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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
521

Tecnologia Analítica em processo (PAT): método espectroscópico como alternativa ao método clássico para uniformidade de conteúdo e doseamento de lamivudina e zidovudina em comprimidos revestidos / Process Analytical Technology (PAT): spectroscopic method as an alternative to the classical method for content uniformity and quantification of lamivudine and zidovudine in tablets.

André Luís da Silva Novaes 12 August 2013 (has links)
A zidovudina, conhecida como AZT, é um inibidor da transcriptase reversa, enquanto que a lamivudina é um fármaco antirretroviral que atua na inibição da síntese de ácidos nucléicos. Estes são dois dos 21 fármacos componentes dos medicamentos distribuídas pelo Ministério da Saúde Brasileiro em programas de combate a Síndrome da imunodeficiência Adquirida (Acquired Immunodeficiency Syndrome - AIDS), configurando-se assim uma grande demanda de produção de medicamentos com estes fármacos. Programas de Tecnologia Analítica em Processo (Process Analytical techology - PAT), embasadas por avanços nos guias internacionais da Conferência Internacional sobre a Harmonização dos Requerimentos Técnicos para o Registro de Produtos Farmacêuticos para o uso Humano (International Conference on Harmonisation of Technical Requirements for Registration of Pharmaceuticals for Human Use - ICH) e pela agência norte-americana para a Administração de Alimentos e Medicamentos (Food and Drugs Administration - FDA), estão ganhando força como alternativas para aumentar a eficiência e a segurança na produção de medicamentos, tanto para aqueles já em processo produtivo como também para medicamentos em fase de desenvolvimento. Estes últimos são denominados desenvolvimento em programas de Qualidade por Design (QbD). Métodos de quantificação por espectroscopia (NIR, MID, RAMAM, entre outras) são reconhecidos como ferramentas para a PAT. Neste contexto propôs-se comparar objetivamente o método tradicional de quantificação destes dois fármacos frente a um método de quantificação desenvolvido utilizando-se a espectroscopia no infravermelho médio (MID). Prepararam-se assim 41 amostras de calibração e 23 amostras de validação, compostas por misturas de zidovudina, lamivudina e placebo (qs) em escala laboratorial, na faixa de 80 a 120% da concentração nominal de uma associação comercial dos dois fármacos. As concentrações de referência de todas as preparações foram determinadas empregando-se o método de referência por Cromatografia Líquida de Alta Eficiência (CLAE) da Farmacopeia Americana (United States Pharmacopeia - USP). Subsequentemente, obtiveram-se cinco espectros no infravermelho de cada uma das preparações, na faixa de 450 a 4000 cm-1. Os espectros foram então pré-processados e utilizados para a construção de um modelo de calibração multivariado por PLS (mínimo quadrados parciais), de acordo com a ASTM E1655-05. Adicionalmente, o método de CLAE foi transferido para um método de UPLC de acordo com o Capitulo Geral descrito no volume 37(3) do Fórum da USP (United States Pharmacopeia). O desempenho do método MID foi então comparado com o método tradicional, bem como com o novo método de quantificação por UPLC. Foram definidaLs assim regiões de confiança para embasar a utilização dos métodos desenvolvidos. O método de quantificação por MID apresentou uma grande variabilidade enquanto que o método por UPLC foi totalmente comparável com o método tradicional, reduzindo o tempo de corrida de 60 minutos para 12.55 minutos. / Zidovudine, also known as AZT is a reverse transcriptase inhibitor, whereas lamivudine is an antiretroviral drug that acts on the inhibition of nucleic acid synthesis. These are two of the 21 active ingredients components of medicines distributed by Brazilian Health Ministry in programs against the Acquired Immunodeficiency Syndrome (AIDS), becoming thus a great demand for production of these two drugs. Process Analytical Technology (PAT) programs, supported by advances in international guides from the International Conference on Harmonisation of Technical Requirements for Registration of Pharmaceuticals for Human Use (ICH) and by the FDA (Food and Drugs Administration), are gaining momentum as alternatives to increase efficiency and safety in the production of medicines, both for those medicines already in the production process as well as to those medicines under development. The latter are called Quality by Design (QbD) programs. Spectroscopy quantification methodologies methodologies (NIR, MID, Ramam, among others) are recognized as PAT tools. In this context it was proposed to compare objectively the traditional method for quantification of these two drugs against a quantification method developed using the MID (middle infrared spectroscopy). Thus 41 calibration and 23 validation samples, comprising of laboratorial scale mixtures of lamivudine, zidovudine and placebo (qs), were prepared in the range equivalent to 80 to 120% of the nominal concentration of the commercial tablets product. The concentrations of all calibration and validation samples were determined using the HPLC reference method of USP (United States Pharmacopeia). Subsequently, there were obtained five infrared spectra of each of the preparations in the range 450-4000 cm-1. The spectra were then pre-processed and used to build a multivariate calibration model for PLS (Partial Least Squares) according to ASTM E1655-05. Additionally, the HPLC method was transferred to a UPLC method according to General Chapter described in volume 37 (3) Forum USP (United States Pharmacopeia). The performance of the method MID was then compared with the traditional method and with the new method of quantification by UPLC. Confidence regions were built to support the use of the methods developed. The MID quantification method presented considerable variability, while the method the UPLC method was fully comparable to the traditional method. Another advantage of the UPLC method was the reduction of running time from 60 minutes to 12:55 minutes.
522

