Дисертації з теми "AuNC"

La biosensibilité et la bio-imagerie basées sur la fluorescence jouent des rôles cruciaux dans le développement d'outils de diagnostic rapides et hautement sensibles pour la détection précoce des maladies et la mise en oeuvre d’une médecine de terrain efficace. Cependant, ces techniques nécessitent une certaine optimisation pour obtenir des images haute résolution et des limites de détection très faibles. Cette thèse se concentre sur l'utilisation de nanoparticules optiques et de mécanismes de transfert d'énergie résonant pour des applications avancées en bio-imagerie et en détection de biomolécules. Je présente les analyses spectroscopiques de nanoclusters d'or luminescents encapsulés dans des polymères (AuNC-NPs) adaptés à la bio-imagerie dans la région infrarouge à ondes courtes (SWIR). L’étude des deux temps de vie de luminescence communément décrits dans les AuNCs m’a permis d’obtenir de nouveaux éléments pour comprendre l’origine de leur luminescence. J’ai découvert que ces temps de vie ne sont pas sensibles de la même manière à l’extinction par homoFRET ce qui suggèrent qu’ils sont causés par des mécanismes différents et des parties distincts de ces nano-objets telles que leur surface constituée de thiolate d’or et leur coeur. J'ai également caractérisé une nouvelle famille de complexes de terbium de CoraFluor (CRF) avec plusieurs méthodes spectroscopiques. J'ai découvert qu'ils sont un donneur de transfert d'énergie applicable en tant que sonde FRET et NSET. J'ai atteint des limites sub-nanomolaires pour la détection de points quantiques et j'ai appliqué ce système pour détecter le récepteur du facteur de croissance épidermique (EGFR). Cette thèse décrit le rôle pivot des mécanismes RET, en particulier du FRET, dans l'avancement des technologies de biosensibilité et de bio-imagerie basées sur la fluorescence. Grâce à des conceptions innovantes de nanoparticules et à une utilisation stratégique des complexes Corafluor Tb, l'étude vise à améliorer la résolution de la bio-imagerie dans la région SWIR et à améliorer la sensibilité, la spécificité et l'applicabilité des outils de diagnostic, contribuant ainsi à l'avancement de la médecine de précision et de la gestion des maladies
Fluorescence-based biosensing and bioimaging play crucial roles in developing rapid and highly sensitive diagnostic tools for early detection of diseases and effective point-of-care medicine. However, these techniques require some optimisation to attain high-resolution images and very low detection limits. This thesis focuses on utilising luminescent nanoparticles and Resonance energy transfer mechanisms for advanced bioimaging and biosensing applications. I present the spectroscopic analyses of bright polymer encapsulated gold nanoclusters (AuNC-NPs) suitable for bioimaging in the shortwave infrared (SWIR) region. My study of the two photoluminescence lifetimes commonly measured in AuNCs allowed me to gather new insight to understand the origin of their luminescence. I discovered that each of these lifetimes are not sensitive in the same way to homo FRET suggesting that they originate from distinct mechanisms and distinct parts of the AuNCs such as the gold thiolate surface or the core of the nano-object. I have also characterised a new family of terbium complexes from CoraFluor (CRF) with several spectroscopic methods. I have found that they are a suitable energy transfer donor for FRET and NSET biosensing applications with gold nanoparticles. I attained sub-nanomolar limits of detection of quantum dots and have applied the system to detect the epidermal growth factor receptor (EGFR). This thesis describes the pivotal role of RET mechanisms, particularly FRET, in advancing fluorescence-based biosensing and bioimaging technologies. With innovative nanoparticle designs and strategic use of Corafluor Tb complexes, the study aims to enhance the bioimaging resolution in the SWIR region and improve diagnostic tool sensitivity, specificity and applicability, contributing to advancing precision medicine and disease management

Analytical ultracentrifugation (AUC) has made an important contribution to polymer and particle characterization since its invention by Svedberg (Svedberg and Nichols 1923; Svedberg and Pederson 1940) in 1923. In 1926, Svedberg won the Nobel price for his scientific work on disperse systems including work with AUC. The first important discovery performed with AUC was to show the existence of macromolecules. Since that time AUC has become an important tool to study polymers in biophysics and biochemistry. AUC is an absolute technique that does not need any standard. Molar masses between 200 and 1014 g/mol and particle size between 1 and 5000 nm can be detected by AUC. Sample can be fractionated into its components due to its molar mass, particle size, structure or density without any stationary phase requirement as it is the case in chromatographic techniques. This very property of AUC earns it an important status in the analysis of polymers and particles. The distribution of molar mass, particle sizes and densities can be measured with the fractionation. Different types of experiments can give complementary physicochemical parameters. For example, sedimentation equilibrium experiments can lead to the study of pure thermodynamics. For complex mixtures, AUC is the main method