The vapor phase photochemistry of the three isomeric cyanopyridines and the three methylpyridines was studied by irradiating their vapors at 254 nm. It was found that direct irradiation of any one cyanopyridine isomer resulted in the formation of the other two isomers of cyanopyridine or methylpyridines respectively. The reactivity of each isomer was found to be different. This was suggested to be based on the stability of their azaprefulvene intermediates formed during interconversion. The phototransposition of these molecules was suggested to result from 2,6-bonding, nitrogen migration around the five sides of cyclopentenyl ring followed by rearomatization. This mechanism was found to be consistent with the results of deuterium labeling studies of cyanopyridines These result suggest that cyanopyridines undergo phototransposition via the intermediacy of azaprefulvenes instead of Dewar-pyridine and azaprismane. Thus, photochemical studies showed that the six trideuteriopyridine isomers constitute two separate photochemical triads. Each triad consists of three isomers that are photointerconverting upon irradiation at 254 nm in the vapor phase. Similary, it was found that the three isomeric tetradeuteriopyridine isomers also constitute a photochemical triad and are interconverting upon irradiation at 254 nm in the vapor phase. These phototranspositions are best explained by the cyclization, nitrogen migration, and rearomatization mechanism. These results are in contrast to the long-held belief that pyridine is photostable in the vapor phase. Instead, unlabeled pyridine undergoes a hidden phototransposition leading back to itself.

Introdução. A epidemia global de obesidade e suas consequências ocorrem simultaneamente a uma maior consciência quanto às escolhas que promovem a saúde, padrões estéticos cada vez mais magros e oferta crescente de alimentos industrializados de alta densidade calórica, saborosos e práticos. Este cenário estimula a indústria de alimentos a utilizar apelos de saúde como estratégia de concorrência. Objetivo. Analisar a utilização de apelos de saúde e outras estratégias de incentivo ao consumo presentes na rotulagem de alimentos industrializados, sua coerência com os teores de calorias, gorduras, açúcares e sal presentes nesses alimentos e sua convergência com a legislação pertinente. Metodologia. A definição de teores elevados de calorias, gorduras, açúcares e sódio e dos quesitos que nortearam a análise foi feita a partir da legislação pertinente e da literatura. Um formulário foi criado e a análise baseou-se nas informações declaradas na rotulagem pelo fabricante. A categoria estudada foi Biscoitos e Salgadinhos. Os produtos foram escolhidos pela análise do gasto das famílias paulistanas com alimentação a partir da base de micro dados da Pesquisa de Orçamento Familiar (POF), da Fundação Instituto de Pesquisas Econômicas (FIPE). Foram identificadas 64 marcas e adquiridos 209 produtos em supermercados da cidade de São Paulo. Foram avaliados densidade calórica, teores de açúcar, gorduras saturada e trans, e sódio. Quatro dos quesitos tratam de diversas formas de estímulo ao consumo (apelos de saúde, selos de certificação, brindes e prêmios e apresentação do produto); o último trata da obrigatoriedade de informar os teores de gorduras, açúcar e sódio em destaque. Produtos com um ou mais teores elevados não deveriam apresentar nenhuma ação relativa aos quatro primeiros quesitos, e todos deveriam atender ao último, por ser exigência legal. Resultados. A totalidade dos produtos apresentou densidade calórica elevada e para 99% a quantidade de Kcal/100g foi maior que o dobro do limite; 48% não informaram os teores de açúcar separadamente; 22% declararam quantidades elevadas de açúcar; 64% apresentaram teores elevados de gordura saturada. Mais da metade dos produtos continha gordura vegetal, mas declarou 0% de gordura trans na porção; 35% eram alimentos livres de gordura vegetal; 53% apresentaram teores de sódio elevados sendo 17% entre 50% e 100% acima e 20%, mais que o dobro do limite. Noventa e quatro por cento dos produtos apresentaram teores concomitantemente elevados; 27%, calorias, gordura saturada e sódio; 20%, calorias e sódio e 17%, calorias e gordura saturada. Setenta e um por cento dos produtos com um ou mais dos teores elevados utilizaram apelos de saúde na sua rotulagem; 4%, selos de certificação de sociedades médicas; 6% bonificações, prêmios ou brindes e 16%, embalagens especiais; 66% dos produtos não apresentaram teores de gorduras, açúcar e sódio em destaque apesar de esta ser exigência legal. Conclusão. Os produtos estudados apresentaram um ou mais dos teores avaliados acima dos parâmetros estabelecidos; apelos de saúde e outras estratégias de marketing nutricional foram identificados em produtos que não deveriam ser associados a uma alimentação saudável ou ter seu consumo incentivado. / Introduction. The global epidemic of obesity and its consequences occur simultaneously to a greater awareness of the choices that promote health, aesthetic standards increasingly thin and an increasing availability of foods of high caloric density, tasty and practical. This scenario encourages the food industry to use health claims as competitive strategy. Objective. To analyze the use of health claims and other strategies to boost consumption present in food labeling, the consistency with the levels of calories, fat, sugar and salt in these products and its