Estudo espectroscópico e eletroquímico da redução de íons perclorato sobre superfícies eletromodificadas de estanho / Study of spectroscopic and electrochemical reduction perchlorate ions on tin surfaces electromodified

Edson Barbosa de Sousa 23 November 2005 (has links)
Medidas eletroquímicas, incluindo cronoamperometria, voltametria cíclica, procedimentos eletroquímicos de envelhecimento de filmes superficiais, espectroscopia de absorção no infravermelho, espectroscopia Raman in situ e ex situ, incluindo o efeito SERS, foram empregados no estudo da redução eletroquímica de íons perclorato a cloreto sobre eletrodo de estanho. Solução de perclorato de sódio 0,5 mol L-1 foi utilizada como eletrólito. Observou-se que a concentração máxima de cloreto produzida em decorrência da redução de íons perclorato (5,0 x 10-5 mol L-1) ocorre na região de potenciais localizada no final da contribuição de corrente da dupla camada elétrica e início da região de desprendimento de hidrogênio. A concentração limite de cloreto é decorrente do estabelecimento de um equilíbrio entre os íons cloreto na solução e cloreto adsorvido que inativa os sítios na superfície, impedindo a continuidade do processo. Programas de perturbação de potencial visando a eletromodificação da superfície do estanho foram aplicados, com o objetivo de verificar a ocorrência de mudanças das propriedades eletrocatalíticas dessas superfícies. A influência das variáveis, velocidade da perturbação, tempo de duração e limites de potencial na cinética de redução de perclorato e na concentração máxima de cloreto foi estudada. Em todos os casos a concentração máxima de cloreto detectada na solução foi de 2,0 x 10-5 mol L-1, exceto no tratamento de ativação eletroquímica quando essa concentração atinge 5,0 x 10-5 mol L-1. A influência da presença de óxidos superficiais, temperatura e agitação da solução, pH, e tempo de polarização no processo de redução de perclorato também foi avaliada. Concluiu-se que (i) a presença de óxidos catalisa o processo de redução; (ii) a influência da temperatura é significativa a 70 °C; (iii) a agitação e o pH da solução não exercem influência na concentração máxima de cloreto produzida e (iv) a concentração máxima de cloreto estabiliza-se após cerca de 150 minutos de polarização. / Electrochemical measurements including chronoamperometry, cyclic voltammetry, film surface electrochemical ageing procedures, FTIR and Raman spectroscopy including the SERS effect were carried out in order to study the electrochemical reduction of perchlorate ions at tin electrodes. Sodium perchlorate solution 0.5 mol L-1 was employed as electrolyte. It was observed that maximum chloride concentration produced by the perchlorate reduction (5.0 x 10-5 mol L-1), takes place within a potential range comprising the negative side of de double layer region and the positive side of the hydrogen evolution region. The upper limit of chloride concentration occurs due to the establishment of an equilibrium between the chloride ions in solution and the adsorbed chloride ions that blocks the surface sites where the reduction process takes place. In order to electromodify the tin surface, the electrode was subjected to perturbing potential programs, aiming to evaluate changes in the electrocatalytic properties of the modified sufaces. The influence of the experimental variables perturbation sweep rate as well as perturbation time and potential limits on the perchrolate reduction kinetic and on the maximum chloride concentration was studied. Except to the activation treatment, the maximum chloride concentration was 2.0 x 10-5 mol L-1 for all the applied perturbation programs. The influence of the oxides on the electrode surface, stirring, temperature, pH and polarization time on the reduction process was evaluated too. It was shown that (i) the presence of oxides on the electrode surface favors the reduction reaction; (ii) there is significant influence of temperature at 70 °C; (iii) pH and stirring the solution exerts no influence on the maximum chloride concentration produced and (iv) the maximum chloride concentration produced by electroreduction is reached after 150 minutes.
523

