Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-05-03T17:33:41Z No. of bitstreams: 1 tatianabittencourtvillelaneves.pdf: 6602146 bytes, checksum: 41b92396bb426d51f4362a8117b77115 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-05-13T13:39:32Z (GMT) No. of bitstreams: 1 tatianabittencourtvillelaneves.pdf: 6602146 bytes, checksum: 41b92396bb426d51f4362a8117b77115 (MD5) / Made available in DSpace on 2017-05-13T13:39:32Z (GMT). No. of bitstreams: 1 tatianabittencourtvillelaneves.pdf: 6602146 bytes, checksum: 41b92396bb426d51f4362a8117b77115 (MD5) Previous issue date: 2014-03-19 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Os estudos visando o entendimento da interface metal/molécula levaram à descoberta do efeito SERS. Esse efeito foi descoberto casualmente e pode aumentar a intensidade Raman de espécies adsorvidas ca. 106 vezes. O desempenho SERS depende de alguns parâmetros, como: tamanho e forma das nanoestruturas metálicas e natureza do metal. Para evitar agregação e deposição das nanopartículas, uma nova metodologia é proposta nessa dissertação: recobrir a NPs com materiais inertes, como SiO2 e MnO2. A esta metodologia dá-se o nome de SHINERS. Outra técnica que tem ganhado notoriedade devido às aplicações em sistemas biológicos é o efeito SEF. Para que o SEF seja observado é necessário um espaçamento entre o fluoróforo e as NPs, que também pode ser realizado pelo recobrimento com óxidos inertes, quando se utiliza a denominação SHINEF. O distanciamento da superfície provoca um decaimento do sinal; logo, as camadas devem ter alto controle da espessura para que os resultados sejam otimizados. Para o fim de obter desempenho otimizado SHINERS e SHINEF, nessa dissertação foram preparadas NPs de Au e Ag recobertas por camadas ultrafinas de SiO2 e MnO2 de diferentes espessuras. Foi possível caracterizar o recobrimento das NPs metálicas pelos óxidos utilizando TEM. Verificou-se o recobrimento com camadas de 2-6 nm de espessura. O recobrimento das NPs causa um deslocamento para maior comprimento de onda das bandas LSPR das nanopartículas sem recobrimento quando comparadas às NPs com recobrimento, atribuído à mudança do índice de refração local sobre as NPs. Os nanomateriais resultantes tiveram seu desempenho estudado utilizando o corante IR820, que teve seu espectro vibracional atribuído nessa dissertação, como moléculaprova para os dois efeitos de intensificação. Verificou-se uma diminuição da intensidade SHINERS com o aumento da espessura do recobrimento em relação à intensidade SERS, atribuída ao aumento da distância entre adsorbato e superfície das NPs. Para o efeito SHINEF, verificou-se que ocorre uma intensificação apreciável da emissão de fluorescência quando o corante IR-820 na presença das NPs recobertas foi excitado em 785 nm. Os resultados obtidos são promissores para a aplicação das metodologias de preparação de NPs metálicas recobertas como substratos de alto desempenho para as técnicas SHINERS e SHINEF / The studies to aimed the interface metal/molecule resulted in the discovery of the SERS effect. The SERS effect was discovered accidentally and can increase the intensity of scattering adsorbed species ca. 106 times. The SERS performance depends on several parameters such as: size, shape and nature of the metallic nanostructures. To avoid aggregation and deposition of nanoparticles, a new methodology is proposed in this dissertation: coat the NPs with inert materials like SiO2 and MnO2. The cited methodology receives the name of SHINERS. Another technique that has been receiving great notoriety due to applications in biological systems is the SEF effect. A specific spacing between the fluorophore and NP is necessary for the SEF effect to occur and it can be accomplished by coating with inert oxides, which takes the denomination of SHINEF. The distance from the surface causes a decay of the signal, therefore, the layers are supposed to be ultrathin with precise thickness control for optimized results. In order to obtain a good SHINERS and SHINEF performance, in this dissertation, Ag and AuNPs coated with ultrafine layers of SiO2 and MnO2 to different thicknesses were prepared. It had been possible to characterize the coating of metal oxide NPs by using TEM. It has been determined covering oxide layer thickness of 2-6 nm. The coating of NPs causes a shift of LSPR bands for higher wavelength of the coating nanoparticles compared to uncoated NPs, assigned to increasing changes in the local refractive index of the NPs with the oxide layer thickness. The resulting nanomaterials performances for SHINERS and SEF effect were studied using IR-820 dye, which had its vibrational spectrum assigned. There has been observed a decrease in the SHINERS intensity with the increasing thickness of the coating in relation to the SERS intensity attributed to the increasing distance of the adsorbate from the NPs surface. For SHINEF effect, it has been found that a significant enhancement of fluorescence emission occurs when IR- 820 dye in the presence of the coated NPs excited at 785 nm. The preparative methodologies proposed in this dissertation are promising for the application of coated Ag and Au NPs as substrates for high performance SHINERS and SHINEF techniques.

