No abstract provided. / Thesis / Doctor of Philosophy (PhD) / Scope and contents: The principal aim of the present investigation is to extend our knowledge of the merits and demerits of the mass spectroscopic method of solid analysis. This dissertation provides information concerning relative ionization efficiencies for several elements and factors which effect these efficiencies. Secondary purposes of this work are 1) to make an independent determination of the temperature of the vacuum spark, 2) to resolve the current discrepancy concerning the value of the C3+/C2+ ratio from graphite electrodes in a spark and, finally, 3) to provide an accurate value for the Ni58/Ni60 abundance ratio.

Mechanical ventilation has been a major therapy used by physicians in support of surgery as well as for treating patients with reduced lung function. Despite its many positive outcomes and ability to maintain life, in many cases, it has also led to increased injury of the lungs, further exacerbating the diseased state. Numerous studies have investigated the effects of long term ventilation with respect to lungs, however, the connection between the global deformation of the whole organ and the strains reaching the alveolar walls remains unclear. The walls of lung alveoli also called the alveolar septum are characterized as a multilayer heterogeneous biological tissue. In cases where damage to this parenchymal structure insist, alveolar overdistension occurs. Therefore, damage is most profound at the alveolar level and the deformation as a result of such mechanical forces must be investigated thoroughly. This study investigates a three-dimensional lung alveolar model from generations 22 (alveolar ducts) through 24 (alveoli sacs) in order to estimate the strain/stress levels under mechanical ventilation conditions. Additionally, a multilayer alveolar tissue model was generated to investigate localized damage at the alveolar wall. Using ANSYS, a commercial finite element software package, a fluid-structure interaction analysis (FSI) was performed on both models. Various cases were simulated that included a normal healthy lung, normal lung with structural changes to model disease and normal lung with mechanical property changes to model aging. In the alveolar tissue analysis, strains obtained from the aged lung alveolar analysis were applied as a boundary condition and used to obtain the mechanical forces exerted as a result. This work seeks to give both a qualitative and quantitative description of the stress/strain fields exerted at the alveolar region of the lungs. Regions of stress/strain concentration will be identified in order to gain perspective on where excess damage may occur. Such damage can lead to overdistension and possible collapse of a single alveolus. Furthermore, such regions of intensified stress/strain are translated to the cellular level and offset a signaling cascade. Hence, this work will provide distributions of mechanical forces across alveolar and tissue models as well as significant quantifications of damaging stresses and strains.

A cultura da cana-de-açúcar no Brasil é uma das atividades mais relevantes na agroindústria nacional devido ao alto potencial de produção e elevada importância econômica de seus subprodutos como e.g. açúcar e etanol. Embora o Si não seja considerado um elemento essencial, a adubação silicatada tem proporcionado aumentos apreciáveis na produtividade da cana-de-açúcar e na resistência a algumas pragas e doenças. Ainda não existem métodos bem estabelecidos para a determinação de Si em material vegetal visando à diagnose foliar. O objetivo deste trabalho foi desenvolver um método para determinação de Si em pastilhas de folhas de cana-de-açúcar por espectrometria de emissão óptica com plasma induzido por laser (LIBS). O arranjo experimental foi composto por um laser pulsado de Nd:YAG a 1064 nm (pulsos de 5 ns, 360 mJ, 10 Hz) e os sinais de emissão foram coletados por um telescópio acoplado por fibra óptica ao espectrômetro Echelle com detector ICCD. Amostras laboratoriais consistiram de pastilhas preparadas com folhas de cana-de-açúcar moídas criogenicamente por 40 min. Melhores resultados foram obtidos quando a linha de emissão Si I 212,412 nm foi selecionada e os parâmetros instrumentais foram ajustados em 25 pulsos acumulados, 50 J cm-2, diâmetro de focalização de 750 \'mü\'m, 2,0 \'mü\'s de atraso e 4,5 \'mü\'s de integração. Os resultados obtidos por LIBS na análise de pastilhas de 20 amostras laboratoriais foram comparados com os obtidos por espectrometria de emissão óptica com plasma acoplado indutivamente (ICP OES) após decomposição alcalina e por espectrometria de micro-fluorescência de raio-X por energia dispersiva (\'mü\'ED-XRF) após análise direta das pastilhas. Aplicando-se o teste t de Student pareado, não foram verificadas diferenças significativas ao nível de 95% de confiança nas determinações de Si por LIBS, ICP OES e \'mü\'ED-XRF. Os resultados obtidos nesta tese indicam a viabilidade de LIBS para determinação direta de Si em pastilhas de folhas de cana-de-açúcar e abrem uma expectativa para futuras explorações de LIBS em análises em campo / The high production of sugarcane and its subproducts (e.g. sugar and ethanol fuel) make this crop one of the most important for the Brazilian agro-industrial economy. Although Si is not considered an essential element, the Si-based fertilizers have provided considerable improvement in productivity of sugarcane and resistance to some pests and diseases. At moment, there are no well-established methods for the determination of Si in plant materials aiming at nutritional diagnosis. The aim of this work was to develop a method for Si determination in pellets of sugarcane leaves by laser-induced breakdown spectroscopy (LIBS). The experimental setup was designed by using a Q-switched Nd:YAG laser (5 ns, 360 mJ, 10 Hz, \'lâmbda\' = 1064 nm) and the emission signals were collected by lenses into an optical fiber coupled to an Echelle spectrometer equipped with an ICCD. Pellets prepared from cryogenically ground sugarcane leaves were used as laboratory samples. Best results were obtained when the Si I 212.412 nm emission line was selected and the instrumental parameters were adjusted at 25 laser shots, 50 J cm-2, 750 \'mü\'m laser spot size, 2.0 \'mü\'s delay time and 4.5 \'mü\'s integration time gate. The results obtained by LIBS in the analysis of pellets of 20 laboratory samples were compared with those from inductively coupled plasma optical emission spectrometry (ICP OES) after alkaline digestion and by microenergy dispersive X-ray fluorescence (\'mü\'ED-XRF) after direct analysis of pellets. By applying a paired t-test at 95 % confidence level, there was no significant difference in the Si determination by LIBS, ICP OES and \'mü\'ED-XRF. The findings of this thesis indicate the feasibility of LIBS for the direct determination of Si in pellets of sugarcane leaves and open expectations for future investigations of LIBS for field analysis

