Evaluation and FMEA of Fabrication Techniques for Metallic Grating Couplers on Polymer Substrates with Low Glass Transition Temperatures

The main task is to analyze the state of the art of grating couplers production and low-cost polymer substrates. Then to provide a recommendation of a new or adapted process for the production of metallic gratings on polymer sheets, based on a Failure Mode and Effect Analysis (FMEA). In order to achieve that, this thesis is divided into four chapters. After the first introductory chapter, the second section provides details about the state-of-the-art in optical technology platforms with focus on polymers and their main features for the aimed application, such as flexibility, low cost and roll to roll compatibility. It defines then the diffraction gratings and their specifications and closes with the explanation of adhesion mechanisms of inorganic materials on polymer substrates. The third chapter discusses processing of grating couplers. It introduces the basic fabrication methods and details a selection of current fabrication schemes found in literature with an assessment of their potential use for the desired application. The last chapter is a FMEA analysis of the retained fabrication process, called Flip and Fuse, in order to check its capability to realize the grating structure.

Transdermal delivery of cyclosporin A by electrically enhanced permeation techniques

Transdermal drug delivery has recently received increasing attention in the face of growing challenges to deliver peptide and protein drugs. Controlled transdermal delivery is an important route for the delivery of peptides and proteins that can maintain the therapeutic effectiveness of the drug by minimizing enzymatic degradation which is a major concern in other noninvasive routes of delivery such as the oral route. Although the advantages of transdermal delivery are very desirable, the natural obstacle to drug entry imposed by the skin's barrier function makes it one of the most difficult route of administration. Iontophoresis and electroporation have been reported to be useful as permeation enhancing techniques in the transdermal delivery of protein and peptide drugs. The objective of present study is to use the above enhancement techniques to deliver cyclosporin A (CSA) to treat psoriasis. The in vitro experiments were performed using hairless rat skin as the model with Franz diffusion cells for iontophoresis and custom made diffusion cells for electroporation. The donor drug solution of CSA consisted of an aqueous solution of CSA - polymer solid dispersion, coevaporate, and/or a hydroethanolic solution of CSA PBS was used as the receiver solution. ³H labelled CSA and ¹⁴C labelled ethanol were used to facilitate analysis using a liquid scintillation counter. The control experiment consisted of passive diffusion study. Silver/silver chloride electrodes were used in all studies. In the iontophoresis experiments a constant DC current (0.5 mA/cm²) was used. In the electroporation experiments different delivery parameters were studied: (1) applied electrode voltage (Uelectrode), (2) decay time constant (τ), (3) the number of pulses delivered - single or multiple, and { 4) the time of diffusive contact with drug after electroporation ('contact duration'). Compared to the passive diffusion, iontophoresis did not result in a significant increase in the amount of CSA delivered transdermally with both the CSA-polymer donor and hydroethanolic drug solutions. With the use of electroporation there was a significant increase in the transdermal delivery, compared to passive transport. With the CSA-polymer coevaporate donor solution the increase in delivery was only about 6 fold higher whereas with the hydroethanolic solution the increase was about 60 times higher compared to passive diffusion. The 'contact duration• was an important fader and a 4-hour 'contact duration' was found to be the optimum time period required for effective transdermal delivery. Use of single pulse (τ=5.6 ms) electroporation resulted in a significant increase {p<0.05) in the delivery of CSA in skin {CSA.n) and EtOH in receiver (EtOHreceiver). With multiple pulse (τ=10 ms. 25 pulses) the increase in CSAskin was more pronounced with a 60 fold increase than compared to the passive delivery. However there was no significant increase in the other two quantities viz. CSAreceiver, and EtCHreceiver.

Active Data Collection Techniques to Understand Online Scammers and Cybercriminals