that can analyze the system. Interactions between molecules can be studied at different concentrations without destroying the chemical equilibrium (Kim et al. 1977). Biologically relevant weak interactions can also be monitored (K ≈ 10-100 M-1). An analytical ultracentrifuge experiment can yield the following information: • Molecular weight of the sample • Number of the components in the sample if the sample is not a single component • Homogeneity of the sample • Molecular weight distribution if the sample is not a single component • Size and shape of macromolecules & particles • Aggregation & interaction of macromolecules • Conformational changes of macromolecules • Sedimentation coefficient and density distribution Such an extremely wide application area of AUC allows the investigation of all samples consisting of a solvent and a dispersed or dissolved substance including gels, micro gels, dispersions, emulsions and solutions. Another fact is that solvent or pH limitation does not exist for this method. A lot of new application areas are still flourishing, although the technique is 80 years old. In 1970s, 1500 AUC were operational throughout the world. At those times, due to the limitation in detection technologies, experimental results were obtained with photographic records. As time passed, faster techniques such as size exclusion chromatography (SEC), light scattering (LS) or SDS-gel electrophoresis occupied the same research fields with AUC. Due to these relatively new techniques, AUC began to loose its importance. In the 1980s, only a few AUC were in use throughout the world. In the beginning of the 1990s a modern AUC -the Optima XL-A - was released by Beckman Instruments (Giebeler 1992). The Optima XL-A was equipped with a modern computerized scanning absorption detector. The addition of Rayleigh Interference Optics is introduced which is called XL-I AUC. Furthermore, major development in computers made the analysis easier with the help of new analysis software. Today, about 400 XL-I AUC exist worldwide. It is usually applied in the industry of pharmacy, biopharmacy and polymer companies as well as in academic research fields such as biochemistry, biophysics, molecular biology and material science. About 350 core scientific publications which use analytical ultracentrifugation are published every year (source: SciFinder 2008 ) with an increasing number of references (436 reference in 2008). A tremendous progress has been made in method and analysis software after digitalization of experimental data with the release of XL-I. In comparison to the previous decade, data analysis became more efficient and reliable. Today, AUC labs can routinely use sophisticated data analysis methods for determination of sedimentation coefficient distributions (Demeler and van Holde 2004; Schuck 2000; Stafford 1992), molar mass distributions (Brookes and Demeler 2008; Brookes et al. 2006; Brown and Schuck 2006), interaction constants (Cao and Demeler 2008; Schuck 1998; Stafford and Sherwood 2004), particle size distributions with Angstrom resolution (Cölfen and Pauck 1997) and the simulations determination of size and shape distributions from sedimentation velocity experiments (Brookes and Demeler 2005; Brookes et al. 2006). These methods are also available in powerful software packages that combines various methods, such as, Ultrascan (Demeler 2005), Sedift/Sedphat (Schuck 1998; Vistica et al. 2004) and Sedanal (Stafford and Sherwood 2004). All these powerful packages are free of charge. Furthermore, Ultrascans source code is licensed under the GNU Public License (http://www.gnu.org/copyleft/gpl.html). Thus, Ultrascan can be further improved by any research group. Workshops are organized to support these software packages. Despite of the tremendous developments in data analysis, hardware for the system has not developed much. Although there are various user developed detectors in research laboratories, they are not commercially available. Since 1992, only one new optical system called “the fluorescence optics” (Schmidt and Reisner, 1992, MacGregor et al. 2004, MacGregor, 2006, Laue and Kroe, in press) has been commercialized. However, except that, there has been no commercially available improvement in the optical system. The interesting fact about the current hardware of the XL-I is that it is 20 years old, although there has been an enormous development in microelectronics, software and in optical systems in the last 20 years, which could be utilized for improved detectors. As examples of user developed detector, Bhattacharyya (Bhattacharyya 2006) described a Multiwavelength-Analytical Ultracentrifuge (MWL-AUC), a Raman detector and a small angle laser light scattering detector in his PhD thesis. MWL-AUC became operational, but a very high noise level prevented to work with real samples. Tests with the Raman detector were not successful due to the low light intensity and thus high integration time is required. The small angle laser light scattering detector could only detect latex particles but failed to detect smaller particles and molecules due to low sensitivity of the detector (a photodiode was used as detector). The primary motivation of this work is to construct a detector which can measure new physico-chemical properties with AUC with a nicely fractionated sample in the cell. The final goal is to obtain