conventional oven. It was also aimed to determine the optimum processing conditions in these ovens. In the first part of the study, as independent variables, baking time, baking temperature for conventional oven / microwave power for microwave oven and microwave power and halogen power for combination oven was used. Weight loss, specific volume, firmness and color of the breads were measured during the study. The optimum baking conditions were determined as 13 min at 200&deg / C in conventional oven, 0.75 min at 100% power in microwave oven, 10 min at 60% power in halogen lamp oven, and 3 min at 30% microwave power and 70% halogen lamp power in halogen lamp-microwave combination oven. In the case of combination oven, specific volume and color values of breads were comparable with the conventionally baked breads but weight loss and firmness of them were still higher. The effects of different enzymes (&amp / #945 / -amylase, xylanase, lipase &amp / protease) were studied to reduce the quality problems of breads baked in microwave and halogen lamp-microwave combination oven. The optimum baking conditions determined for each type of oven in the first part of the study were used in the investigation of the functions of enzymes on bread quality during baking and staling. As a control, no enzyme added breads baked at 200&deg / C for 13 min in conventional oven were used. All the enzymes were found to be effective in reducing initial firmness and increasing specific volume of breads baked in microwave and halogen lamp-microwave combination ovens. However, in conventional baking, the effects of enzymes on crumb firmness were seen mostly during storage. The usage of enzyme protease in the bread formulation resulted in breads with higher volume and darker color in all of the ovens. All of the enzymes were found to be effective to retard the staling of breads baked in conventional, microwave and halogen lamp-microwave combination ovens.

As the world moves towards eliminating lead from consumer products, the microelectronics industry has put effort into developing lead-free solder paste. The major drawback of lead-free solder is the problems caused by its high reflow temperature. Variable frequency microwave (VFM) processing has been shown to allow some materials to be processed at lower temperatures. Issues addressed in this study include using VFM to reduce the solder reflow temperature, comparing the heating rate of different size solder particles, and comparing the reliability of VFM reflowed solder versus conventionally reflowed solder. Results comparing the effect of particle size on the heating rate of solder showed that the differences were negligible. This is due in part to the particle sizes overlapping. Many lead-free solder pastes reflow around 250℃. Results indicate that when using the VFM, lead-free solder paste will reflow at 220℃. The reliability of solder that was reflowed using the VFM at the reduced temperature was found to be comparable to solder reflowed in a conventional manner. Based on these findings, VFM processing can eliminate the major obstacles to making lead-free solder paste a more attractive option for use in the microelectronics industry.

<p>This thesis compiles results of research in two mutuallydependent parts: 1) development of ferromagnetic resonance(FMR) spectrometer to study microwave properties offerromagnetic materials, and 2) characterization of new irongarnets: pulsed laser deposited Y₃Fe₅O₁₂and Bi₃Fe₅O₁₂films and Ce:Y₃Fe₅O₁₂single crystal.</p><p>First part describes a novel<i>Broadband</i>FMR<i>Spectrometer</i>designed to characterize thin ferromagneticfilms. The spectrometer uses two probeheads: one is the X-bandmicrowave reflection cavity for room temperature measurementsand the in-cryostat microstrip line probe to perform FMRexperiments in the frequency range from 50 MHz to 40 GHz. Veryuniform and stable magnetic field up to 2.4 T, temperatures 4 Kto 420 K, and continuous frequency scan performed by<i>HP8722D</i>vector network analyzer provide various modes ofoperation. Both probeheads are equipped with two-circlegoniometers to ensure accurate study of magneticanisotropy.</p><p>The spectrometer was used to make express-analysis ofquality thus to optimize processing parameters of epitaxialiron garnet films grown by pulsed laser deposition (PLD).Comprehensive study of uniaxial and cubic magnetocrystallineanisotropy has been performed for Ce:Y₃Fe₅O₁₂bulk crystal as well as for Y₃Fe₅O₁₂and Bi₃Fe₅O₁₂films grown on different substrates by PLD andreactive ion beam sputtering techniques. BroadbandFMR-spectroscopy revealed difference in spectra of domain wallresonances: instead of“soft”spin modes in filmsgrown by liquid phase epitaxy, PLD-made films show“diffuse”transformation of domains near thesaturation field. This effect indicates non-uniformity ofsaturation magnetization and field of uniaxial anisotropy inPLD-iron garnets. Spin wave resonances in comparison withuniform FMR have been studied to evaluate“localquality”of ferromagnetic films. The resonance field andFMR linewidth behavior were studied at various crystallographicdirections determined by X-ray diffraction.</p><p>FMR was used to choose PLD-made YIG films with low losses atmicrowave frequencies and to build magnetostatic surface wavesmicrowave bandpass filter. The filter was designed as a planarfilm structure with a microstrip line for transducers. It is afirst demonstration of feasibility to introduce PLD processingtechnique to magnetostatic wave technology.</p><p>Magneto-optical study of Ce:Y₃Fe₅O₁₂single crystal complements results ofFMR-spectroscopy of new garnets.</p><p><b>Keywords:</b>ferrites, thin films, ferromagnetic resonance,microwaves, FMR spectrometer, magnetic anisotropy,magnetostatic waves.</p>