Submitted by Maria Aparecida (cidazen@gmail.com) on 2017-04-04T13:23:13Z No. of bitstreams: 1 AleffCruzdeCastro.pdf: 1452660 bytes, checksum: 8c8c4baa89c5a3373105fcb0cd29e65c (MD5) / Made available in DSpace on 2017-04-04T13:23:13Z (GMT). No. of bitstreams: 1 AleffCruzdeCastro.pdf: 1452660 bytes, checksum: 8c8c4baa89c5a3373105fcb0cd29e65c (MD5) Previous issue date: 2017-03-06 / CNPq, FAPEMA, CAPES, FSADU / Zeolites are microporous inorganic materials with a variety of applications in several areas of science and engineering. Their physical and chemical properties are attributed to the large internal surface area, and the chemical and hydrothermal stability, which are induced by the existence of well defined channels and/or cavities. These structural characteristics promote the use of zeolites as catalysts, molecular sieves, ion exchangers and, more recently, as electrochemical sensors. Taking in consideration these premises, this work describes the development of an electrochemical sensor obtained from the modification of the polyurethane graphite composite electrode with NiAlPO-5, a nickel-modified AFI aluminophosphate, and its application for determination of Cu2+ in ethanol biofuel. The synthesis of the aluminophosphates were conducted by the hydrothermal method and the obtained materials were characterized by X-ray diffraction, scanning electron microscopy, 31P nuclear magnetic resonance and UV-Vis and infrared spectroscopy. After synthesis and characterization, materials were used as modifiers (10%) in GPU electrodes in order to compare the performance of the unmodified and modified electrodes by Square Wave Anodic Stripping Voltammetry. The results showed that the incorporation of Ni to the material structure promotes an improvement in the electrical properties and analytical properties of the electrode. The analytical response of the sensor in the copper ion determination showed that the NiAlPO-5 electrode is more sensitive in terms of peak current than the electrolyte based on AlPO-5 only. The best response was obtained with the Ni/Al ratio of 0.5 on the NiAlPO-5 sensor. The experimental conditions of potential and deposition time, pulse amplitude, step potential, frequency and pH were optimized in an electrochemical cell containing 2 mL of ethanol, 8 mL of HCl 0.1 mol L-1 and Cu2+ concentration of 2.5×10-7 mol L-1. GPU/NiAlPO-5 modified sensor was then evaluated for electroanalytical determination of Cu2+ in ethanol biofuel samples presenting a linear response for Cu2+. Good results were obtained for the limit of detection (9.44×10-9 mol L-1), accuracy (recovery of 115%) and precision (RSD of 5.92%). / As zeólitas são materiais inorgânicos microporosos que apresentam uma grande variedade de aplicações em diversas áreas das ciências e engenharias. Suas propriedades físicas e químicas são atribuídas à grande área superficial interna e à estabilidade química e hidrotérmica, as quais são induzidas pela existência de canais e/ou cavidades bem definidos, tornando possível a sua utilização como catalisadores, peneiras moleculares, trocadores iônicos e, mais recentemente, como sensores eletroquímicos. Com base nisto, este trabalho apresenta o desenvolvimento de um sensor eletroquímico obtido a partir da modificação do eletrodo compósito de grafite poliuretana com NiAlPO-5, um aluminofosfato de estrutura AFI modificado com níquel, e sua aplicação na determinação de Cu2+ em amostras de etanol combustível. Os aluminofosfatos foram sintetizados através do método hidrotérmico e caracterizados por difração de raios-X, microscopia eletrônica de varredura, ressonância magnética nuclear de 31P e espectroscopia de UV-Vis e de infravermelho. Os materiais obtidos foram, então, utilizados como modificadores na proporção de 10% em eletrodos GPU, a fim de realizar-se uma comparação entre os eletrodos sem modificação e modificados com AlPO-5 e NiAlPO-5 mediante a utilização da técnica de voltametria de redissolução anódica com varredura de onda quadrada e o método de adição padrão. Os resultados mostraram que a incorporação do Ni à estrutura do material promove uma melhora nas propriedades elétricas e analíticas do eletrodo. A resposta analítica do sensor na determinação do íon Cu2+, mostrou que o eletrodo NiAlPO-5 é mais sensível, em termos de corrente de pico, que o eletrodo baseado apenas em AlPO-5. A melhor resposta foi obtida com a razão Ni/Al de 0,5 no sensor NiAlPO-5. As condições experimentais, potencial e tempo de deposição, amplitude de pulso, potencial de escada, frequência e pH foram otimizadas em uma célula eletroquímica contendo 2 mL de etanol, 8 mL de HCl 0,1 mol L-1 e uma concentração de Cu2+ de 2,5×10-7 mol L-1. O sensor modificado com NiAlPO-5 foi então avaliado para determinação eletroanalítica de Cu2+ em amostras de etanol combustível apresentando resposta linear para Cu2+. Bons resultados foram obtidos para o limite de detecção (9,44×10-9 mol L-1), limite de quantificação (3,15 x10-8 mol L-1), recuperação (115%) e precisão (5,92%).