a multiwavelength detector for the AUC that measures complementary quantities. Instrument development is an option for a scientist only when there is a huge potential benefit but there is no available commercial enterprise developing appropriate equipment, or if there is not enough financial support to buy it. The first case was our motivation for developing detectors for AUC. Our aim is to use today’s technological advances in microelectronics, programming, mechanics in order to develop new detectors for AUC and improve the existing MWL detector to routine operation mode. The project has multiple aspects which can be listed as mechanical, electronical, optical, software, hardware, chemical, industrial and biological. Hence, by its nature it is a multidisciplinary project. Again by its nature it contains the structural problem of its kind; the problem of determining the exact discipline to follow at each new step. It comprises the risk of becoming lost in some direction. Having that fact in mind, we have chosen the simplest possible solution to any optical, mechanical, electronic, software or hardware problem we have encountered and we have always tried to see the overall picture. In this research, we have designed CCD-C-AUC (CCD Camera UV/Vis absorption detector for AUC) and SLS-AUC (Static Light Scattering detector for AUC) and tested them. One of the SLS-AUC designs produced successful test results, but the design could not be brought to the operational stage. However, the operational state Multiwavelength Analytical Ultracentrifuge (MWL-AUC) AUC has been developed which is an important detector in the fields of chemistry, biology and industry. In this thesis, the operational state Multiwavelength Analytical Ultracentrifuge (MWL-AUC) AUC is to be introduced. Consequently, three different applications of MWL-AUC to the aforementioned disciplines shall be presented. First of all, application of MWL-AUC to a biological system which is a mixture of proteins lgG, aldolase and BSA is presented. An application of MWL-AUC to a mass-produced industrial sample (β-carotene gelatin composite particles) which is manufactured by BASF AG, is presented. Finally, it is shown how MWL-AUC will impact on nano-particle science by investigating the quantum size effect of CdTe and its growth mechanism. In this thesis, mainly the relation between new technological developments and detector development for AUC is investigated. Pioneering results are obtained that indicate the possible direction to be followed for the future of AUC. As an example, each MWL-AUC data contains thousands of wavelengths. MWL-AUC data also contains spectral information at each radial point. Data can be separated to its single wavelength files and can be analyzed classically with existing software packages. All the existing software packages including Ultrascan, Sedfit, Sedanal can analyze only single wavelength data, so new extraordinary software developments are needed. As a first attempt, Emre Brookes and Borries Demeler have developed mutliwavelength module in order to analyze the MWL-AUC data. This module analyzes each wavelength separately and independently. We appreciate Emre Brookes and Borries Demeler for their important contribution to the development of the software. Unfortunately, this module requires huge amount of computer power and does not take into account the spectral information during the analysis. New software algorithms are needed which take into account the spectral information and analyze all wavelengths accordingly. We would like also invite the programmers of Ultrascan, Sedfit, Sedanal and the other programs, to develop new algorithms in this direction.
Die analytische Chemie versucht die chemische Zusammensetzung, chemische und physikalische Eigenschaften von biologischen oder künstlichen Materialien zu bestimmen. Mit der Entwicklung deren Methoden können genauere Informationen über die Umweltverschmutzung, das Ozonloch, Proteinfunktionen und Wechselwirkungen im menschlichen Körper erlangt werden. Es sind eine Vielzahl von analytischen Techniken vorhanden, die durch Verbesserungen in der Mikroelektronik, Mechanik, Informatik und Nanotechnologie einer markanten Entwicklung unterworfen wurden. In dieser Arbeit wurde versucht die Detektionskapazität der analytischen Ultrazentrifuge zu erhöhen. Die analytische Ultrazentrifuge (AUZ) ist eine gut bekannte, sehr leistungsstarke Trennungsmethode. AUZ benutzt die Zentrifugalkraft zum Trennen von Stoffen. Die Probe kann für die Messung gelöst oder in einer Flüssigkeit dispergiert werden. Makromoleküle, Proteine und kolloidale Systeme in Lösung können in einer AUZ Zelle zwischen 1000-60000 Rotationen pro Minute zentrifugiert werden, wie beispielsweise in der kommerziellen Beckmann AUZ. Die Rotationsbeschleunigung entspricht 73-262mal der Erdschwerebeschleunigung (= 9.81 m s-2) für eine radiale Position von 6.5 Zentimeter. Diese Kraft ist der Schlüsselfaktor für die Fähigkeit der AUZ sogar kleine Moleküle und Ionen zu trennen. Die Experimente wurden bei kontrollierter Rotationsgeschwindigkeit und Temperatur ausgeführt. Drei verschiedene, neue Detektoren wurden im Rahmen dieser Arbeit konstruiert und getestet. Diese Detektoren haben die analytischen Informationen sehr verbessert. Dies wurde für Proteine, halbleitende Nanopartikel sowie auch für industrielle Produkte gezeigt.