Nigerian scam, also known as advance fee fraud or 419 scam, is a prevalent form of online fraudulent activity that causes financial loss to individuals and businesses. Nigerian scam has evolved from simple non-targeted email messages to more sophisticated scams targeted at users of classifieds, dating and other websites. Even though such scams are observed and reported by users frequently, the community’s understanding of Nigerian scams is limited since the scammers operate “underground”. To better understand the underground Nigerian scam ecosystem and seek effective methods to deter Nigerian scam and cybercrime in general, we conduct a series of active and passive measurement studies. Relying upon the analysis and insight gained from the measurement studies, we make four contributions: (1) we analyze the taxonomy of Nigerian scam and derive long-term trends in scams; (2) we provide an insight on Nigerian scam and cybercrime ecosystems and their underground operation; (3) we propose a payment intervention as a potential deterrent to cybercrime operation in general and evaluate its effectiveness; and (4) we offer active and passive measurement tools and techniques that enable in-depth analysis of cybercrime ecosystems and deterrence on them. We first created and analyze a repository of more than two hundred thousand user-reported scam emails, stretching from 2006 to 2014, from four major scam reporting websites. We select ten most commonly observed scam categories and tag 2,000 scam emails randomly selected from our repository. Based upon the manually tagged dataset, we train a machine learning classifier and cluster all scam emails in the repository. From the clustering result, we find a strong and sustained upward trend for targeted scams and downward trend for non-targeted scams. We then focus on two types of targeted scams: sales scams and rental scams targeted users on Craigslist. We built an automated scam data collection system and gathered large-scale sales scam emails. Using the system we posted honeypot ads on Craigslist and conversed automatically with the scammers. Through the email conversation, the system obtained additional confirmation of likely scam activities and collected additional information such as IP addresses and shipping addresses. Our analysis revealed that around 10 groups were responsible for nearly half of the over 13,000 total scam attempts we received. These groups used IP addresses and shipping addresses in both Nigeria and the U.S. We also crawled rental ads on Craigslist, identified rental scam ads amongst the large number of benign ads and conversed with the potential scammers. Through in-depth analysis of the rental scams, we found seven major scam campaigns employing various operations and monetization methods. We also found that unlike sales scammers, most rental scammers were in the U.S. The large-scale scam data and in-depth analysis provide useful insights on how to design effective deterrence techniques against cybercrime in general. We study underground DDoS-for-hire services, also known as booters, and measure the effectiveness of undermining a payment system of DDoS Services. Our analysis shows that the payment intervention can have the desired effect of limiting cybercriminals’ ability and increasing the risk of accepting payments.

Reconstructability of 3-Dimensional Upper Ocean Circulation from SWOT Sea Surface Height Measurements

Utilizing the framework of effective surface quasi-geostrophic (eSQG) theory, we explored the potential of reconstructing the 3D upper ocean circulation structures, including the balanced vertical velocity (w) field, from high-resolution sea surface height (SSH) data of the planned SWOT satellite mission. Specifically, we utilized the 1/30°, submesoscale-resolving, OFES model output and subjected it through the SWOT simulator that generates the along-swath SSH data with expected measurement errors. Focusing on the Kuroshio Extension region in the North Pacific where regional Rossby numbers range from 0.22 to 0.32, we found that the eSQG dynamics constitutes an effective framework for reconstructing the 3D upper ocean circulation field. Using the modeled SSH data as input, the eSQG-reconstructed relative vorticity (ζ) and w fields are found to reach a correlation of 0.7–0.9 and 0.6–0.7, respectively, in the 1,000m upper ocean when compared to the original model output. Degradation due to the SWOT sampling and measurement errors in the input SSH data for the ζ and w reconstructions is found to be moderate, 5–25% for the 3D ζ field and 15-35% for the 3D w field. There exists a tendency for this degradation ratio to decrease in regions where the regional eddy variability (or Rossby number) increases.

Conception d’outils (autoévaluation, liste de vérification, grille d’évaluation à échelle descriptive) pour l’évaluation formative des savoir-être professionnels chez les stagiaires du programme collégial Techniques d’inhalothérapie