convergence with relevant legislation. Methodology. The definition of high levels of calories, fats, sugars and sodium and the questions that guided the analysis were based was based on the relevant legislation and the literature. A form was created and the analysis was based on the information declared on the label by the manufacturer. The category studied was Cookies and Snacks. Products were chosen by the analysis of the household spending from Sao Paulo city with food from the Household Budget Survey (POF) database, run by Economic Research Institute Foundation (FIPE). Sixty four brands were identified and 209 products were purchased in supermarkets in the city of São Paulo. Energy density, sugar content, saturated and trans fats, and sodium were evaluated. Four of the questions dealt with various forms of promotion (health claims, certification, gifts and prizes and product presentation) and one with the obligation to highlight the levels of fat, sugar and sodium. Products with high levels of one or more of these contents should not present any elements relating to the first four questions, and all of them should serve the latter, because it is a legal requirement. Results. All the products showed high caloric density and for 99% of them the amount of Kcal/100g was higher than twice the threshold; 48% did not report sugar levels separately; 22% informed high amounts of sugar; 64% had elevated levels of saturated fat. More than half of the products contained vegetable fat, but stated 0% trans-fat per portion; 35% were vegetable fat free products; 53% of the sample showed elevated levels of sodium; 17% informed sodium levels between 50% and 100% above while 20% report more than double the limit . Ninety-four percent of the products showed high levels simultaneously; 27%, calories, sodium and saturated fat; 20%, calories and sodium and 17%, saturated fat and calories. Seventy-one percent of the products with one or more elevated levels used health claims in its labeling; 4% presented medical societies seal certification, 16% used special packaging and 6% offered bonuses, prizes or giveaways; 66% of the products did not show the levels of fat, sugar and sodium highlighted despite it being a legal requirement. Conclusion. The products included in this study had one or more of the assessed levels above established parameters; health claims and other marketing strategies were identified in nutritional products that should not be associated with healthy eating or have their consumption encouraged.

L’Imagerie par Résonance Magnétique (IRM) est une technique prometteuse largement répandue dans les milieux hospitaliers. Elle est non invasive, présente une bonne résolution spatiale et permet de visualiser en profondeur dans un organisme vivant. Elle possède cependant quelques défauts, dont sa faible sensibilité. Pour palier ce problème, il est possible d'utiliser des espèces hyperpolarisables telles que le xénon. Cependant, n’étant spécifique d’aucun récepteur biologique, le xénon nécessite d’être vectorisé. Pour ce faire, des auteurs ont proposé son encapsulation dans une cage moléculaire capable de reconnaître la cible biologique à imager. Les meilleurs candidats à ce jour sont les cryptophanes.Nous nous sommes fixés comme objectif dans cette thèse de concevoir et de synthétiser de nouvelles cages plus adaptées pour les applications en IRM 129Xe ainsi que des biosondes pertinentes pour se rapprocher d’applications in vivo. Dans une première partie de ma thèse, nous nous sommes intéressés au développement de nouvelles cages afin d’étudier et d’affiner les propriétés d’encapsulation du xénon au sein des cryptophanes. Dans les parties suivantes, nous nous sommes concentrés sur la conception de biosondes par fonctionnalisation de cryptophanes déjà décrits pour diverses applications d’intérêt biologique. D’une part, nous avons évalué la possibilité de détecter des métaux de manière plus spécifique et plus sensible grâce à l’IRM xénon hyperpolarisé. D’autre part, nous avons travaillé sur la conception de biosondes bimodales, afin de coupler des techniques complémentaires d’imagerie médicale. / Today, Magnetic Resonance Imaging (MRI) is a powerful clinically used imaging method which provides three-dimensional images with excellent resolution. However, conventional molecular MRI techniques that rely on the observation of water protons still suffer from reduced sensitivity and often lack selectivity. The use of hyperpolarized xenon can improve both the selectivity and sensitivity of the MRI method. As xenon has no specificity for any biological receptor, it needs to be vectorized. For this purpose, authors have proposed to encapsulate xenon inside molecular cages functionalized to recognize specific biological targets. The best candidates so far as biosensors are cryptophanes.The aim of this work is to design and synthesize new cryptophanes that are better suited for 129Xe MRI applications and relevant biosensors for future in vivo applications. In a first part, new cages were developed in order to study the encapsulation properties of xenon inside different cryptophanes. Then, biosensors were synthesized by functionnalization of known water-soluble cryptophanes for different applications of biological interest. We have therefore assessed the possibility of detecting metal ions specifically in a very sensitive way thanks to 129Xe MRI. New bimodal sensors were also designed and tested.