When exposed to light, metal nanoparticles exhibit a phenomenon known as LSPR, Localized Surface Plasmon Resonance. The wavelengths at which LSPR occurs is very dependent on the refractive index of the surrounding medium. Binding of biomolecules to the surface of gold nanoparticles result in a change in the refractive index that can be detected spectrophotometrically by monitoring the LSPR peak shift. When functionalized with the corresponding ligand(s), gold nanoparticles can be utilized in biosensors to detect the presence and concentration of a predetermined analyte. However, the system must exhibit high specificity and give rise to a detectable shift for analytes in the desired concentration range to be of commercial interest. The aim of the diploma project was to investigate and optimize the biofunctionalization and performance of a fiber optics based LSPR biosensor.  Three ligand systems were investigated for detection of antibodies (IgG), insulin and avidin. Binding of the analyte to the ligand caused a shift of a few nanometers when using spherical gold nanoparticles. The shifts were significantly larger when using gold nanorods. When using the IgG and insulin ligands, only minor unspecific binding was observed. The setup thus shows great potential for use in a wide range of sensing applications.

Dissertação (mestrado) - Universidade Federal de Santa Catarina, Centro de Comunicação e Expressão. Programa de Pós-Graduação em Letras/Inglês e Literatura Correspondente.
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Nos dias atuais, há uma crescente necessidade de socializar problemas pessoais e, notavelmente, as revistas femininas são um bom veículo para o compartilhamento de experiências. Nesta dissertação, investigo um gênero textual específico em revistas femininas, as colunas de aconselhamento. A função principal dessas colunas é responder e aconselhar leitoras sobre questões pessoais, normalmente relacionadas a problemas conjugais envolvendo sexo e amor, assim como relacionamento entre amigos. Este estudo propõe uma investigação lingüística de duas colunas de aconselhamento publicadas na revista Glamour. O objetivo principal é mostrar como as experiências são representadas nas cartas das leitoras e também nas cartas de aconselhamento. Para esse fim, em uma macro aborgadem, a análise deste gênero textual revela a estrutura esquemática das cartas sob consideração. E, em uma micro abordagem, este estudo examina a representação de experiências realizadas pelas escolhas de transitividade. O arcabouço analítico aplicado a esta pesquisa baseia-se na teoria sistêmico-funcional, principalmente nos estudos de Halliday (1985, 1994) e Halliday & Matthiessen (2004). Os resultados do presente trabalho indicam que: 1) as colunas de aconselhamento publicadas na revista Glamour podem ser consideradas um gênero textual híbrido, no qual as cartas das leitoras apresentam características narrativas, enquanto as cartas de aconselhamento apresentam estrutura exortativa; 2) a análise da transitividade revela que: (i) até mesmo em uma dimensão profissional, as experiências femininas estão relacionadas a emoções e relacionamentos pessoais; (ii) os processos materiais, relacionais e mentais aparecem em maior número, indicando que as experiências são construídas geralmente por representações de ações, relações de atribuição/identidade e compartilhamento de sentimentos/pensamentos; (iii) esses processos associam as experiências femininas aos contextos privado e profissional, à idealização de soluções para os problemas expostos, e à ações abstratas; (iv) as leitoras se representam em papéis passivos, como "vítimas" socialmente oprimidas, visto que a conselheira é representada de maneira autoconfiante, como uma solucionadora de problemas. Os resultados desta pesquisa esperam contribuir para a conscientização dos leitores, estimulando-os a refletir sobre as práticas textuais vigentes, bem como fornecer ferramentas teórico-analíticas para que possam discutir e desvendar significados freqüentemente obscuros nos textos. In contemporary days, there seems to be a growing need to socialize personal problems, and notably, women's magazines appear to be a good vehicle for sharing experiences. In this thesis, I investigate a specific genre in women's magazines, the Agony Aunt Columns, also known as advice columns. The main function of Agony Aunt Columns is to answer readers' letters by providing pieces of advice on personal issues, normally related to love, sex, and relationships in general. The present study proposes a linguistic investigation of two Agony Aunt Columns, published on Glamour magazine. The main objective of this work is to show how experiential meanings are construed in both, advice-seeking and advice-giving letters. For that purpose, at a macro level, a genre analysis reveals the schematic structure of the letters under consideration. And, at a micro level, this study examines the representation of experiential meanings realized by the transitivity choices. The analytical framework applied to this research is based on Systemic Functional theory, mainly on the works of Halliday (1985, 1994) and Halliday & Matthiessen (2004). The results of this study indicate that: 1) Glamour Agony Aunt Columns may be considered an example of hybrid genre, in which advice-seeking letters present narrative features, while advice-giving letters resemble the structure of hortatory text-types; 2) the transitivity analysis of the two Agony Aunt Columns reveals that: (i) even in a workplace dimension, women's experiences are related to emotions and private affairs; (ii) material, relational and mental processes appear in a major number, indicating that women's experiences are construed mostly by representations of actions, relationships of being and sharing of feelings/thoughts; (iii) the processes associate women's experiences with identification in the two contexts (private and professional), idealization (the solutions for their problems), and with abstract and non-abstract actions; (iv) advice-seekers tend to represent themselves in passive roles, as "victims" socially oppressed, whereas the advice-giver is strongly represented as a reliable self-confident problem solver. The findings of this research hope to contribute to raise language awareness, stimulate readers to reflect on textual practices, as well as empowering them with theoretically-oriented analytical tools for discussing and unveiling often hidden textual meanings.