Plusieurs programmes de formation offrent des stages pour compléter la formation et valider les apprentissages des stagiaires en regard du développement de leurs compétences. L’évaluation des savoirs et des savoir-faire occupe une grande place lors de la prestation des stagiaires et permet d’établir leur niveau de compétence. Mais qu’en est-il de l’évaluation de leurs savoir-être professionnels ? Pourtant le savoir-être est une composante indispensable au plein développement de la compétence. Les stagiaires manifestent leurs savoir-être professionnels en milieu clinique. Sans s’en rendre compte, leurs comportements influencent leur future embauche par une institution de santé. C’est la plus value qui fait la différence. Dans notre pratique enseignante, souvent nous éprouvons des difficultés dans l’accompagnement des stagiaires pour le plein développement de leurs savoir-être professionnels. Lorsque surviennent des difficultés, l’absence d’outil rend difficile la tâche d’évaluation des savoir-être professionnels. Cette réalité nous amène au thème de cet essai qui vise la conception d’outils d’évaluation des savoir-être professionnels pour les stagiaires du programme collégial Techniques d’inhalothérapie. Les difficultés d’évaluation des savoir-être professionnels dues à l’absence d’outils a entraîné une réflexion nous menant tout droit à nous questionner sur les caractéristiques essentielles des outils d’évaluation permettant aux enseignantes et aux enseignants de porter un jugement objectif sur les savoir-être professionnels des stagiaires du programme collégial Techniques d’inhalothérapie. Suite à une recension d’écrits en lien avec les concepts des savoir-être professionnels, de l’évaluation et des outils d’évaluation, nous nous sommes fixé cinq objectifs spécifiques pour répondre à notre question générale de l’essai : 1) Établir une nomenclature des savoir-être professionnels pour le programme collégial Techniques d’inhalothérapie; 2) Décrire les savoir-être professionnels en manifestations observables; 3) Concevoir un outil d’autoévaluation en regard du développement des savoir-être professionnels pour les stagiaires du programme collégial Techniques d’inhalothérapie; 4) Concevoir une liste de vérification des comportements observables pour évaluer les savoir-être professionnels des stagiaires du programme collégial Techniques d’inhalothérapie; et 5) Concevoir une grille d’évaluation à échelle descriptive pour évaluer les savoir-être professionnels des stagiaires du programme collégial Techniques d’inhalothérapie. Avec une posture épistémologique interprétative et une approche qualitative, nous avons opté pour un essai de type recherche développement, selon Harvey et Loiselle (2009), visant la conception de trois outils d’évaluation des savoir-être professionnels, soit : a) un outil d’autoévaluation, b) une liste de vérification des comportements observables et c) une grille d’évaluation à échelle descriptive. Après avoir réalisé les deux premiers objectifs spécifiques de cet essai, nous avons sollicité les enseignantes et les enseignants des départements de Techniques d’inhalothérapie du Collège de Rosemont et du Collège de Valleyfield pour procéder à la validation des outils d’évaluation des savoir-être professionnels. Pour accompagner les cinq enseignantes et les trois enseignants dans leur démarche de validation, nous avons privilégié un questionnaire de validation, des entrevues semidirigées et un groupe de discussion pour recueillir les données qualitatives et quantitatives que nous avons traitées en deux temps.L’analyse et l’interprétation des résultats ont permis l’atteinte des objectifs spécifiques fixés. En plus d’établir la nomenclature des savoir-être professionnels, les données recueillies portent un regard critique sur la conception des outils d’évaluation des savoir-être professionnels destinés aux stagiaires du programme collégial Techniques d’inhalothérapie. Grâce aux commentaires et aux suggestions obtenus, nous peaufinerons nos outils pour les rendre plus efficaces après cet essai pour ensuite les remettre aux enseignantes et aux enseignants cliniques participants qui décideront avec leur département respectif s’ils désirent les utiliser. Cet essai identifie huit savoir-être professionnels que doivent démontrer les stagiaires du programme collégial Techniques d’inhalothérapie. Ces savoir-être professionnels se manifestent à partir de quarante-deux comportements observables. La conception de nos outils d’évaluation permet de porter un regard objectif sur le développement des savoir-être professionnels de nos stagiaires. Cet essai ne vise pas à généraliser ces résultats. Nous souhaitons plutôt la transférabilité des résultats à d’autres programmes afin d’accompagner d’autres enseignantes et enseignants qui éprouvent des difficultés lors de l’évaluation des savoir-être professionnels.

Prática de ensino supervisionada em educação pré-escolar e ensino do 1º ciclo do ensino básico: a aprendizagem da leitura e da escrita na primeira infância (dos 3 aos 10 anos)