A cultura da cana-de-açúcar no Brasil é uma das atividades mais relevantes na agroindústria nacional devido ao alto potencial de produção e elevada importância econômica de seus subprodutos como e.g. açúcar e etanol. Embora o Si não seja considerado um elemento essencial, a adubação silicatada tem proporcionado aumentos apreciáveis na produtividade da cana-de-açúcar e na resistência a algumas pragas e doenças. Ainda não existem métodos bem estabelecidos para a determinação de Si em material vegetal visando à diagnose foliar. O objetivo deste trabalho foi desenvolver um método para determinação de Si em pastilhas de folhas de cana-de-açúcar por espectrometria de emissão óptica com plasma induzido por laser (LIBS). O arranjo experimental foi composto por um laser pulsado de Nd:YAG a 1064 nm (pulsos de 5 ns, 360 mJ, 10 Hz) e os sinais de emissão foram coletados por um telescópio acoplado por fibra óptica ao espectrômetro Echelle com detector ICCD. Amostras laboratoriais consistiram de pastilhas preparadas com folhas de cana-de-açúcar moídas criogenicamente por 40 min. Melhores resultados foram obtidos quando a linha de emissão Si I 212,412 nm foi selecionada e os parâmetros instrumentais foram ajustados em 25 pulsos acumulados, 50 J cm-2, diâmetro de focalização de 750 \'mü\'m, 2,0 \'mü\'s de atraso e 4,5 \'mü\'s de integração. Os resultados obtidos por LIBS na análise de pastilhas de 20 amostras laboratoriais foram comparados com os obtidos por espectrometria de emissão óptica com plasma acoplado indutivamente (ICP OES) após decomposição alcalina e por espectrometria de micro-fluorescência de raio-X por energia dispersiva (\'mü\'ED-XRF) após análise direta das pastilhas. Aplicando-se o teste t de Student pareado, não foram verificadas diferenças significativas ao nível de 95% de confiança nas determinações de Si por LIBS, ICP OES e \'mü\'ED-XRF. Os resultados obtidos nesta tese indicam a viabilidade de LIBS para determinação direta de Si em pastilhas de folhas de cana-de-açúcar e abrem uma expectativa para futuras explorações de LIBS em análises em campo / The high production of sugarcane and its subproducts (e.g. sugar and ethanol fuel) make this crop one of the most important for the Brazilian agro-industrial economy. Although Si is not considered an essential element, the Si-based fertilizers have provided considerable improvement in productivity of sugarcane and resistance to some pests and diseases. At moment, there are no well-established methods for the determination of Si in plant materials aiming at nutritional diagnosis. The aim of this work was to develop a method for Si determination in pellets of sugarcane leaves by laser-induced breakdown spectroscopy (LIBS). The experimental setup was designed by using a Q-switched Nd:YAG laser (5 ns, 360 mJ, 10 Hz, \'lâmbda\' = 1064 nm) and the emission signals were collected by lenses into an optical fiber coupled to an Echelle spectrometer equipped with an ICCD. Pellets prepared from cryogenically ground sugarcane leaves were used as laboratory samples. Best results were obtained when the Si I 212.412 nm emission line was selected and the instrumental parameters were adjusted at 25 laser shots, 50 J cm-2, 750 \'mü\'m laser spot size, 2.0 \'mü\'s delay time and 4.5 \'mü\'s integration time gate. The results obtained by LIBS in the analysis of pellets of 20 laboratory samples were compared with those from inductively coupled plasma optical emission spectrometry (ICP OES) after alkaline digestion and by microenergy dispersive X-ray fluorescence (\'mü\'ED-XRF) after direct analysis of pellets. By applying a paired t-test at 95 % confidence level, there was no significant difference in the Si determination by LIBS, ICP OES and \'mü\'ED-XRF. The findings of this thesis indicate the feasibility of LIBS for the direct determination of Si in pellets of sugarcane leaves and open expectations for future investigations of LIBS for field analysis