This project was designed to investigate whether spending more class time and instructor planning time on teaching vocabulary would lead to improvement of student learning, attitude toward scientific vocabulary, and science literacy skills. Throughout the treatment the students spent more time working with terms chosen for each unit. This included activities that encouraged analysis of word meaning and comparison and analysis of relationships between terms. Summative assessments showed improvement in student comprehension along with increased confidence in their ability to perform lesson objectives. Additionally, the attitude students had toward science vocabulary and science literacy skills were more positive. The students also improved in their writing skills and use of appropriate terminology when working in groups and on projects.

Project FRESH is about creating a sustainable food system for our future. It is the goal of this project to design a large scaled environmentally controlled farm. The vision of this farm is to relieve many of the social and environmental stress that arise out of our current food systems. Furthermore this book is a compilation of research that investigates the problems and solutions that pertain to our modern food system. The first part of the book is research that expresses the current issues that exist with our food system today. This research will state and elaborate on the problems for which Project FRESH is attempting to combat. The second part of this book is the design proposal for Project FRESH. The design goal of this project is to create a fresh perspective on agriculture and its connection to the city. Creating a symbol for our future that patches agriculture back into our cities urban fabric. This symbol is to express the importances of locally grown food and its impact not only on the environment but its overall social and health benefits as well.

Nesse trabalho foi feito um estudo comparativo de sílicas do tipo SBA-15 organofuncionalizadas com mercaptopropiltrimetoxisilano e/ou silsesquioxano iônico contendo o grupo 1,4-diazoniabiciclo[2,2,2]octano. Foram avaliadas as suas habilidades como estabilizadores e controladores de tamanho de nanopartículas de ouro, bem como a sua capacidade de ancoramento das nanopartículas no interior dos poros das sílicas, usando-se diferentes quantidades de ouro. Também foi avaliada a habilidade de um xerogel de sílica modificado com o mesmo silsesquioxano iônico, como suporte de íons Au (III) adsorvido via troca-iônica. Estes materiais foram caraterizados usando várias técnicas, tais como: análise elementar, termogravimetria, isotermas de adsorção-dessorção de nitrogênio, difração de raios X, espectroscopia na região do UV-Vis e do infravermelho e microscopia eletrônica de transmissão. Foi possível avaliar que o uso do silsesquioxano iônico leva a um maior controle na forma, no tamanho e na distribuição de tamanho das nanopartículas presentes nos poros das sílicas. Além disso, o silsesquioxano iônico se mostrou eficiente como ancorador de íons Au (III) na superfície de xerogel de sílica. A sílica contendo nanopartículas de ouro e íons Au (III) mostrou-se promissora para ser aplicada como catalisador heterogêneo.
In this work, it was made a comparative study of organofunctionalized SBA-15 type silicas with mercaptopropyltrimethoxysilane and/or ionic silsesquioxane containing 1,4-diazoniabicyclo [2,2,2] octane group. Their abilities as stabilizers and size controllers for gold nanoparticles, as well as, the capacities to anchor nanoparticles inside of silica pores, using different amounts of gold, were evaluated. It was also studied a silica xerogel modified with the same ionic silsesquioxano, as adsorbent for Au (III) by ion-exchange. These materials were characterized using several techniques such as: elemental analysis, thermogravimetry, nitrogen adsorption-desorption isotherms, X-ray diffraction, UV-Vis and infrared spectroscopy, and transmission electron microscopy. It was possible to evaluate that the use of ionic silsesquioxane leads to a greater control in the shape, size and distribution of the nanoparticles present in the silica pores. In addition, the ionic silsesquioxane proved to be efficient as an adhesion agent of Au (III) ions on the silica xerogel surface. Silica containing gold nanoparticles and Au (III) ions showed promising results as heterogeneous catalysts.

Mestrado em Estudos Editoriais
The present work intends to make a brief reflection about traditional oral tale in Portugal. A special emphasis was placed on the traditional tale The Ten Magic Dwarves of Aunt Aquamarine, including the study of part of its editorial history in three editions of the tale. These editions were made by three different publishers, in different periods of time and for that reason we can see the evolution that occurred in the editorial process. The last aim of this work was to present a new editorial proposal with a new and updated version of the story present in the tale. We concluded that the editorial market for Children Literature in Portugal is growing in the last decades. Today, a new generation of authors is giving renovated attention to it in close collaboration with other professionals, like designers and illustrators. In the basis of Children Literature was the traditional oral tales which carry symbols and myths of the past generations. These tales are often rewritten into new versions, with adaptations and updates that may convert them into Children’s Literature or into Adult Literature. Finally, editorial options, such as book size, illustrations or typefaces, also help to define the target audience of a publication. The edition process of a publication has several phases. Starting on a manuscript, which is revised several times, passing through all the book creation chain. Options taken until the book release to the market including not only design decisions, but also marketing and management decisions. Finally, the result of this work is the mockup of a small publication with the titled Did Aunt Aquamarine lend only ten magic dwarves to help? Its intention was to make an updated version which reflected a renovated look over the traditional oral tale under study in this work.