Made available in DSpace on 2014-06-12T23:16:08Z (GMT). No. of bitstreams: 2 arquivo943_1.pdf: 1281013 bytes, checksum: ddc6b54734ee04c82c863ce15355d1d6 (MD5) license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) Previous issue date: 2010 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / O biodiesel, combustível originado de óleos vegetais ou gorduras animais, vem se consolidando como fonte de energia alternativa em substituição ao diesel mineral. Este trabalho reporta o desenvolvimento de métodos analíticos para monitorar a qualidade do biodiesel e de suas misturas com diesel mineral. As propriedades estudadas para o biodiesel puro (B100) foram estabilidade oxidativa, índice de acidez e teor de água. Para as misturas, as propriedades determinadas foram massa específica, temperaturas de destilação (T50% e T85%) e teor de enxofre. Em ambos os casos, foram desenvolvidos modelos de calibração multivariada, usando dados obtidos por espectroscopia na região do infravermelho (IR). As técnicas de regressão por mínimos quadrados parciais (PLS) e a regressão linear múltipla (MLR) foram usadas para a modelagem. No desenvolvimento dos modelos para o controle de qualidade do B100, três técnicas de seleção de variáveis foram avaliadas: o algoritmo das projeções sucessivas (APS) associada à MLR, a regressão por mínimos quadrados parciais por intervalos (iPLS) e o Jack Knifing (PLS). Os resultados obtidos para misturas mostraram que os modelos globais foram adequados para previsão das propriedades tanto das misturas diesel-biodiesel quanto para o diesel puro. Os modelos apresentaram boas correlações que variaram de 0,74 a 0,98, com erros médios quadráticos de previsão (RMSEP) menores que a reprodutibilidade dos métodos de referência, exceto para a massa específica no infravermelho médio (MIR). Em relação ao B100, correlações que variaram entre 0,83 a 0,99 foram obtidas para os modelos desenvolvidos. Os RMSEPs apresentaram-se menores que a reprodutibilidade dos métodos oficiais. De uma forma geral, a espectroscopia na região do infravermelho em ambas as regiões NIR e MIR, combinada com a calibração multivariada mostrou-se eficiente na previsão das propriedades, tanto da mistura diesel-biodiesel, quanto do B100. Foi proposto ainda, empregar um sistema de análise por injeção em fluxo (FIA), usando detecção espectrofotométrica, para determinar fósforo em B100 com amostras digeridas. Uma avaliação sobre os procedimentos de digestão de amostras, em bloco digestor e forno de micro-ondas com cavidade, foi realizada, sendo o procedimento usando bloco digestor escolhido para digerir as amostras que foram usadas no método do FIA-SD. O procedimento com bloco digestor foi escolhido por apresentar menor acidez (2,2 mol L-1) e carbono residual (0,16%) comparando-se ao procedimento usando micro-ondas com cavidade. Para Validar o método, testes de recuperação foram realizados e os resultados mostraram valores entre 98 a 114,8%. O Limite de detecção (LD) foi de 1,4 mg Kg-1 e o Limite de Quantificação (LQ) de 4,6 mg Kg-1. As concentrações de fósforo em biodiesel apresentaram-se semelhantes às encontradas empregando a Espectrometria de Emissão Óptica com Plasma Indutivamente Acoplado (ICP OES) usando amostras digeridas e também amostras dissolvidas em querosene. A espectroscopia IR e o sistema de análise em fluxo (FIA) acoplado a técnica UV-VIS apresentam-se vantajosos, quando comparados aos métodos oficiais, pois possuem custos reduzidos e trabalham com uma quantidade mínima de amostras. Além disso, a espectroscopia IR e o FIA são rápidos e geram pouco resíduo