Objectifs : Les thérapies régénératives cardiaques ont connu un essor considérable au cours des 10 dernières années. Malgré des effets positifs démontrés chez l’animal, les bénéfices cliniques obtenus chez l’homme sont encore relativement modestes. L’objectif de ce travail a été de mieux comprendre les facteurs liés à l’implantation des cellules souches grâce aux techniques de détection cellulaire en imagerie par résonance magnétique (IRM), afin d’optimiser la thérapie cellulaire cardiaque.Matériel et méthodes : Un protocole de détection cellulaire en IRM cardiaque in vivo ainsi qu’une méthode de détection des microvaisseaux en IRM cardiaque ex vivo haute résolution avec des séquences Susceptibility Weighted Imaging (SWI) ont été développés, puis mis en application pour l’étude de la vectorisation de progéniteurs des cellules endothéliales marqués magnétiquement par des nanoparticules d’oxyde de Fer et injectés par voie intraveineuse, ainsi que pour l’évaluation de l’intégration et de l’efficacité de cellules souches mésenchymateuses administrées via des patchs de fibrine cellularisés chez des rats adultes indemnes de toute pathologie (un groupe contrôle vs un groupe infarctus via ligature définitive de l’artère interventriculaire antérieure).Résultats : Après injection intraveineuse et malgré la vectorisation magnétique (n=16 rats), l’imagerie de détection cellulaire a montré qu’aucune cellule n’était implantée dans le myocarde et que les paramètres fonctionnels cardiaques n’étaient pas améliorés. Avec les patchs cellularisés (n=37 rats), la fraction d’éjection ventriculaire gauche (FEVG) était améliorée dans les groupes de patchs cellularisés par rapport aux groupes contrôles. La densité microvasculaire était augmentée dans la zone infarcie et peri-infarcie dans les groupes cellularisés par rapport aux groupes contrôles, à la fois en immunohistochimie et en IRM sur les séquences SWI. L’IRM a montré l’absence de migration des cellules dans le myocarde à partir du patch, confirmé en immunohistochimie. La persistance de cellules dans la zone d’implantation du patch à la surface épicardique à J21 post greffe et l’étude en cytométrie en flux des cytokines et facteurs de croissance produits par les cellules souches plaident pour une efficacité de la thérapie cellulaire en rapport avec la sécrétion de facteurs paracrines par les cellules souches.Conclusion : L’imagerie de susceptibilité magnétique permet d’une part d’étudier les vaisseaux myocardiques sur des séquences pondérées en SWI ex vivo et d’autre part d’évaluer l’implantation des cellules souches sur des séquences en écho de gradient T2* in vivo. Ces techniques ont permis de mieux caractériser le mode d’action des patchs cardiaques en tant que réservoir de facteurs paracrines pour le traitement de l’insuffisance cardiaque dans un modèle murin. Ces résultats confirment l’intérêt fort à développer et optimiser l’utilisation de biomatériaux intelligents délivrant spécifiquement des molécules d’intérêt comme les cytokines ou les facteurs de croissance et permettant ainsi de contourner les contraintes immunogènes et tératogènes liés aux cellules souches. / Objectives: Cardiac regenerative therapies have grown considerably over the past 10 years. Despite positive effects demonstrated in animals, the clinical benefits obtained in humans are still relatively modest. The objective of this work was to better understand the factors associated with implantation of stem cells through the cell detection techniques in magnetic resonance imaging (MRI) and to improve cardiac stem cell therapy in a murine model of myocardial infarction.Materials and methods: A protocol for cell detection with gradient echo T2* sequences in cardiac MRI in vivo and a method for detection of microvessels in cardiac MRI ex vivo with high resolution Susceptibility Weighted Imaging sequences (SWI) were developed and implemented for the study of vectorization of intravenously injected endothelial progenitors cells (EPC) and the integration and evaluation of the impact of mesenchymal stem cells (MSC) administered via cellularized fibrin patches. A permanent ligation of the left anterior coronary artery was performed in adult rats. The stem cells were magnetically labeled with iron oxide nanoparticles by endocytosis.Results: Cell detection imaging showed no cell implantation in the myocardium and no improvement in cardiac functional parameters after intravenous injection of EPC, despite the aid of magnetic vectorization (n = 16 rats). With a local administration of MSC via cardiac patches (n = 37 rats), the left ventricular ejection fraction (LVEF) was improved in cellularized patches groups compared to controls. Microvascular density was increased in the infarcted and peri – infarcted areas in cellularized patches groups compared to controls in immunohistochemistry and in MRI on SWI sequences. The MRI showed no migration of cells into the myocardium from the