Les zéolithes sont des solides cristallins caractérisés par l'existence de canaux pouvant accueillir des ions et molécules hôtes. Ces matériaux sont donc utilisés dans de nombreux procédés physico-chimiques, tels que la séparation moléculaire, la catalyse, l'échange cationique, et plus récemment comme constituant de nouveaux matériaux composites. Dans ce travail nous nous sommes intéressés à la caractérisation des interactions dans les tamis moléculaires de type MFI, AFI et AlPO4-15 via la diffraction des rayons X à haute résolution sur monocristal et la thermogravimétrie et calorimétrie.<br /> Les monocristaux nécessaires ont été obtenus au laboratoire par synthèse hydrothermale. L'étude de la densité de charge de AlPO4-15 a révélé les interactions hôte / invité dans ce composé et, avec l'analyse de sa topologie, a permis d'en modéliser le potentiel électrostatique. L'étude de la zéolithe MFI a permis de localiser l'ion fluorure qui se trouve être lié à un atome de silicium de la charpente.

¿Cuántas opciones de respuesta hay que utilizar para responder un cuestionario de personalidad? Durante más de ochenta años, numerosas investigaciones previas han examinado este tópico sin lograr alcanzar un consenso. El presente trabajo se aborda esta cuestión de forma exhaustiva.MÉTODO:Se aplican dos escalas de personalidad [(Orientación Negativa hacia los Problemas (NPO) del Social Problem Solving Inventory-Revised (SPSI-R) y la escala Satisfacción con la Vida (SWLS)], cada una a una muestra independiente (Estudio A = 746 participantes y Estudio B = 426 participantes), variando el número de opciones de respuesta en dos, tres y cinco alternativas. Cada sujeto debe responder a los tres tipos de formato de respuesta dentro de una misma sesión. Para evitar que éstos noten que están contestando el mismo cuestionario en más de una ocasión, cada escala experimental se inserta dentro de una batería de "tests". De esta forma, se construyen tres baterías de "test" (una para cada muestra), contrabalanceando la aparición de los distintos formatos de respuesta y manteniendo constante el resto de las condiciones experimentales. Por otro lado, se utiliza como criterio para evaluar el efecto del número de opciones de respuesta sobre las propiedades psicométricas las escalas NPO y SWLS tanto su fiabilidad (consistencia interna y estabilidad temporal) como su validez (evidencia basada en la estructura interna y evidencia basada en el grado de relación con otras variables).Estas se evalúan desde tres modelos psicométricos diferentes: Teoría Clásica de los Tests (TCT), Análisis Factorial de los Ítems (AFI) y Teoría de Respuesta a los Ítems (TRI).APORTE:Tres son los principales aportes de este trabajo de Tesis de Doctorado. En primer lugar, se aplican dos escalas de personalidad diferentes a muestras independientes, manteniendo constante el resto de las condiciones experimentales. Con ello se espera controlar que los resultados observados son producto del efecto ejercido por los distintos formatos de respuesta utilizados y no por otras variables. En segundo lugar, cada sujeto contesta su respectiva escala experimental utilizando los tres formatos de respuesta propuestos. Ello permite disponer de información directa respecto de cómo ha respondido realmente cada sujeto -y no sólo con una estimación indirecta, derivada de la comparación de muestras independientes, como ha sido lo habitual hasta este momento. Finalmente, el análisis de las propiedades psicométricas de las escalas experimentales se aborda por primera vez, simultáneamente, desde tres perspectivas diferentes (TCT, AFI y TRI). Esto permite controlar que los resultados observados no son consecuencia inmediata del modelo psicométrico utilizado, sino producto del efecto ejercido por los distintos formatos de respuesta propuestos. El análisis de la validez de los cuestionarios se realiza aplicando Modelos de Ecuaciones Estructurales (SEM).RESULTADOS Y DISCUSIÓN:En su conjunto, los resultados observados sugieren que el número de opciones de respuesta afecta de forma leve a moderada la estructura interna y, parcialmente, la consistencia interna de las escalas utilizadas en este trabajo de Tesis de Doctorado. Por el contrario, el número de alternativas de respuesta no afecta aspectos tales como la evidencia basada en la relación con otras variables o la estabilidad temporal (estabilidad test-retest) de las escalas analizadas.PALABRAS CLAVE:Número óptimo de opciones de respuesta, Cuestionarios de personalidad, Satisfaction with Life Scale (SWLS), Social Problem-Solving Inventory-Revised (SPSI-R), Teoría Clásica de los Tests (TCT), Análisis Factorial de los Ítems (AFI), Teoría de Respuesta a los Ítems (TRI), Modelos de Ecuaciones Estructurales (SEM), Propiedades psicométricas, Fiabilidad, Validez, evidencia basada en la estructura interna, evidencia basada en la relación con otras variables, consistencia interna, estabilidad temporal. / Numerous studies have attempted to answer the