O presente relatório surgiu da nossa investigação e da nossa praxis tanto no contexto da Prática de Ensino Supervisionada em Educação Pré-Escolar, como em Ensino do 1º Ciclo do Ensino Básico, em instituições da cidade de Évora. O principal objetivo foi compreender a finalidade e funcionalidade atribuída pelas crianças à aprendizagem da leitura e da escrita. Neste sentido, foi construído um referencial teórico que sustentou todo o processo de investigação. Desta forma, considero fundamental, contextualizar de forma breve, os ambientes educativos e a conceção da ação educativa que regeu a minha prática. O presente relatório foi construído com base na investigação-ação, levando assim, à utilização de algumas técnicas e instrumentos de recolha de dados, de forma a atingir os objetivos propostos. Ao longo da investigação procurei promover o desenvolvimento da leitura e da escrita, por parte das crianças, no contexto educativo, bem como, promover uma exploração da língua portuguesa articulada com os diversos domínios curriculares. Os resultados que surgiram deste trabalho veem evidenciar que as crianças já apresentam diversos conhecimentos acerca do que é a leitura e a escrita, bem como a sua funcionalidade. Por outro lado, é notória a separação entre a educação pré-escolar e o 1º Ciclo do Ensino Básico, no sentido em que, no primeiro contexto, as crianças apresentam um papel central na aprendizagem, pois tudo é realizado com base nos seus interesses e necessidades, ao passo que, no segundo contexto, as atividades são planeadas para as crianças, mas elas não são participantes nesses processos. Assim, este relatório encontra-se organizado em quatro capítulos. O primeiro capítulo refere-se à fundamentação teórica que sustenta a investigação do tema. O segundo capítulo encontra-se relacionado com a conceção da ação educativa, na qual são apresentados os contextos onde desenvolvi a minha prática. No terceiro capítulo encontra-se a metodologia aplicada ao longo da PES, tendo por base a questão do educador/professor-investigador, bem como a análise, interpretação dos dados obtidos através da entrevista individual semiestruturada e respetivas conclusões. Por fim, no quarto capítulo tecerei implicações e investigações futuras acerca do estudo realizado; Supervised Teaching Practice in Pre-School Education and Teaching of the 1st Basic Education: Learning reading and writing in early childhood (from 3 to 10 years old) Abstract: This report emerged from our research and our praxis both in the context of Supervised Teaching Practice in Pre-School Education, as in teaching of the 1st Cycle of Basic Education in some institutions of the city of Évora. The main objective was to understand the purpose and function assigned by the learners to reading and writing. In this sense, a theoretical framework was created which underpinned the whole process of investigation. In this way, I consider fundamental to contextualize briefly the educational environments and the design of the educational action that conducted my practice. This report was built on the basis of research–action leading to the use of some techniques and tools for data collection in order to achieve the proposed objectives. Throughout the investigation I tried to promote the development of reading and writing by children in the educational context, as well as to promote an exploration of the Portuguese language in conjunction with the diverse curricular areas. The results that have emerged from this work prove that children have already a wide knowledge about what reading and writing are as well as its functionality. On the other hand, it is evident the separation of pre-school education from the first cycle of basic education in the sense that, in the first context, the children have a central role in learning, because everything is done based on their interests and needs, while in the second context activities are planned for the children, but they do not participate in those processes. Thus, this report is organized into four chapters. The first chapter refers to the theoretical background that supports research on the theme. The second chapter is related to the design of educational activity, which presents the contexts where I developed my practice. The third chapter presents the methodology applied along the PES based on the issue of educator/teacher-researcher, as well as the analysis, interpretation of data obtained through the individual semi-structured interview and the corresponding conclusions. Finally, in the fourth chapter I will discuss the implications and the future investigations about the study performed.

Prática de ensino supervisionada relativo ao ano letivo 2014/2015, realizada na Escola Básica de 2º e 3º ciclos com Ensino Secundário Cunha Rivara

O presente relatório é fruto da Prática de Ensino Supervisionada, realizada no ano letivo 2014/2015 na Escola Básica 2, 3 com Ensino Secundário Cunha Rivara, no âmbito do Mestrado em Ensino do Português no 3.º Ciclo do Ensino Básico e Ensino Secundário e de Espanhol nos Ensinos Básico e Secundário, sob a orientação do Professor Doutor António Ricardo Mira. Esta fase prática do mestrado assume-se como momento charneira na formação de futuros professores, porquanto representa o espaço ideal para aferir e testar métodos e técnicas aplicáveis aos processos de ensino/aprendizagem. Nesse sentido, e partindo do pressuposto de que o aluno deve ser o ator principal ao longo deste processo, este relatório assume uma função descritiva, mas, em simultâneo, outra dimensão, tão ou mais importante, no domínio da reflexão e da interiorização de práticas pedagógico-didáticas e de comportamentos relacionais, assumidos durante este processo. Assim, desenvolve-se em cinco componentes, que se complementam: preparação científica, pedagógica e didática; planificação e condução de aulas e avaliação de aprendizagens; análise da prática de ensino; participação na escola e desenvolvimento profissional; ABSTRACT: This report is the result of Supervised Teaching Practice, held in the school year 2014/2015 at the Basic and Secondary School 2, 3 “Cunha Rivara”, within the Master degree: “Teaching Portuguese in the 3rd cycle of Basic Education and Secondary Education and Spanish in basic and secondary education”, under the guidance of Professor Ricardo Antonio Mira. This practice of master stage is assumed as a key moment in the training of future teachers, because it is the ideal place and moment to measure and test methods and techniques applicable to teaching / learning processes. Accordingly, and assuming that the student must be the main actor throughout this process, this report takes a descriptive function, but at the same time, another dimension, equally important in the field of reflection and practices internalization, pedagogical-didactic and relational behaviors made during this process. Thus it develops into five components, which complement each other: scientific, pedagogical and didactic preparation; planning and conducting classes and learning evaluation; analysis of the teaching practice; participation in school and professional development.