This thesis describes the design and implementation of a prototype LLVM compiler backend, x86-64p, that compiles code written for a DSP architecture, FADER, into executables for the x86-64 architecture. The prototype takes LLVM IR generated for the FADER architecture and compiles x86-64 executables that emulate the properties of the DSP architecture, e.g. the multiple address spaces, the big-endianness and the support for fixed-point arithmetics. The backend is compared to a previous solution, C-Emu, that converts the DSP code to normal C code that is compiled using a normal x86-64 compiler. The two solutions are compared in terms of their correctness, debuggability and performance. The created prototype handles code containing low-level architectural assumptions better than C-Emu. However, the added emulation reduces the debuggability and performance of the generated executables. We have measured a runtime overhead of up to a factor of two compared to C-Emu. We also present some possible solutions for these issues.

Notre étude porte sur l’identification des mécanismes de sorption des ions (poly)molybdate et (poly)tungstate sur différents substrats : les hydroxydes doubles lamellaires (LDH) et les (hydr)oxydes de fer (hématite, goethite, akaganéite et lépidocrocite). La spectroscopie infrarouge en réflexion totale atténuée (ATR-FTIR) est l’une des rares méthodes à permettre l’analyse in situ et l’observation des phénomènes de sorption en temps réel directement sur les surfaces. Il est ainsi possible d’obtenir des informations sur la spéciation de surface et de connaitre la géométrie des espèces adsorbées (monodentate, bidentate, polymère, …). Nous avons ainsi pu déterminer la différence de réactivité entre les différents matériaux lors de la sorption. Un échange d’ion (sphère externe) impliquant les anions polyoxométalate a lieu avec les hydroxydes doubles lamellaires tandis que des complexes de sphère interne ont été observés sur les oxydes de fer, avec des géométries différentes selon la structure de surface du solide. Cette étude expérimentale a été complétée par différents calculs de spectres vibrationnels, réalisé par DFT ab initio, qui ont confirmé la géométrie de surface des espèces adsorbées observées par infra-rouge. / Our study focuses on the identification of (poly)molybdate and (poly)tungstate ions sorption mechanisms on various substrates : layered double hydroxides (LDH) and iron (hydr)oxide (hematite, goethite, akaganeite and lepidocrocite). Attenuated total reflection infrared spectroscopy (ATR-FTIR) is one of the few methods that allow in situ analysis and observation of sorption mechanisms in real time directly on surfaces. Thus, information on surface speciation and the geometry of the sorbed species (monodentate, bidentate, polyanion, …) can be obtained. We were able to determine the reactivity differences between the materials during the sorption. Ion exchange (outer sphere) with polyoxometalate takes place within layered double hydroxides, while inner sphere complexes were observed on iron (hydr)oxides, with different geometries according to the structure of the solid surface. The experimental study was supported by vibrational calculations by ab initio DFT, which confirmed the surface geometry of the absorbed species observed by infrared spectroscopy.

Magister Artium (Sport, Recreation and Exercise Science) - MA(SRES) / Insulin resistance has shown to be a precursor to a number of lifestylerelated chronic diseases and abnormalities in adults and is affected by a number of factors including genetics, age, physical activity and acute exercise, diet, obesity, body fat distribution and medication. Physical activity has shown to have marked effects on improving sensitivity to insulin though various physiological mechanisms, and numerous correlation studies have identified a relationship between these two variables, suggesting the beneficial role of exercise on insulin resistance. This study aimed to identify a relationship between current levels of physical activity, physical fitness and insulin resistance in adults between the ages of 35 and 65 years of age residing in a northern suburb community in Cape Town. A total of 186 volunteers participated in this study ranging from healthy individuals to those with diagnosed chronic conditions. Insulin resistance (determined by the homeostasis model assessment of insulin resistance), physical activity (measured by the Global Physical Activity Questionnaire) and five health-related physical fitness tests were measured. The five components included body composition, determined by body mass index and waist circumference, the 3-minute cardiorespiratory step test, the handgrip muscle strength test, one-minute crunches for muscle endurance and the sit-and-reach flexibility test. Spearman correlation was used to identify the relationships between the homeostasis model assessment of insulin resistance, age, body composition and physical activity and fitness.Results showed that body mass index and waist circumference were the only two variables which produced significant correlations with the homeostasis model assessment of insulin resistance (p < 0.019). No physical activity or fitness data produced significant scores with the homeostasis model assessment of insulin resistance. Body mass index in men was the only significant predictor of HOMA-IR and explained 37% of the variance in insulin resistance, whereas in women, only waist circumference was related to HOMA-IR, but explained less than 16% of the variance. Associations between reported MET-minutes from the Global Physical Activity Questionnaire and the four fitness tests indicated significance with handgrip strength (&rho; = 0.17; p =0.039), one-minute crunches (&rho; = 0.18; p = 0.024) and sit-and-reach flexibility (&rho; = 0.17; 0.034). This study has shown that body composition is an important component in influencing insulin resistance therefore physical activity interventions should be targeted at increasing physical activity levels and reducing body weight. / South Africa