question of what is the optimal number of response options in personality questionnaires. Some authors argue that the number of response options do not affect at all the reliability or the validity of the measurement tool, whereas others suggest to use from 2- to 25-response alternatives in order to maximize the psychometric properties of the instrument. The present PhD Dissertation work attempts to aboard in an exhaustive manner this question.METHOD:All subjects have responded, within the same session, a questionnaire with two-, three- and five-response options. In order to avoid that the subjects notice that they are responding to the same questionnaire, within a same session, these are applied within a tests battery. Likewise, two independent samples (A and B) and two personality questionnaires [Negative Problem Orientation (NPO) of the Social Problem Solving Inventory-Revised (SPSI-R) and Satisfaction with Life Scale (SWLS)] are used, to ensure that the answer does not depend on the instrument investigated. Both, the reliability and validity of the instrument will be used as criteria to determine the optimum number of response alternatives. Finally, the reliability and validity of each response format is analysed using three different psychometric models: "Classical Test Theory" (CTT), "Item Factor Analysis" (IFA), and "Item Response Theory" (IRT). Add, we used Structural Equation Models (SEM) to analyze the validity of the NPO and SWLS scales.RESULTS AND DISCUSSION:As a whole, the observed results suggest that the number of response options affects form slight to moderate aspects such as the internal structure and, partially, the internal consistency of the scales analyzed in this work. Contrary, the number of response alternatives does not affect aspects such as the evidence based on the relation with other variables or the temporary stability (test-retest stability) of the examined scales.KEYWORDS:Optimal number of response options, Classical Tests Theory (CCT), Item Factor Analysis (IFA), Item Response Theory (IRT), Structural Equation Models (SEM), Psychometric properties, Reliability, Validity, Personality rating scales, Satisfaction with Life Scale (SWLS), Social Problem-Solving Inventory-Revised (SPSI-R), evidence based on the internal structure, evidence based on the relation with other variables, internal consistency, temporary stability.

This dissertation focuses on the contributions of Phonetics in the teaching and learning processes of languages pronunciation in Singing. For that, it investigates a teaching proposal based on this discipline of Linguistics, the Phonetics, with emphasis on articulation and representation of speech sounds - the Articulatory Phonetics and the International Phonetic Alphabet (IPA) in practice, the phonetic transcription. It is based on the literature on Phonetics and Phonology, in the Linguistics area, on the Teaching of Languages, in the Applied Linguistics, and on the Diction for Singers, in the Arts - specifically, the field of Music, singing. Based on the diagnosis made on the subject of Diction in technical and undergraduate courses of Singing in institutions in the triangle region of Minas Gerais, it reflects and suggests changes on didactic and pedagogical aspects, related to the training of singers and singing teachers. It intends to contribute with theoretical reflections, teaching materials and methodological approaches for the teaching of pronunciation of the major languages in the classical repertoire performed in Brazil. / Esta dissertação centra-se nas contribuições da Fonética no processo ensino e aprendizagem da pronúncia de línguas no Canto. Para isto, investiga uma proposta de ensino elaborada com base nesta disciplina da Linguística, a Fonética, com ênfase na articulação e representação dos sons da fala a Fonética Articulatória e o Alfabeto Fonético Internacional (AFI) em sua prática, a transcrição fonética. Fundamenta-se em literaturas sobre Fonética e Fonologia, da área de Linguística, sobre o Ensino de Línguas, da Linguística Aplicada e, sobre Dicção para Cantores, das Artes especificamente, da subárea Música, o instrumento Canto. Com base no diagnóstico da disciplina Dicção em cursos técnicos e graduação em Canto de algumas instituições na região do Triângulo Mineiro, reflete e sugere mudanças de aspectos didáticos e pedagógicos, em função da formação de cantores professores de Canto. Pretende contribuir com reflexões teóricas, material didático e abordagens para o ensino da pronúncia das principais línguas do repertório erudito praticado no Brasil. / Mestre em Artes