Catalytic CO2 hydrogenation: study at the molecular scale using field emission techniques

An accurate characterization of the rhodium specimen was obtained via FIM experiments. Reaction behaviors between H2 and CO2 were observed in FEM mode at 700 K. At this temperature, CO desorption occurs, preventing CO+H2 reaction. Surface is mainly recovered by oxygen; reaction with hydrogen occurs. Finally, we can identify the reaction as the Reverse Water Gas Shift.

Análise multivariada aplicada ao (in)sucesso escolar a matemática no 3º ciclo : estudo de caso

O insucesso escolar em Portugal é preocupante e é um tema que vem despertando interesse crescente por parte dos políticos, dos professores, dos pais e do público em geral. Entre as disciplinas que mais contribuem para esse insucesso está a Matemática. O insucesso na Matemática é uma realidade incontornável, visível não apenas pelos maus resultados alcançados pelos alunos em testes e exames, mas também pelas enormes dificuldades manifestadas por eles na resolução de problemas, no raciocínio matemático e, sobretudo, pelo seu desinteresse em relação à Matemática. Nesta dissertação procurou aliar-se as metodologias de Estatística Multivariada, nomeadamente de Regressão Logística e de Análise de Clusters, ao insucesso escolar. As técnicas estatísticas foram aplicadas a uma base de dados construída para o efeito a partir dos resultados obtidos num inquérito aplicado aos alunos de uma escola, com o objetivo de investigar associações entre o (in)sucesso dos alunos 3.º Ciclo do Ensino Básico na disciplina de Matemática e um conjunto de variáveis referentes a dados pessoais, familiares e escolares dos alunos. Os resultados obtidos através da Análise de Regressão Logistica sugerem que a repetência a Matemática (nível inferior a 3 no final do ano letivo) está dependente da idade do aluno, das dificuldades sentidas, da participação nas aulas, do empenho e do comportamento do aluno. A Análise de Clusters procurou agrupar as variáveis em grupos homogéneos relativamente a características comuns. Verificou-se que as variáveis comportamento do aluno, fazer os trabalhos de casa e a relação com a professora estão fortemente correlacionadas, bem como as variáveis dificuldades e repetência, mas estas duas últimas bastante distantes das restantes. Da aplicação do Método Duas Etapas às variáveis de opinião, fatores de insucesso escolar e medidas para colmatar esse insucesso, resultou três Clusters, dois grandes grupos, um em que predomina a resposta não concordo nem discordo e outro em que predomina o concordo totalmente. Nesta dissertação conseguiu-se identificar importantes factores que podem ajudar a reduzir o insucesso, pelo que os seus resultados poderão ser usados no futuro na elaboração de medidas para melhorar o sucesso.

Design of Mm-Wave RLSA with lossy waveguides by slot coupling control techniques

This paper discusses how to design a Radial Line Slot Antenna (RLSA) whose waveguide is filled with high loss dielectric materials. We introduce a new design for the aperture slot coupling synthesis to restrain the dielectric losses and improve the antenna gain. Based on a newly defined slot coupling, a number of RLSAs with different sizes and loss factors are analyzed and their performances are predicted. Theoretical calculations suggest that the gain is sensitive to the material losses in the radial lines. The gain enhancement by using the new coupling formula is notable for larger antenna size and higher loss factor of the dielectric material. Three prototype RLSAs are designed and fabricated at 60GHz following different slot coupling syntheses, and their measured performances consolidate our theory.