Processing of Si in the semiconductor and solar cell industry has been dominated by the Diode Pumped Solid State (DPSS) Ultraviolet (UV) laser. Recent advances in laser source technology have produced fibre lasers with Master Oscillator Power Amplifier (MOPA) architectures that offer high repetition rates, high operational efficiencies, and pulse modulation controls exceeding those of typical Q-switched DPSS lasers. The aim of this research is to investigate 1 μm fibre laser machining of Si with a view to identifying the influential laser parameters for optimum processing of high quality, high efficiency micro drilling and surface texturing applications. A secondary aim is to develop a greater understanding of the laser material interactions and material removal mechanism when using fast rise-time nanosecond laser pulse envelopes. The IR fibre laser was able to perform percussion drilling and single pulse machining on the polished Si over a range of intensities up to 1.22 GW/cm2. With the optimum parameters, the micro-sized holes generated by the IR laser have a well defined edge, no heavy recast and no cracks. With a pulse shape of fast rise time (<7.5 ns for a 10-90% rise in signal), a high front peak power zone (approaching 14 kW) and an energetic long tail (40-180 ns), the absorption coefficient of Si at IR wavelength increased dramatically with time and temperature due to the fact that the liquid Si has a metal like absorption behavior. As a result, Si was quickly melted and the rest of pulse energy was able to remove the liquid Si effectively. The machining process left a limited amount of resolidified melt droplets and vapor condensates, which could be washed off ultrasonically. The drilling process was energy efficient when melt expulsion dominated the machining mechanism (0.08-0.2 mJ pulse energy depending on the pulse durations). The low energy pulse (~0.2 mJ) can achieve similar depth as the high energy pulse (~0.7 mJ), so high repetition rates of 100 kHz can be used to instead of 25 kHz, resulted in high processing speed. In addition, by comparing the single pulse machining with the state of the art UV laser, the IR fibre laser machined deeper features and better surface finish in the pulse energy region of >0.07 mJ. With the pulse shaping capability, the material properties can be varied and the wavelength factor can be minimized. The results suggest that applications like microvia drilling can now be carried out with the more flexible and low cost IR fibre laser. The increased repetition rates of fibre laser can increase production speed to satisfy the needs of drilling ~10 thousands holes per second, required by the modern semiconductor and solar cell production. The shortened optical penetration length of 1 μm wavelength laser on Si with increasing temperature and sufficient thermal diffusion length resulted from the asymmetrical fibre laser pulse and the dynamic properties of Si produced a thick liquid layer. A one-dimensional heat conduction model based on the surface heating source predicted that this superheated liquid layer was able to stay above 4706 K (0.905 times the thermal critical temperature 5200 K of Si) for longer than 70 ns to induce explosive boiling. This proposed material removal mechanism was also confirmed by the shadowgraph images, showing particulates ejection lasting up to ten microseconds after the laser pulse. The estimated hole depth based on the explosive boiling alone were different from the measured ones at varying peak power densities (<1.22 GW/cm2) but fixed pulse duration (200 ns), since Si was removed by a mixture of mechanisms. With varying pulse durations (40-200 ns) but fixed peak power density (~0.63 GW/cm2), the estimated depth based on the explosive boiling was in close agreement with the measured ones (6% difference on average). The SEM images at this power density showed a micron- /submicron-sized debris field, which was also observed with the explosive boiling in the past. Although the improved quality of Si machining was demonstrated with the 1 μm MOPA based fibre laser, the setup of this system was only applicable to surface texturing, blind holes and through holes of less than 100 μm in depth. Further research is required to demonstrate the capability of more energetic pulse with higher peak power and large pulse duration range to explore more machining options.