patch, as confirmed by immunohistochemistry and Perls staining. The persistence of MSCs on the epicardial surface at D21 after implantation and flow cytometry profiling of cytokines and growth factors produced by MSC argue for cell therapy effectiveness related to the secretion of paracrine factors by stem cells.Conclusion: Susceptibility imaging allows: (1) to study myocardial vessels on SWI sequences ex vivo and (2) to assess the implementation of stem cells on gradient echo sequences T2 * in vivo. These techniques have shown that cardiac patches act as a reservoir of soluble mediators which paracrinally target the angiogenesis in the treatment of heart failure in a murine model. This is in favor of a move towards “cell free” biomaterials containing only molecules of interest such as cytokines or growth factors to circumvent immunogenic and teratogenic constraints related to the use of stem cells.

Green marketi ng is aimed at directing a company‘s efforts to undertake the processes of designing a product, its promotion, pricing, and distribution in a way that can help to protect the environment. The current study is aimed at investigating the influence of green marketing practices including eco-labeling, green branding and green advertising on consumer buying behavior in Pakistan which is a developing country. The study has also analyzed the mediating effect of environmental knowledge in the relationship between green marketing practices and consumer buying behavior. The research useda quantitative approach and a structured survey questionnaire to collect data from 300 respondents. The study results revealed that green advertising and green branding has a significant positive relationship with consumer buying behavior while eco-labeling is not a significant predictor for this purpose. Moreover, environmental knowledge partially mediates the relationship between green marketing and consumer buying behavior. In this way, the current study has contributed to literature by analyzing the green marketing practices with and without the presence of environmental knowledge in Pakistan. The results of the research are helpful for marketers to emphasize more on green advertising being the strong predictor of consumer buying behavior. It also urges them to make their environmental friendly activities closer to reality in order to gain greater acceptability from consumers. However, the study has not taken into account alldimensions of green marketing and the sample responses belong to the population in only urban areas of Pakistan.

Food allergies within the United States and Europe have become exceedingly prevalent in children, adolescents, and adults. In the United States alone, over 12 million people have been diagnosed with at least one food allergy. If the allergen is accidentally consumed, the food allergy sufferer may suffer a life-threatening condition known as anaphylaxis. More than 200 U.S. food allergic consumers die annually as a result of anaphylaxis due to ingestion of food allergens. To safely manage food allergies, food allergy sufferers and stakeholders (such as caregivers) require clear and complete ingredient information to avoid certain allergens in packaged food products. Despite U.S. legislative mandates designed to assist the food allergic consumers and stakeholders to make safe food selection choices, food allergy labeling on consumer packaged food products remains unclear. To properly manage food allergy, it is imperative that food allergy stakeholders have access to clear and unambiguous food allergen ingredients located on the food product labels. The purpose of this research was to capture the impact of current United States food allergen labeling guidelines on U.S. food allergy stakeholders. With the elaboration likelihood framework, this research aimed to better understand how the congruence of allergen ingredient information on the Product Label Claim on the front of the package and Nutrition Facts Panel information on the back of the package affected food allergic consumers and stakeholders in evaluation of product packaging allergen information. A total of 223 food allergy stakeholders were administered four surveys depicting food allergen labeling variations found on U.S. food product labels. Seventeen hypotheses were formulated and analyzed with ANCOVA and t tests to measure the impact of congruence and elaboration of the food allergen messages on the food product labels, with a specific focus on purchase intention. Findings indicated that food allergy stakeholders had difficulties using and understanding existing food allergen labels under current U.S. food allergen labeling guidelines. The results also showed confusion among U.S. food allergic stakeholders with safe food selection choices when the label claims did not align with the actual allergen ingredient information. Research, public policy, and managerial implications were thoroughly discussed.