O presente trabalho tem como objetivo fazer uma breve reflexão sobre o conto tradicional em Portugal. Foi realizado o estudo do conto tradicional Os dez anõezinhos da Tia Verde-Água com principal ênfase nos aspetos editoriais de três versões diferentes, de três editoras diferentes e publicadas em diferentes períodos de tempo. Por fim, o último objetivo deste trabalho foi apresentar uma proposta editorial com uma nova versão da história presente no conto. Concluímos que o mercado editorial para a Literatura Infantojuvenil em Portugal continua a crescer. Hoje, uma nova geração de autores está a prestar atenção renovada a este campo editorial, em estreita colaboração com profissionais como designers e ilustradores. Na base da Literatura Infantojuvenil estiveram os contos tradicionais que carregam consigo símbolos e mitos de gerações passadas. Esses contos são muitas vezes reescritos, com adaptações e atualizações que podem convertê-los em Literatura Infantojuvenil ou em Literatura para Adultos. Finalmente, opções editoriais, como tamanho do livro, ilustrações ou tipos de letra, também ajudam a definir o público-alvo de uma publicação. O processo de edição de uma publicação tem várias fases. Começando por um original, que após aceitação e revisão, passa por toda a cadeia de edição até chegar ao leitor. As opções tomadas até ao lançamento do livro incluem não apenas decisões de design, mas também decisões de marketing e gestão. Por fim, o resultado deste trabalho é a maqueta de uma pequena publicação com o título Did Aunt Aquamarine lend only ten magic dwarves to help? Cumprindo assim o objetivo de fazer uma nova versão que refletisse um olhar renovado sobre o conto oral em estudo neste trabalho.

Tesis entregada a la Universidad de Chile en cumplimiento parcial de los Requisitos para optar al Grado de Magíster en Ciencias Químicas.
Se realizó un estudio de las propiedades electrónicas y geométricas de moléculas de ftalocianina libre H2Pc y ftalocianina de oro AuPc depositadas sobre una superficie metálica de oro representada mediante un cluster de 26 y 58 átomos respectivamente, usando la metodología de teoría de funcionales de la densidad. Mediante la inclusión de una corrección semi-empírica para dar cuenta de las fuerzas de dispersión, la metodología D3, se mostró que la interacción entre las moléculas y la superficie está regida por fuerzas atractivas de tipo van der Waals, que determinan la estabilización de los sistemas estudiados, así como sus propiedades geométricas que se evidencia en la disminución de la distancia molécula-superficie. Esto se fundamenta tanto en el análisis de las energías de interacción como en la visualización de las fuerzas de dispersión mediante la metodología NCI. Cálculos de Densidad de Estados muestran que los sistemas molécula-superficie exhiben una estructura electrónica de interfase metal-orgánica, lo que provee evidencia de que el modelo de cluster es viable en la aproximación supermolécula para el estudio de fenómenos de superficie. También se analizó la capacidad electrocatalítica del sistema AuPc y se observó que reproduce la tendencia de los sistemas experimentales con configuraciones electrónicas similares.
A study of the electronic and geometric properties of metal-free phthalocyanine H2Pc and gold phthalocyanine AuPc deposited over a gold metallic surface represented by a cluster of 26 and 58 atoms respectively, using the density functional theory methodology. Through the inclusion of a semi-empirical correction to take into account the dispersion forces, the D3 methodology, it has been shown that the interaction between molecules and surface is ruled by van der Waals attractive forces, which determine the stabilization of the studied systems and their geometric properties, demonstrated by the dropping of the molecule-surface distance. This is explained by the analysis of the interaction energies and by the visualization of dispersion forces by means of the NCI methodology. Calculations of Density of States show that molecule-surface systems display a metalorganic interface electronic structure, which provides evidence for the cluster model as a feasible one in the supermolecule approximation for the study of surface related phenomena. Also, the electrocatalytic behavior of the AuPc system was analyzed and it was observed that it reproduces the experimental tendencies of systems with similar electronic configurations.
Fondecyt Regular N° 1140503 y N° 1180158.