Caracterização do petróleo por técnicas espectroscópicas e sua utilização na avaliação e desenvolvimento de métodos de inferência em processo de refino. / Characterization of petroleum by spectroscopic techniques and their use in the evaluation and development of inference methods for the refining process.

Patricia Araujo Pantoja 26 November 2010 (has links)
A classificação e caracterização do petróleo cru em tempo real é um dos mais importantes desafios atuais da indústria petroquímica e agencias ambientais. Um método rápido e econômico antes da destilação do petróleo iria a fornecer informações químicas de grande importância para o ajuste em tempo real dos parâmetros críticos de uma refinaria, permitindo a otimização do processo, resultando em benefícios econômicos e ambientais. Uma variedade de técnicas espectroscópicas está sendo utilizadas nas ultima décadas para as analises, classificação e caracterização de petróleo cru nos campos de perfuração, para as análises dos produtos petrolíferos e para detecção de derrames. As vantagens do uso desta técnica incluem uma rápida resposta, requerimento mínimo de preparação da amostra e equipamentos relativamente econômicos. As técnicas espectroscópicas envolvidas na tese (NIR) mostraram o maior potencial no campo. No entanto, os estudos realizados com todas estas técnicas não foram enfocados em aplicações em linha. O NIR é tradicionalmente a técnica espectroscópica mais utilizada para a análise de petróleo cru. Mas os problemas típicos que esta técnica apresenta são sobreposição das diferentes bandas de absorção e saturação do sinal devido à alta absorbância característico do petróleo cru. A Fluorescência é um fenômeno mais complexo do que a absorção (NIR) e efeitos como quenchinge transferência de energia têm que ser consideradas. No entanto, a espectroscopia de fluorescência pode fornecer sinais bidimensionais com muito mais informação do que uma emissão unidimensional do espectro de absorção. Enquanto a espectrometria de massa, a técnica MALDI TOF faz possível a ionização de macromoléculas que são difíceis de serem ionizadas por não ser facilmente decompostas. Neste trabalho, as vantagens e limitações das técnicas disponíveis são analisadas e o potencial do analises remoto em linha do petróleo cru é avaliado. A pesar da boa analise e classificação obtida com algumas técnicas, nem sempre é possível integrá-los em um sistema em linha quando uma preparação previa da amostra é necessária ou quando o sistema é demasiado complexo. Para a extração da informação química contida nos espectros foram utilizados métodos matemáticos e estatísticos (quimiométricos) nos espectros: Mínimos Quadrados Parciais (PLS). / Online remote characterization and real-time classification of crude petroleum is one of the most important current challenges faced by the petrochemical industry and environmental agencies. A rapid and inexpensive method for the remote analysis and classification of petroleum prior to distillation of the crude would provide chemical information of great importance for real time adjustment of the critical parameters of a refinery, permitting an optimization of the process and resulting in economic and environmental benefits. A variety of spectroscopic techniques have been used over the last few decades for the analysis, characterization and classification of crude oil in drilling fields, for the analysis of petroleum products and for the detection of oil-spills. The advantages of using these techniques include rapid response, the requirement of minimal sample preparation and relatively inexpensive equipment costs. The spectroscopic techniques involved in the thesis (NIR, fluorescence and mass spectrometry) showed the greatest potential in the field. Nevertheless, the studies carried out with these techniques typically do not focus on online applications. NIR is traditionally the spectroscopic techniques most used for crude petroleum analysis. Overlap of the different absorption bands and saturation of the signal due to the high absorbance of crude petroleum are typical problems encountered with this technique. Fluorescence is a more complex phenomenon than absorption (NIR) and effects such as quenching and energy transfer have to be considered. However, fluorescence spectroscopy can provide two-dimensional signals with much more information than a one-dimensional emission or absorption spectrum. While mass spectrometry, MALDI TOF technique makes possible the ionization of macromolecules that are difficult to be ionized not be easily broken. In this work, the advantages and limitations of the available techniques are analyzed and the potential for remote on-line analysis of crude petroleum is evaluated. In spite of the good analysis and classification obtained with some of the techniques, it is not always possible to integrate them into a remote on-line analytical system when some prior sample preparation is required or when the system is too complex. For the extraction of chemical information contained in the spectra were used mathematical and statistical (chemometric) in the spectra: Partial Least Squares (PLS).
524