Este trabalho tem por finalidade avaliar os ganhos em eficiência energética através da classificação de níveis, atribuídos a sistemas de iluminação das instalações, com a aplicação da proposta de regulamentação para etiquetagem voluntária do nível de eficiência energética de edificações comerciais, de serviços e públicos, em fase de homologação. Foi realizada uma contextualização da importância da referida proposta de regulamentação, com uma abordagem dos principais sistemas de avaliação de desempenho ambiental de edifícios em âmbito internacional e no Brasil, considerando as principais iniciativas e estado atual das mesmas. Com o uso da referida metodologia, foram realizados três estudos distintos: o primeiro, considerando um levantamento de dados em uma edificação existente que se caracteriza por sediar uma organização administrativa que faz parte do poder público, composta de 275 dependências. O segundo e o terceiro estudo tratam da aplicação em um projeto luminotécnico, no mesmo empreendimento, de duas luminárias distintas (compostas de sistemas ópticos com e sem aletas, respectivamente). A partir dessas atividades que norteiam a aplicação direta da metodologia para confecção de projetos, foram estabelecidas comparações entre os resultados obtidos e realizadas considerações sobre os índices de iluminância, de densidade de potência instalada total em iluminação e da densidade de potência em iluminação. De posse de todos os resultados obtidos em uma edificação com relevante representatividade no segmento dos prédios públicos, bem como das considerações pertinentes, podemos inferir que com o uso somente de iluminação geral, sem iluminação local é possível atingir no máximo a classificação B e que temos a possibilidade de uso dos dois tipos de luminárias adotadas sem alterar a classificação dos níveis de eficiência energética encontrados. / This study aims to assess the gains in energy efficiency through the classification levels, assigned to the installation of lighting systems, with the implementation of the proposed regulations for voluntary labeling of the level of energy efficiency in commercial buildings, of services and public in stage of approval. One contextualization of the importance of the proposed regulation was held with major systems for evaluating environmental of buildings in the international and Brazil, considering the major initiatives and current status of them. With the use of that methodology, three separate studies were conducted: first, considering a survey of data in an existing building which is hosting an administrative organization of the public power, composed of 275 dependences. The second and third studies dealing with the application in a lighting project in the same enterprise, in two different luminaries (composed of optical systems with and without fins, respectively). From these activities that guide the direct application of the methodology for preparation of projects there have been established comparisons between the results and made comments on the levels of illuminance, the density of total installed power in lighting and in lighting power density. In possession of all results obtained in a building with significant representation in the segment of public buildings, as well as the relevant considerations, we can infer that with the use only of general lighting, local lighting is not possible to achieve the maximum rating B and we have the possibility to use both types of luminaires adopted without changing the classification of levels of energy efficiency found.

O crescimento anual no número de procedimentos realizados em Medicina Nuclear se deve em primeiro lugar à vantagem de não serem invasivos. Cerca de 80% dos diagnósticos realizados em Medicina Nuclear utilizam radiofármacos preparados com tecnécio-99m devido a suas características físicas ideais, disponibilidade e baixo custo. Dentre os radiofármacos utilizados para identificar processos de infecção e inflamação estão os leucócitos marcados com tecnécio-99m, considerado o padrão ouro e o citrato de gálio (67 Ga), atualmente comercializado no Brasi. Os leucócitos marcados possuem a desvantagem da técnica laboriosa de marcação nem sempre disponível nos centros de Medicina Nuclear, enquanto o citrato de gálio (67 Ga) não é específico e possui energias desfavoráveis para a dosimetria do paciente e para a aquisição de imagens. Neste cenário, novas moléculas para diagnóstico de focos de infecção têm sido pesquisadas, particularmente envolvendo biomoléculas, como os peptídeos antimicrobianos. Nesta categoria, a Ubiquicidina na forma de um fragmento sintético (UBI 29-41) despertou o interesse de pesquisadores que estudaram a marcação com