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This study aims to analyze the work of the Colombian esoteric Samael Aun Weor based on the concept of "secularization of esotericism" proposed by the historian Wouter Hanegraaff. Contributing to the interdisciplinary debate that articulates the field of Cultural History, History of Religions and the recent History of Western Esotericism, it is intended to analyze the reversing relations and mutual influences that guide the construction of the modern Western culture, its rationality paradigms and empirical science; and on the other hand, the establishment of an esoteric tradition that seeks to harmonize these paradigms with a design strongly "enchanted" of the universe, and the mutual process of appropriation/ reinterpretation involved.This debate also dialogues to a more specific discussion in the field of Science of Religions, which seeks to understand the changes occurring in Western religious field opposite the new secularized society. Specifically, this paper seeks to contribute to the debate by offering a perspective of these processes from its Latin American component in order to identify how these dynamics are reproduced on the continent and its specificities. With this purpose, taking the work of Samael Aun Weor as a case study, it was conducted a long-term historical context by inserting the author in a more general constitution process of modern Western esotericism, and specifically, in the constitution process of an esoteric spiritualities field in Colombia, birth cradle of the Gnostic Movement. From a historical-comparative analysis of his work evolution, its institutionalization and practices - which takes into account conceptual and methodological contributions of Italian History of Religions School, historiography on Western esotericism and theoretical proposition Bourdieu from the concept of "field" - the work highlights the doctrinal transition that the Colombian esoteric Aun Weor operates in his work, moving from Rosicrucianism towards the conceptions of a psychological esotericism, proposed by the Russian esoteric Gurdjieff. Such a transition is analyzed by the dominant imagery in the esoteric milieu of his time, a perspective that offers an important analytical material for understanding the structural dynamics that guide the institutionalization of Gnosticism in Latin America and the specifics that guide their reversing relations with the social universe in which they are inserted.
O presente trabalho tem o prop?sito de analisar a obra do esoterista colombiano Samael Aun Weor ? luz do conceito de seculariza??o do esoterismo do historiador Wouter Hanegraaff, que integra um importante debate, no campo da Hist?ria Cultural, que analisa as rela??es reversivas e as influ?ncias m?tuas que pautam, de um lado, a constru??o da moderna cultura ocidental e seus paradigmas de racionalidade e ci?ncia emp?rica, e do outro a constitui??o de uma tradi??o esot?rica que busca harmonizar estes paradigmas com uma concep??o fortemente encantada do universo, e dos m?tuos processos de apropria??o/reinterpreta??o envolvidos. Esse debate tamb?m dialoga com uma discuss?o mais espec?fica ao campo da Ci?ncia das Religi?es, que busca compreender as transforma??es que ocorrem no campo religioso ocidental frente ? nova sociedade secularizada. Nesse sentido, nosso trabalho busca contribuir com o debate oferecendo uma perspectiva destes processos a partir da periferia do ocidente , a Am?rica Latina, buscando identificar em que medida essas din?micas s?o reproduzidas no Novo Continente, e o que elas possuem de espec?fico. Com esse prop?sito, tomando-se a obra de Samael Aun Weor como estudo de caso, conduziu-se uma contextualiza??o hist?rica de longa dura??o, inserindo o autor no processo mais geral de constitui??o do moderno esoterismo ocidental, e de maneira mais espec?fica no processo de constitui??o de um campo de espiritualidades esot?ricas na Col?mbia. A partir de uma an?lise hist?rico-comparativa da evolu??o de sua obra, de sua institucionaliza??o e de suas pr?ticas, que leva em conta contribui??es conceituais e metodol?gicas da Escola Italiana de Hist?ria das Religi?es, nosso trabalho destaca a transi??o doutrin?ria que o autor opera em sua obra, deslocando-se do Rosacrucianismo em dire??o ?s concep??es de um Esoterismo Psicol?gico do esoterista russo Gurdjieff. Essa transi??o ? analisada ? luz do imagin?rio dominante no milieu esot?rico de sua ?poca, perspectiva que oferece um importante material anal?tico para a compreens?o das din?micas estruturais que norteiam a institucionaliza??o do gnosticismo na Am?rica Latina e das especificidades que definem suas rela??es reversivas com o universo social em que est?o inseridas.

Having spent over 20 years under house arrest fighting for democracy in Myanmar, Aung San Suu Kyi has been a bastion for peace for decades. She has received many international awards, including the Nobel Peace Prize in 1991, which she accepted in person in 2012. The plight of the Rohingya, a Muslim minority in Myanmar, has marred Suu Kyi’s reputation as a bastion of peace, leading to calls for her to lose her Peace Prize. Why is it that Suu Kyi’s image as the future of peace so different from reality? That question is what this research attempts to answer. Through a rhetorical analysis of Suu Kyi’s Nobel lecture and the media coverage that followed it, the impact of the use of tropes becomes evident. Metonymy, synecdoche, and narrative emerge in both the lecture and media coverage. Suu Kyi’s use of tropes heavily influences public perception of her.