Preliminary structure-activity relationship studies on some novel s-substituted aliphatic analogues of 5-{1-[(4- chlorophenyl) sulfonyl]-3-piperidinyl}-1, 3, 4-oxadiazol-2-yl sulfide

Purpose: To study the structure-activity relationships of synthetic multifunctional sulfides through evaluation of lipoxygenase and anti-bacterial activities. Methods: S-substituted derivatives of the parent compound 5-(1-(4-chlorophenylsulfonyl) piperidin-3- yl)-1, 3, 4-oxadiazole-2-thiol were synthesized through reaction with different saturated and unsaturated alkyl halides in DMF medium, with NaH catalyst. Spectral characterization of each derivative was carried out with respect to IR, 1H - NMR, 13C - NMR and EI - MS. The lipoxygenase inhibitory and antibacterial activities of the derivatives were determined using standard procedures. Results: Compound 5e exhibited higher lipoxygenase inhibitory potential than the standard (Baicalein®), with % inhibition of 94.71 ± 0.45 and IC50 of 20.72 ± 0.34 μmoles/L. Compound 5b showed significant antibacterial potential against all the bacterial strains with % inhibition ranging from 62.04 ± 2.78, 69.49 ± 0.41, 63.38 ± 1.97 and 59.70 ± 3.70 to 78.32 ± 0.41, while MIC ranged from 8.18 ± 2.00, 10.60 ± 1.83, 10.84 ± 3.00, 9.81 ± 1.86 and 11.73 ± 5.00 μmoles/L for S. typhi, E. coli, P. aeruginosa, B. subtilis and S. aureus, respectively. Compounds 5d, 5e and 5g showed good antibacterial activity against S. typhi and B. subtilis bacterial strains. Conclusion: The results suggest that compound 5e bearing n-pentyl group is a potent lipoxygenase inhibitor, while compound 5b with n-propyl substitution is a strong antibacterial agent. In addition, compounds 5d, 5e and 5g bearing n-butyl, n-pentyl and n-octyl groups, respectively, are good antibacterial agents against S. typhi and B. subtilis.

S-Alkylated/aralkylated 2-(1H-indol-3-yl-methyl)-1,3,4- oxadiazole-5-thiol derivatives. 1. Synthesis and characterization

Purpose: To synthesize and characterize S-alkylated/aralkylated 2-(1H-indol-3-ylmethyl)-1,3,4- oxadiazole-5-thiol derivatives. Methods: 2-(1H-indol-3-yl)acetic acid (1) was reacted with absolute ethanol and catalytic amount of sulfuric acid to form ethyl 2-(1H-indol-3-yl)acetate (2) which was transformed to 2-(1H-indol-3- yl)acetohydrazide (3) by refluxing with hydrazine hydrate in methanol. Ring closure reaction of 3 with carbon disulfide and ethanolic potassium hydroxide yielded 2-(1H-indol-3-ylmethyl)-1,3,4-oxadiazole-5- thiol (4) which was finally treated with alkyl/aralkyl halides (5a-u) in DMF and NaH to yield Salkylated/ aralkylated 2-(1H-indol-3-ylmethyl)-1,3,4-oxadiazole-5-thiols (6a-u). Structural elucidation was done by IR, 1H-NMR and EI-MS techniques Results: 2-(1H-indol-3-ylmethyl)-1,3,4-oxadiazole-5-thiol (4) was synthesized as the parent molecule and was characterized by IR and the spectrum showed peaks resonating at (cm-1) 2925 (Ar-H), 2250 (S-H ), 1593 (C=N ) and 1527 (Ar C=C ); 1H-NMR spectrum showed signals at δ 11.00 (s, 1H, NH-1ʹ), 7.49 ( br.d, J = 7.6 Hz, 1H, H-4\'), 7.37 (br.d, J = 8.0 Hz, 1H, H-7\'), 7.34 (br.s, 1H, H-2\'), 7.09 (t, J = 7.6 Hz, 1H, H-5\'), 7.00 (t, J = 7.6 Hz, 1H, H-6\') and 4.20 (s, 2H, CH2-10ʹ). EI-MS presented different fragments peaks at m/z 233 (C11H9N3OS)˙+ [M+2]+, 231 (C11H9N3OS)˙+ [M]+, 158 (C10H8NO)+, 156 (C10H8N2)˙+, 130 (C9H8N)+. The derivatives (6a-6u) were prepared and characterized accordingly. Conclusion: S-alkylated/aralkylated 2-(1H-indol-3-ylmethyl)-1,3,4-oxadiazole-5-thiols (6a-u) were successfully synthesized.