No description available.

The thesis deals with one of the international relations theories - realism. It examines the presence of realism in discussions about the German foreign policy on the ground of the parliament of Germany. Key concepts of realism and liberalism are defined in the introduction. The aim is to evaluate the presence of the realistic rhethoric used by particular political parties. The situation is described on three cases of the German foreign policy - discussions about China, Georgia and Turkey. The thesis is based on stenographic protocols of parliamentary debates covering the proper period.

Metabolomics approaches have recently been used to understand the complex molecular interactions of biological systems. One popular area in which these methods are being developed is to understand the biochemical changes during abiotic and biotic stresses; for example, how a cell may respond to a drug. Since metabolites are the end products of gene expression, these can be used to indicate the result of the activities and interaction of the cell or organism with its environment. The investigation of the level and compositional changes of metabolites against metabolic stresses such as chemotherapeutic treatment (drug exposure) are required to understand more fully abiotic perturbation to biological systems. The aim of this project was to understand the metabolic effect that the anti-viral drugs indinavir and lopinavir (currently used by HIV patients) have on HPV-related cervical cancer cell lines by measuring changes in metabolism using a wide range of analytical techniques; including Fourier transform infrared (FT-IR) and Raman spectroscopies, and gas and liquid chromatography-mass spectrometry (GC and LC-MS). The analyses and interpretation of the large volumes of complex multidimensional data generated by metabolomics approaches were performed with a combination of multivariate data analysis techniques such as principal components analysis (PCA) and canonical variates analysis (CVA), as well as univariate approaches such as N-Way analysis of variance (ANOVA). By combining biochemical imaging, metabolite fingerprinting and footprinting, and metabolite profiling, with multi- and uni-variate analyses, the actions and effects of the anti-viral drugs were investigated. FT-IR spectroscopy was initially used to generate global biochemical finger- and foot-prints, and Raman spectroscopy was employed to investigate intracellular distribution of metabolites, and other cellular species, as well as the localisation of drug molecules within cells. FT-IR spectroscopy ascertained that the intra- and extra-cellular metabolomes were being directly influenced in a fashion that correlated with increasing anti-viral dosing; these effects were phenotypic rather than measurements of the drug level. Raman imaging spectroscopy indicated that the indinavir but not lopinavir was being compartmentalised within the cell nucleus, but only in HPV early protein 6 (E6) expressing cells. This observation was further confirmed by fractionation of cell samples into nuclear and cytoplasmic fractions and assessing the indinavir concentrations via LC-MS. Finally, LC-MS and GC-MS metabolite profiling were employed to investigate changes in the intracellular metabolome in response to the anti-viral compounds across a range of physiologically relevant concentrations and in the presence and absence of the E6 oncoprotein. General effects of both anti-viral compounds included the regulation of metabolites such as glutathione, octenedionoic and octadecenoic acids, which may be involved in stress related responses, reduced levels of sugars and sugar-phosphates indicating a potential arrest of glycolysis, and reduced levels of malic acid indicating potential decreased flux into the TCA cycle; all indicating that central metabolism was being reduced. Finally, LC-MS based quantification indicated that in the presence of E6, lopinavir was actively removed from the cell, whereas the indinavir intracellular concentration increased concomitantly with the level of dosing. These investigations have revealed that metabolomics approaches are an apt tool for the study of anti-viral effects within cell cultures, but improvements need to be made with respect to the major limitation of metabolite identification.

Democracies are argued to be imperative for the advancement of LGBTQ human rights. In the last two decades, however, the picture regarding LGBTQ rights has been extremely contradictory with countries adopting ‘LGBTQ friendly’ policies such as same-sex marriage or adoption while other democratic nation-states have constrained or not developed the rights of sexual minorities. Flaws in the democratic political system and the international human right regime are believed to be responsible for that. The aim of this paper is to investigate the significance of democracy in relation to sexual and gender minority human rights. This is done by (a) framing the study through previous studies related to the topic, the use of Queer IR and democratic theory, and (b) conducting a small-N comparison with content analysis where Brazil, Bulgaria and Namibia are analysed to answer the research question. Democracy is demonstrated to be a necessary factor in the process of LGBTQ right advancement, but not essential. Other factors are believed to influence the process, especially social movements and their effect in norm internalisation processes.