tecnécio-99m utilizando métodos direto e indireto. Um reagente liofilizado de UBI 29-41descrito na literatura demonstrou eficácia no diagnóstico de focos de infecção utilizando-se imagens cintilográficas, porém o produto não está disponível no Brasil. O objetivo deste trabalho foi estudar a marcação do fragmento de UBI 29-41 com tecnécio-99m por método direto e avaliar a utilização de soluções tampão no procedimento de marcação, de modo a flexibilizar o volume da solução de pertecnetato de sódio a ser utilizado, o que constitui aspecto de ineditismo deste trabalho. O fragmento foi radiomarcado com diferentes volumes de soluções tampão alcalinas (carbonato e fosfato) e a utilização dos tampões em substituição à solução de hidróxido de sódio possibilitou realizar a marcação com diferentes volumes da solução de pertecnetato de sódio, sem comprometimento do rendimento de marcação. Uma formulação liofilizada foi avaliada, demonstrando estabilidade por período de 12 meses, viabilizando a produção rotineira do agente de marcação. Os estudos de biodistribuição das preparações efetuadas com os diferentes tampões demonstraram que os complexos formados apresentam características gerais de biodistribuição semelhantes ao composto padrão descrito na literatura, incluindo rápido clareamento sanguíneo e alta captação renal, condizente com a eliminação do produto por esta via. Entretanto, as preparações estudadas apresentaram captação hepática maior e captação renal menor que o composto padrão. As preparações estudadas captaram no foco de infecção provocado por S.aureus e demonstraram potencial para aplicação clínica no diagnóstico em Medicina Nuclear. Como pré-requisito para a realização de estudos clínicos de um novo composto foi realizado estudo de cito e genotoxicidade, cujos resultados demonstraram a segurança das preparações estudadas. / The annual growth in the number of Nuclear Medicine procedures is directly related to the fact that they are non invasive techniques. About 80% of diagnostic procedures in Nuclear Medicine use technetium-labelled radiopharmaceuticals, because of ideal physics characteristics of this radionuclide, disponibility and low cost. Some radiopharmaceuticas employed in the diagnostic of infection and inflammation is technetium labeled leukocytes, considered the gold standard, and gallium citrate (67 Ga) that are commercialized in Brazil. The procedures for labeling leukocytes are laborious and not always aviable in the Nuclear Medicine Centers, that constitutes a disadvantage of this radiopharmaceutical. On the other hand, galium citrate (67 Ga) is not specific and its energies are not favourable for patient dosimetry and image. In this context, new molecules for diagnostic of infection have been studied, particularly biomolecules, as the antimicrobians peptides. In this category, the Ubiquicidine, as a synthetic fragment (UBI 29-41), was particularly investigated by many researchers for labeling with technetium-99m by direct and indirect methods. A liophylized kit described in the literature showed good results in the diagnostic of infection focous by scintilographic images, but this product is not aviable in Brazil. The objective of this work was to study the labeling of the UBI 29-41 fragment with technetium-99m by direct method using buffer solutions on labeling procedure, that results in a less restrictive labeling technique concerning the volume of sodium pertechnetate solution employed, that constitutes in the originality of this work. UBI fragment was labeled with different volumes of alkaline buffers (carbonate and phosphate) and the use of buffers instead sodium hydroxide solution resulted in labeling procedures that employed different volumes of sodium pertechnetate solution without loss in the labeling yield. A liophylized kit was prepared, showing stability for 12 months, that supports a rotine production of this labeling agent. The biodistribution studies using the radiopharmaceutical prepared with different buffers showed that the resulted complexes presented biodistribution characteristics similar to the standard preparation described in the literature, including fast blood clearance and renal excretion. However, the studied preparations showed higher liver uptake and lower renal uptake when compared to the standard preparation. The studied preparations presented good uptake on infection focus produced by inoculation of S.aureus and showed potential for application in clinical procedures in Nuclear Medicine. Citotoxicity and genotoxicity studies were conducted with the peptide fragment as prerequisit for future clinical studies and the results showed the security of the compound for clinical application.