Utilização da fase para estimativa das propriedades ópticas absolutas do tecido biológico com espectroscopia óptica de difusão / Using the phase to estimate the absolute optical properties of biological tissue with diffuse optical spectroscopy

Cano Rodriguez, Reember, 1987- 11 October 2014 (has links)
Orientador: Rickson Coelho Mesquita / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-25T21:15:48Z (GMT). No. of bitstreams: 1 CanoRodriguez_Reember_M.pdf: 7820145 bytes, checksum: a3b06ecbe442d6ecf0266b22a280fb76 (MD5) Previous issue date: 2014 / Resumo: A capacidade de observar a fisiologia funcional do tecido humano tem crescido rapidamente nos últimos anos. Entre outras técnicas, destaca-se a espectroscopia óptica de difusão (DOS), uma técnica emergente que utiliza os princípios da difusão de fótons e permite o monitoramento do tecido biológico de forma continua e portátil. A partir da luz (~ 700 - 900 nm) espalhada pelo tecido é possível determinar variações relativas do seu coeficiente de absorção, que estão relacionadas com as concentrações de oxi-hemoglobina (HbO2) e deoxi-hemoglobina (HbR) presentes no sangue. Neste trabalho, utilizamos a técnica de DOS no domínio da frequência, e a informação da defasagem da onda espalhada (em relação _a onda incidida) para determinação das propriedades ópticas absolutas do tecido biológico e, consequentemente, da sua fisiologia. Em particular, comparamos diferentes modelos de propagação da luz no tecido (semi-infinito e duas camadas) e as propriedades ópticas derivadas destes modelos. Além disso, investigamos métodos de calibração do sinal óptico no tecido, do ponto de vista teórico e experimental, mostrando sua aplicabilidade em experimentos com humanos, no estado de repouso e em intervenções cirúrgicas / Abstract: The ability to observe the functional physiology of human tissue has grown rapidly in recent years. Among other techniques, we highlight diffuse optical spectroscopy (DOS), an emerging technique that utilizes the principles of diffusion of photons and allows monitoring of biological tissue continuously and portable way. From the light (~700 - 900 nm) scattered by tissue it is possible to determine the relative changes in the absorption coefficient, which are related to the concentrations of oxyhemoglobin (HbO2), and deoxyhemoglobin (HbR) in the blood. In this study, we used the technique DOS in the frequency domain, and the phase information of the scattered wave (related to incident wave) for determining the absolute optical properties of biological tissue and, consequently, the physiology. In particular, we compared different models of propagation of light (semi-infinite and two-layer) and the optical properties of tissue derived from these models. Furthermore, we investigated methods of calibration of the optical signal on the tissue from both the experimental and theoretical perspectives, demostrating its applicability in experiments with humans in the resting state and in surgical interventions / Mestrado / Física / Mestre em Física
525