Magnetic Resonance Imaging (MRI) is a non-ionizing form of medical imaging which has practical uses in diagnosing, characterizing, and studying diseases in vivo. Current clinical practice utilizes a highly trained radiologist to view MR images and qualitatively diagnose, characterize, or study a disease. There is no easy way to compare qualitative data. That is why developing quantitative measures in MRI show promise. Quantitative measures of disease can be compared across a population, MRI sites, and over time. Osteoarthritis is one disease where those who have it may benefit from the development of quantitative MRI measures. Those benefits may include earlier diagnosis and treatment of the disease or treatment which may halt or even reverse the damage from the disease.The work presented in this dissertation focuses on analyzing and developing new methods of radiofrequency (B1) field mapping to improve quantitative MRI measures. The dissertation opens with an introduction and a brief primer on MRI physics, followed by an introduction to B1 and flip-angle mapping in MRI (Chapters 1-3). Chapter 4 presents a careful statistical analysis of a recent and popular B1 mapping method, the Bloch-Siegert shift (BSS) method, along with a comparison of the technique to other common B1 mapping methods. The statistical models developed in chapter 4 are verified using both Monte Carlo simulation and actual MRI experiments in phantoms. Chapter 5 analyzes and details the potential errors introduced in B1 mapping when a 3D slab-selective excitation is employed. A method for correcting errors introduced by 3D slab-selective B1 mapping is then introduced in chapter 6, along with metrics to quantify the error involved. The thesis closes with a summary of other scientific contributions made by the author in chapter 7. The chapters comprising the bulk of the presented research (4-7) are briefly summarized below. Chapter 4, the statistical analysis of B1 mapping methods, demonstrates the effectiveness of deriving the B1 estimate from the phase of the MR image. These techniques are shown to perform particularly well in low signal-to-noise ratio (SNR) applications. However, there are benefits and drawbacks of each B1 mapping technique. The BSS method deposits a significant amount of radiofrequency (RF) power into the patient, causing a concern that tissue heating may occur. The Phase-Sensitive (PS) method of B1 mapping outperforms the other techniques in many situations, but suffers from significant sensitivity to off-resonance. The Dual-Angle (DA) method is very simple to implement and the analysis is straightforward, but it can introduce significant mean bias in the estimate. No B1 mapping technique performs well for all situations. Therefore, the best B1 mapping method needs to be determined for each situation. The work in chapter 4 provides guidance for that choice. Many B1 mapping techniques rely on a linear relationship between flip angle and transmit voltage. That assumption breaks down when a 3D slab-selective excitation is used. 3D slab-selective excitation is a common technique used to reduce the field-of-view (FOV) in MRI, which can directly reduce scan time. The problem with slab-selective excitation in conjunction with B1 mapping has been documented, but the potential errors in B1 estimation have never been properly analyzed across different techniques. The analysis in chapter 5 demonstrates that the errors introduced in B1 mapping using a slab-selective excitation in conjunction with the ubiquitous DA B1 mapping method can be significant. It is then shown that another B1 mapping technique, the Actual Flip Angle Imaging (AFI) method, doesn't suffer from the same limitation. The analysis presented in Chapter 6 demonstrates that some errors introduced by 3D slab-selective B1 mapping may be modeled and corrected allowing the use of 3D slab-selective excitation to reduce field-of-view, and potentially reduce scan time. The errors are modeled and corrected with a general numerical method using Bloch simulations. The general method is applied to the DA method as an example, but is general and could easily be extended to other methods as well. Finally, a set of metrics are proposed and briefly explored that can be used to better understand the topology and severity of errors introduced into B1 mapping methods. With a better understanding of the errors introduced, the need for correction can be determined. Chapter 7 details other significant ancillary contributions made by the author including: (1) presentation of a new B1 mapping method, the decoupled RF-pulse phase-sensitive B1 mapping method, which has potential for parallel transmit MRI; (2) demonstration of an ultra-short TE method which has potential for imaging Alzheimers brain lesions in vivo; (3) introduction of a new steady-state diffusion tensor imaging technique; (4) phase-sensitive B1 mapping in sodium is demonstrated, a feat not previously demonstrated; (5) a comparison between a dual-tuned and single-tuned sodium coil; (6) introduction of a water- and fat-separation technique using multiple acquisition SSFP; (7) an inter-site and inter-vendor quantitative MRI study is introduced; (8) a relaxation and contrast optimization for laryngeal imaging at 3T is introduced; and (9) diffusion imaging with insert gradients is introduced.