Made available in DSpace on 2016-03-15T19:46:26Z (GMT). No. of bitstreams: 1 Lais Quinquio Benega.pdf: 572273 bytes, checksum: cb4463af4efd6d0ce59723b0e06b6517 (MD5) Previous issue date: 2015-03-20 / This study aims to verify the usage of referential strategies, focusing on the labeling strategy and how it works organizing opinion articles. As there is space, in this type of text, for the author to express his or her opinion or review, there is opportunity to analyze the performance of labeling as a reference and argumentative cohesion strategy. For that, the study is based on the Functionalist theory, which sees in language usage the aim of developing effective communication between speakers, taking into account the production situation, as well as the social determinants related to the production context. We tried to observe similarities and differences between the sample texts, as well as the most significant lexical choices in the context. The analysis started from the search for referential noun phrases on texts, emphasizing the phrases with a lexical core and the possible evaluative meaning present in this core. It was found that there is a large use of labeling on the chosen texts, mainly in paragraph beginnings, working as a negative evaluation term to resume situations narrated in earlier portions of the text. It was also noticed that the texts showed labeling occurrences with evaluative meaning even in the title, and this use may activate certain semantic fields converging with the proposed argument to be developed in the text. There is a difference in the use of evaluative terms in journalists‟ texts and the ones written by a professional from another area, since in these ones we can observe the choice for evaluative predications terms and labeling. This usage contributes to the conduction of the argumentation, not only to reinforce the author's position, but also to require the reader to rebuild the referent to which the label refers to. / Este trabalho tem como objetivo verificar o uso de estratégias referenciais, especialmente a rotulação, na estruturação de artigos de opinião. Por haver espaço, nesse tipo de texto, para expressão da opinião e de avaliações do autor, analisa-se a atuação da rotulação como estratégia referencial e de coesão argumentativa. Para tanto, o estudo baseia-se na teoria Funcionalista, que vê no uso da língua o objetivo de estabelecer uma comunicação efetiva entre os participantes, segundo a situação de uso, consideradas as determinações sociais ligadas ao contexto de produção. Procurou-se observar semelhanças e diferenças entre os textos da amostra, além das escolhas lexicais mais significativas no contexto. A análise partiu do levantamento dos sintagmas referenciais dos textos, com foco nos sintagmas de núcleo lexical e na possível carga avaliativa presente nesse núcleo. Verificou-se que, entre os sintagmas nominais encontrados, prevalecem rotulações em posição de início de parágrafo, que retomam situações narradas em porções anteriores do texto constituindo termo avaliativo de carga negativa. Percebeu-se, ainda, que os textos apresentavam rotulação com carga avaliativa desde o título, e esse uso pode ativar determinados campos semânticos convergentes com a proposta argumentativa a ser desenvolvida no texto. Há distinção no uso de termos avaliativos em textos de jornalistas e de profissional de outra área, visto que nestes se observa carga avaliativa nas escolhas dos termos predicações e das rotulações. Verificou-se que a rotulação realmente contribui para a condução da linha argumentativa do texto, não apenas por reforçar o posicionamento do autor, mas também por exigir do leitor que, a partir do rótulo de carga negativa, reconstrua o referente a que o rótulo se refere.

Contexto: A Anotação de Papéis Semânticos (APS) é uma tarefa da área de Processamento de Línguas Naturais (PLN) que permite detectar os eventos descritos nas sentenças e os participantes destes eventos (Palmer et al., 2010). A APS responde perguntas como Quem?, Quando?, Onde?, O quê?, e Por quê?, dentre outras e, sendo assim, é importante para várias aplicações de PLN. Para anotar automaticamente um texto com papéis semânticos, a maioria dos sistemas atuais emprega técnicas de Aprendizagem de Máquina (AM). Porém, alguns papéis semânticos são previsíveis e, portanto, não necessitam ser tratados via AM. Além disso, a grande maioria das pesquisas desenvolvidas em APS tem dado foco ao inglês, considerando as particularidades gramaticais e semânticas dessa língua, o que impede que essas ferramentas e resultados sejam diretamente transportados para outras línguas. Revisão da Literatura: Para o português do Brasil, há três trabalhos finalizados recentemente que lidam com textos jornalísticos, porém com performance inferior ao estado da arte para o inglês. O primeiro (Alva- Manchego, 2013) obteve 79,6 de F1 na APS sobre o córpus PropBank.Br; o segundo (Fonseca, 2013), sem fazer uso de um treebank para treinamento, obteve 68,0 de F1 sobre o córpus PropBank.Br; o terceiro (Sequeira et al., 2012) realizou anotação apenas dos papéis Arg0 (sujeito prototípico) e Arg1 (paciente prototípico) no córpus CETEMPúblico, com performance de 31,3 pontos de F1 para o primeiro papel e de 19,0 de F1 para o segundo. Objetivos: O objetivo desse trabalho de mestrado é avançar o estado da arte na APS do português brasileiro no gênero jornalístico, avaliando o desempenho de um sistema de APS treinado com árvores sintáticas geradas por um parser