Mesures par spectroscopie à transformée de Fourier infrarouge de paramètres spectraux absolus pour des molécules d'intérêt atmosphérique

El Hachtouki, Rachid January 2004 (has links)
Doctorat en Sciences / info:eu-repo/semantics/nonPublished
526

Etude de la caractérisation de matières collagéniques pour spectroscopie Infrarouge. : Mise au point et développement d'un système d'analyse en mode dynamique par l'industrie de la Gélatine. / Study of the characterization of collagenic materials for Infrared spectroscopy. : Development and development of a dynamic analysis system by the gelatin industry.

Duthen, Simon 26 January 2018 (has links)
La gélatine est un biopolymère naturel obtenu après dénaturation et hydrolyse partielle de fibres de collagène, une protéine fibrillaire présente dans les tissus conjonctifs de toutes les espèces du règne animal. Elle est utilisée dans différentes industries, parmi lesquelles l’industrie agroalimentaire, pharmaceutique, photographique et cosmétique. Ses propriétés fonctionnelles dépendent du procédé de fabrication, mais également de l’origine des matières collagéniques. L’objectif de ce travail de thèse est la caractérisation de la matière première (couennes de porc), mais également de la gélatine obtenue lors du processus, par une méthode rapide et non destructive. L’utilisation de la spectroscopie proche infrarouge couplée à des méthodes chimiométriques, a permis de travailler à l’échelle du laboratoire, mais également sur la chaîne de production industrielle. Le premier chapitre porte sur l’étude de l’hétérogénéité des couennes de porc au laboratoire, en termes de teneur en protéines, matières grasses, matières sèches et collagène. Plusieurs modèles ont pu être développés pour prédire ces teneurs, à partir de spectres proche infrarouge collectés sur des couennes en mouvement. Les meilleurs modèles présentent des performances compatibles avec une utilisation dans l’usine. Le second chapitre adapte cette méthode à l’échelle industrielle, c’est-à-dire à partir du rendement en gélatine fabriquée pour un lot de 75t de couennes. L’approche prédictive ne s’est pas avérée concluante, cependant des approches de classification ont montré leur intérêt. Les deux essais suivants ont porté sur la gélatine. Le troisième chapitre porte sur le développement de modèles de prédiction des propriétés physico-chimiques d’échantillons de gélatine à partir de spectres proche infrarouge, mettant en évidence de hautes capacités de prédiction de ces paramètres (r²>0,9). Enfin, ce chapitre propose de relier les caractéristiques moléculaires de la gélatine à ses propriétés physico-chimiques, par la technique de Asymmetrical Flow Field-Flow Fractionation couplée à un détecteur de diffusion de la lumière Multiangulaire (MALS). Les paramètres de caractérisation de l’AFlFFF-MALS permettent de discriminer partiellement des échantillons de gélatine dont les paramètres de bloom et de viscosité sont différents. / Gelatin is a natural biopolymer obtained after denaturation and partial hydrolysis of collagen fibers, a fibrillar protein present in the connective tissues of all species of the animal kingdom. It is used in various industries, including the agri-food, pharmaceutical, photographic and cosmetic industries. Its functional properties depend on the manufacturing process, but also on the origin of the collagenous materials. The objective of this thesis is to characterize the raw material (pig rind), but also the gelatin obtained during the process, by a fast and non-destructive tool. The use of near-infrared spectroscopy coupled with chemometric methods allowed us to work on the scale of the laboratory but also on the industrial chain. The first study examines the heterogeneity of pig rinds, under laboratory conditions, in terms of protein, fat, moisture and collagen contents. Several models have been developed to predict these levels, from near infrared spectra collected on moving rinds. The best models have good performances. In the second industrial scale trial, an approach to gelatin yield from 75 tons batches was proposed. The predictive approach has not been conclusive; however, classification approaches have shown interesting results. The next two tests were on gelatin. The third test allowed the development of models for predicting the physicochemical properties of gelatin samples from near-infrared spectra, demonstrating very good predictive capabilities of these parameters (r²> 0.9). Finally, a final test allowed to link the molecular characteristics of the gelatin to its physicochemical properties, by the technique of Asymmetrical Field-Flow Fractionation coupled with a Multiangular Light Scattering Detector (MALS). The characterization parameters of AFlFFF-MALS make it possible to partially discriminate gelatin samples with different bloom and viscosity parameters.
527