La croissance coherente en couches minces d'un materiau presentant un desaccord de parametre de maille avec le substrat sur lequel il est depose entraine des deformations du reseau cristallin qui sont a l'origine de nombreuses modifications thermodynamiques et structurales. La presente etude concerne l'effet des contraintes epitaxiales sur la stabilite d'alliages metalliques a separation de phases, en particulier le systeme auni qui presente une forte difference de taille (14%). La premiere partie est consacree a la modelisation thermodynamique des equilibres de phases coherents. Une extension de la theorie de cahn de la decomposition spinodale aux systemes epitaxies et a fort effet de taille a ete developpee. Les diagrammes d'equilibre de phases du systeme auni a l'etat massif et sous contrainte epitaxiale ont ete calculees a partir de la methode variationnelle des amas (cvm) limitee aux tetraedres. Pour de fortes deformations epitaxiales, une structure quadratique ordonnee de type l1#0 est stabilise pour des compositions proches de 50%. La deuxieme partie porte sur l'etude experimentale de couches minces d'alliages auni elabores par epitaxie par jets moleculaires (ejm) et sur leur evolution structurale au cours de traitements thermiques. Nous avons obtenu des solutions solides auni metastables. Le parametre pertinent est la deformation residuelle dans les couches auni. Les observations en diffraction de rayons x (xrd) et microscopie electronique haute resolution (mehr) montrent qu'une structure modulee, de periode 3 a 4 monocouches (mc), se stabilise pour de fortes deformations epitaxiales (>2%) et pour des temperatures comprises entre 200c et 240c. Ces structures modulees sont obtenues a partir d'etats initiaux tres differents (alliages, multicouches et structures artificielles), ce qui conforte l'hypothese de la stabilisation sous contrainte d'un ordre a longue distance dans un alliage ayant une forte tendance a la demixtion en volume.

Les nanobâtonnets d’or sont des particules plasmoniques présentant des propriétés optiques intéressantes. En particulier, la résonance plasmonique de surface localisée (LSPR) sensible à l’environnement local des particules, permet leur utilisation comme transducteurs de phénomènes d’interactions moléculaires. Cette propriété fait des nanobâtonnets d’or des nanostructures de choix pour la conception de biocapteurs LSPR. Dans cette thèse, nous proposons d’améliorer l’efficacité globale de ces biocapteurs en enrobant ces nanoparticules par une fine coquille de silice. Les conditions de synthèse permettant l’enrobage de nanobâtonnets par une coquille de silice homogène, d’épaisseur et de porosité contrôlée ont été réexaminées et des suspensions stables ont été obtenues tout en préservant les propriétés optiques du coeur d’or. Différentes chimies de surface ont été étudiées permettant l’immobilisation de biorécepteurs IgG, et les nanosondes formées ont permis la détection en solution d’une cible modèle : un IgG de lapin, avec une limite de détection de l’ordre du pM. La possibilité d’utiliser ces nanostructures coeur-coquille comme agents dopant pour la détection in vitro de biomarqueurs cellulaires par microscopie infrarouge est ensuite envisagée. Des résultats préliminaires concernant la caractérisation et fonctionnalisation de ces particules par des biorécepteurs IgG et une sonde moléculaire infrarouge sont présentés
Gold nanorods are plasmonic nanoparticles with interesting optical properties. In particular, the localized surface plasmon resonance (LSPR), sensitive to the local environment of the particles, allows their use as transducers of molecular interaction phenomena. This property makes those nanostructures of interest for the design of LSPR biosensors. In this thesis, we propose to improve the overall efficiency of these biosensors by coating these nanoparticles with a thin silica shell. The synthesis conditions allowing the coating of gold nanorods by a homogeneous silica shell of controlled thickness and porosity have been re-examined and stable suspensions have been obtained while preserving the optical properties of the gold core. Different surface chemistries were studied for the immobilization of IgG bioreceptors and the formed nanoprobes allowed the detection in solution of a model target : a rabbit IgG, with a detection limit in the pM range. The possibility of using these core-shell nanostructures as doping agents for the in vitro detection of cellular biomarkers by infrared microscopy is then considered. Preliminary results regarding the characterization and functionalization of these particles by IgG bioreceptors and an infrared molecular probe are presented

Dans ce travail, nous avons utilise la microscopie electronique in-situ et ex-situ afin d'analyser l'evolution structurale de couches minces metalliques auni sous traitement thermique. Le systeme auni est en effet un excellent modele pour la comprehension des phenomenes gouvernant les systemes a tres forts desaccords parametriques (15%). Les couches minces sont elaborees a temperature ambiante par epitaxie par jets moleculaires, leur direction de croissance etant selon l'axe 001. Elles sont de deux types : soit le ni est depose pur sur au001, soit les deux especes au et ni sont codeposees sur au001. Dans les deux cas, il y a formation d'un alliage auni en couches minces, contraint par le substrat d'or. L'etude par mehr couplee a la simulation d'images a permis de mettre en evidence la formation sous traitement thermique d'une phase anisotrope et partiellement ordonnee dans l'alliage au 1 cni c. Cette phase apparait quel que soit le type de depot, et pour des concentrations c telles que 0. 28