automático (Bick, 2000), sem revisão humana, usando uma amostragem do córpus PLN-Br. Como objetivo adicional, foi avaliada a robustez da tarefa de APS frente a gêneros diferentes, testando o sistema de APS, treinado no gênero jornalístico, em uma amostra de revisões de produtos da web. Esse gênero não foi explorado até então na área de APS e poucas de suas características foram formalizadas. Resultados: Foi compilado o primeiro córpus de opiniões sobre produtos da web, o córpus Buscapé (Hartmann et al., 2014). A diferença de performance entre um sistema treinado sobre árvores revisadas e outro sobre árvores não revisadas ambos no gênero jornalístico foi de 10,48 pontos de F1. A troca de gênero entre as fases de treinamento e teste, em APS, é possível, com perda de performance de 3,78 pontos de F1 (córpus PLN-Br e Buscapé, respectivamente). Foi desenvolvido um sistema de inserção de sujeitos não expressos no texto, com precisão de 87,8% no córpus PLN-Br e de 94,5% no córpus Buscapé. Foi desenvolvido um sistema, baseado em regras, para anotar verbos auxiliares com papéis semânticos modificadores, com confiança de 96,76% no córpus PLN-Br. Conclusões: Foi mostrado que o sistema de Alva-Manchego (2013), baseado em árvores sintáticas, desempenha melhor APS do que o sistema de Fonseca (2013), independente de árvores sintáticas. Foi mostrado que sistemas de APS treinados sobre árvores sintáticas não revisadas desempenham melhor APS sobre árvores não revisadas do que um sistema treinado sobre dados gold-standard. Mostramos que a explicitação de sujeitos não expressos nos textos do Buscapé, um córpus do gênero de opinião de produtos na web, melhora a performance da sua APS. Também mostramos que é possível anotar verbos auxiliares com papéis semânticos modificadores, utilizando um sistema baseado em regras, com alta confiança. Por fim, mostramos que o uso do sentido do verbo, como feature de AM, para APS, não melhora a perfomance dos sistemas treinados sobre o PLN-Br e o Buscapé, por serem córpus pequenos. / Background: Semantic Role Labeling (SRL) is a Natural Language Processing (NLP) task that enables the detection of events described in sentences and the participants of these events (Palmer et al., 2010). SRL answers questions such as Who?, When?, Where?, What? and Why? (and others), that are important for several NLP applications. In order to automatically annotate a text with semantic roles, most current systems use Machine Learning (ML) techniques. However, some semantic roles are predictable, and therefore, do not need to be classified through ML. In spite of SRL being well advanced in English, there are grammatical and semantic particularities that prevents full reuse of tools and results in other languages. Related work: For Brazilian Portuguese, there are three studies recently concluded that performs SRL in journalistic texts. The first one (Alva-Manchego, 2013) obtained 79.6 of F1 on the SRL of the PropBank.Br corpus; the second one (Fonseca, 2013), without using a treebank for training, obtained 68.0 of F1 for the same corpus; and the third one (Sequeira et al., 2012) annotated only the Arg0 (prototypical agent) and Arg1 (prototypical patient) roles on the CETEMPúblico corpus, with a perfomance of 31.3 of F1 for the first semantic role and 19.0 for the second one. None of them, however, reached the state of the art of the English language. Purpose: The goal of this masters dissertation was to advance the state of the art of SRL in Brazilian Portuguese. The training corpus used is from the journalistic genre, as previous works, but the SRL annotation is performed on non-revised syntactic trees, i.e., generated by an automatic parser (Bick, 2000) without human revision, using a sampling of the corpus PLN-Br. To evaluate the resulting SRL classifier in another text genre, a sample of product reviews from web was used. Until now, product reviews was a genre not explored in SRL research, and few of its characteristics are formalized. Results: The first corpus of web product reviews, the Buscapé corpus (Hartmann et al., 2014), was compiled. It is shown that the difference in the performance of a system trained on revised syntactic trees and another trained on non-revised trees both from the journalistic genre was of 10.48 of F1. The change of genres during the training and testing steps in SRL is possible, with a performance loss of 3.78 of F1 (corpus PLN-Br and Buscapé, respectively). A system to insert unexpressed subjects reached 87.8% of precision on the PLN-Br corpus and a 94.5% of precision on the Buscapé corpus. A rule-based system was developed to annotated auxiliary verbs with semantic roles of modifiers (ArgMs), achieving 96.76% confidence on the PLN-Br corpus. Conclusions: First we have shown that Alva-Manchego (2013) SRL system, that is based on syntactic trees, performs better annotation than Fonseca (2013)s system, that is nondependent on syntactic trees. Second the SRL system trained on non-revised syntactic trees performs better over non-revised trees than a system trained on gold-standard data. Third, the explicitation of unexpressed subjects on the Buscapé texts improves their SRL performance. Additionally, we show it is possible to annotate auxiliary verbs with semantic roles of modifiers, using a rule-based system. Last, we have shown that the use of the verb sense as a feature of ML, for SRL, does not improve the performance of the systems trained over PLN-Br and Buscapé corpus, since they are small.