High-resolution infrared studies on deuterated monoiodoacetylene

Sarkkinen, H. (Hannu) 01 December 2004 (has links)
Abstract This thesis deals with infrared spectroscopy investigations on the linear DCCI molecule. The high resolution spectra between 200–5200 cm-1 were measured with the Fourier transform spectrometer at the University of Oulu. The spectra were analyzed taking into account various types of resonances between rovibrational energy levels. As a result, a set of molecular constants and resonance parameters describing the rotational and vibrational energy states of the molecule were obtained. From the resulting molecular constants, together with previous results from literature for HCCI, the structure of monoiodoacetylene was calculated. In addition, eight harmonic force constants with estimated uncertainties for monoiodoacetylene were determined.
528

Perfusive and diffusive oxygen transport in skeletal muscle during incremental handgrip exercise

Hammer, Shane Michael January 1900 (has links)
Master of Science / Department of Kinesiology / Thomas J. Barstow / Limb blood flow increases linearly with exercise intensity; however, invasive measurements of microvascular muscle blood flow during incremental exercise have demonstrated submaximal plateaus. Diffuse correlation spectroscopy (DCS) noninvasively quantifies relative changes in microvascular blood flow at rest via a blood flow index (BFI). The purpose of this study was to quantify relative changes in tissue blood flow during exercise using DCS, compare the BFI of the flexor digitorum superficialis (BFI[subscript]FDS) muscle to brachial artery blood flow (Q̇[subscript]BA) measured via Doppler ultrasound, and employ near infrared spectroscopy (NIRS) alongside DCS to simultaneously measure perfusive and diffusive oxygen transport within a single volume of exercising skeletal muscle tissue. We hypothesized Q̇[subscript]BA would increase with increasing exercise intensity until task failure, BFI[subscript]FDS would plateau at a submaximal work rate, and muscle oxygenation characteristics (total-[heme], deoxy-[heme], and % saturation) measured with NIRS would demonstrate a plateau at a similar work rate as BFI[subscript]FDS. Sixteen subjects (23.3 ± 3.9 yrs; 170.8 ± 1.9 cm; 72.8 ± 3.4 kg) participated in this study. Peak power (P[subscript]peak) was determined for each subject (6.2 ± 1.4W) via an incremental handgrip exercise test to task failure. Measurements of Q̇[subscript]BA, BFI[subscript]FDS, total-[heme], deoxy-[heme], and % saturation were made during each stage of the incremental exercise test. Q̇[subscript]BA increased with exercise intensity until the final work rate transition (p < 0.05). No increases in BFI[subscript]FDS or muscle oxygenation characteristics were observed at exercise intensities greater than 51.5 ± 22.9% of P[subscript]peak and were measured simultaneously in a single volume of exercising skeletal muscle tissue. Differences in muscle recruitment amongst muscles of the whole limb may explain the discrepancies observed in Q̇[subscript]BA and BFI[subscript]FDS responses during incremental exercise and should be further investigated.
529

Control of muscle blood flow during dynamic exercise: muscle contraction / blood flow interactions