Novel Automotive Waste Heat Recovery Techniques

The United States transportation industry is predicted to consume approximately 13 million barrels of liquid fuel per day by 2025. If one percent of the fuel energy were salvaged through waste heat recovery, there would be a reduction of 130 thousand barrels of liquid fuel per day. This dissertation focuses on automotive waste heat recovery techniques with an emphasis on two novel techniques. The first technique investigated was a combination coolant and exhaust-based Rankine cycle system, which utilized a patented piston-in-piston engine technology. The research scope included a simulation of the maximum mass flow rate of steam (700 K and 5.5 MPa) from two heat exchangers, the potential power generation from the secondary piston steam chambers, and the resulting steam quality within the steam chamber. The secondary piston chamber provided supplemental steam power strokes during the engine's compression and exhaust strokes to reduce the pumping work of the engine. A Class-8 diesel engine, operating at 1,500 RPM at full load, had a maximum increase in the brake fuel conversion efficiency of 3.1%. The second technique investigated the implementation of thermoelectric generators on the outer cylinder walls of a liquid-cooled internal combustion engine. The research scope focused on the energy generation, fuel energy distribution, and cylinder wall temperatures. The analysis was conducted over a range of engine speeds and loads in a two cylinder, 19.4 kW, liquid-cooled, spark-ignition engine. The cylinder wall temperatures increased by 17% to 44% which correlated well to the 4.3% to 9.5% decrease in coolant heat transfer. Only 23.3% to 28.2% of the heat transfer to the coolant was transferred through the TEG and TEG surrogate material. The gross indicated work decreased by 0.4% to 1.0%. The exhaust gas energy decreased by 0.8% to 5.9%. Due to coolant contamination, the TEG output was not able to be obtained. TEG output was predicted from cylinder wall temperatures and manufacturer documentation, which was less than 0.1% of the cumulative heat release. Higher TEG conversion efficiencies, combined with greater control of heat transfer paths, would be needed to improve energy output and make this a viable waste heat recovery technique.

Development of measurement and modeling techniques to quantify atmospheric deposition of persistent, bioaccumulative and toxic chemicals in the Great Lakes

Measurement and modeling techniques were developed to improve over-water gaseous air-water exchange measurements for persistent bioaccumulative and toxic chemicals (PBTs). Analytical methods were applied to atmospheric measurements of hexachlorobenzene (HCB), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs). Additionally, the sampling and analytical methods are well suited to study semivolatile organic compounds (SOCs) in air with applications related to secondary organic aerosol formation, urban, and indoor air quality. A novel gas-phase cleanup method is described for use with thermal desorption methods for analysis of atmospheric SOCs using multicapillary denuders. The cleanup selectively removed hydrogen-bonding chemicals from samples, including much of the background matrix of oxidized organic compounds in ambient air, and thereby improved precision and method detection limits for nonpolar analytes. A model is presented that predicts gas collection efficiency and particle collection artifact for SOCs in multicapillary denuders using polydimethylsiloxane (PDMS) sorbent. An approach is presented to estimate the equilibrium PDMS-gas partition coefficient (Kpdms) from an Abraham solvation parameter model for any SOC. A high flow rate (300 L min-1) multicapillary denuder was designed for measurement of trace atmospheric SOCs. Overall method precision and detection limits were determined using field duplicates and compared to the conventional high-volume sampler method. The high-flow denuder is an alternative to high-volume or passive samplers when separation of gas and particle-associated SOCs upstream of a filter and short sample collection time are advantageous. A Lagrangian internal boundary layer transport exchange (IBLTE) Model is described. The model predicts the near-surface variation in several quantities with fetch in coastal, offshore flow: 1) modification in potential temperature and gas mixing ratio, 2) surface fluxes of sensible heat, water vapor, and trace gases using the NOAA COARE Bulk Algorithm and Gas Transfer Model, 3) vertical gradients in potential temperature and mixing ratio. The model was applied to interpret micrometeorological measurements of air-water exchange flux of HCB and several PCB congeners in Lake Superior. The IBLTE Model can be applied to any scalar, including water vapor, carbon dioxide, dimethyl sulfide, and other scalar quantities of interest with respect to hydrology, climate, and ecosystem science.