Lutjemeier, Barbara June January 1900 (has links)
Doctor of Philosophy / Department of Anatomy and Physiology / Thomas J. Barstow / The interaction between dynamic muscle contractions and the associated muscle blood flow is very intriguing leading to questions regarding the net effect of these contractions on oxygen delivery and utilization by the working muscle. Study 1 examined the impact of contractions on muscle blood flow at the level of the femoral artery. We demonstrated that muscle contractions had either a facilitory, neutral, or net impedance effect during upright knee extension exercise as intensity increased from very light to ~70% peak work rate. This led to the question of what impact a change in contraction frequency might have on the coupling of blood flow to metabolic rate during cycling exercise. The blood flow/VO2 relationship has been shown to be linear and robust at both the central (i.e., cardiac output/pulmonary VO2) and peripheral (leg blood flow/leg VO2) levels. However, an increase in contraction frequency has been reported to either decrease, have no effect, or increase the blood flow response during exercise. Study 2 determined if the steady state coupling between muscle blood flow and metabolic rate (centrally and/or peripherally) would be altered by varying contraction frequency. Our results indicate that both central and peripheral blood flow/VO2 relationships are robust and remain tightly coupled regardless of changes in contraction frequency. Study 3 examined muscle microvascular hemoglobin concentration and oxygenation within the contraction/relaxation cycle to determine if microvascular RBC volume was preserved and if oxygen extraction occurred during contractions. We concluded that microvascular RBC volume was preserved during muscle contractions (i.e., RBCs remained in the capillaries), which could facilitate continued oxygen delivery. Further, there was a cyclic pattern of deoxygenation/oxygenation that corresponded with the contraction/relaxation phases of the contraction cycle, with deoxyhemoglobin increasing significantly during the contractile phase. These data suggest that oxygen extraction continues to occur during muscle contractions. Significant insight has been gained on the impact of muscle contractions on oxygen delivery to and exchange in active skeletal muscle. This series of studies forms a base of knowledge that furthers our understanding of the mechanisms which govern the control of skeletal muscle blood flow and its coupling to muscle metabolic rate.
530

Air quality monitoring with polar-orbiting hyperspectral infrared sounders : a fast retrieval scheme for carbon monoxide

Smith, Nadia 07 October 2014 (has links)
D.Phil. (Geography) / The Infrared Atmospheric Sounding Interferometer (lASI), operational in polar-orbit since 2006 on the European MetOp-A satellite, is the most advanced of its kind in space. It has been designed to provide soundings of the troposphere and lower stratosphere at nadir in a spectral interval of 0.25 em" across the range 645-2 760 em". Fine spectral sampling such as this is imperative in the sounding of trace gases. Since its launch, the routine retrievals of greenhouse, species from IASI measurements have made a valuable contribution to atmospheric chemistry studies at a global scale. The main contribution of this thesis is the development of a new trace gas retrieval scheme for IASI measurements. The goal was to improve on the global operational scheme in terms of the algorithm complexity, speed of calculation and spatial resolution achieved in the final solution. This schemedirectly retrieves column integrated trace gas densities at single field-of-view (FOV) from IASI measurements within a 10% accuracy limit. The scheme is built on the Bayesian framework of probability and based on the assumption that the inversion of total column values, as apposed to gas profiles, is a near-linear problem. Performance of the retrieval scheme is demonstrated on simulated noisy measurements for carbon monoxide (CO). Being a linear solution, the scheme is'highly dependent on the accuracy of the a priori. A statistical estimate of the a priori was computed using a principal component regression analysis with 50 eigenvectors. The corresponding root-mean-square (RMS) error of the a priori was calculated to be 9.3%. In general terms, the physical retrieval improved on the a priori, and sensitivity studies were performed to demonstrate the accuracy and stability of the retrieval scheme under a numberof perturbations. A full system characterization and error analysis is additionally preformed to elicidate the nature of this complex problem. The hyperspectral IASI measurements introduce a significant correlation error in the retrieval. The Absorption Line Cluster (ALC) channel selection method was developed in this thesis, to address the correlation error explicitly. When a first neighbour correlation factor of 0.71 is assumed in the measurement error covariance for the clusters of ALC channels, then most of the correlation error is removed in the retrieval. In conclusion, the total column trace gas retrieval scheme developed here is fast, simple, intuitive, transparent and robust. These characteristics together make it highly suitable for implementation in an operational environment intended for air quality monitoring on a regional scale.

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