Fundação de Amparo à Pesquisa do Estado do Rio de Janeiro / Este trabalho de pesquisa descreve dois estudos de caso de métodos quimiométricos empregados para a quantificação de hidrocarbonetos policíclicos aromáticos HPAs (naftaleno, fluoreno, fenantreno e fluoranteno) em água potável usando espectroscopia de fluorescência molecular e a classificação e caracterização de sucos de uva e seus parâmetros de qualidade através de espectroscopia de infravermelho próximo. O objetivo do primeiro estudo é a aplicação combinada de métodos quimiométricos de segunda ordem (N-PLS, U-PLS, U-PLS/RBL e PARAFAC) e espectrofluorimetria para determinação direta de HPAs em água potável, visando contribuir para o conhecimento do potencial destas metodologias como alternativa viável para a determinação tradicional por cromatografia univariada. O segundo estudo de caso destinado à classificação e determinação de parâmetros de qualidade de sucos de uva, densidade relativa e teor de sólidos solúveis totais, foi medida por espectroscopia de infravermelho próximo e métodos quimiométricos. Diversos métodos quimiométricos, tais como HCA, PLS-DA, SVM-DA e SIMCA foram investigados para a classificação amostras de sucos de uva ao mesmo tempo que métodos de calibração multivariada de primeira ordem, tais como PLS, iPLS e SVM-LS foram usadas para a predição dos parâmetros de qualidade. O princípio orientador para o desenvolvimento dos estudos aqui descritos foi a necessidade de metodologias analíticas com custo, tempo de execução e facilidade de operação melhores e menor produção de resíduos do que os métodos atualmente utilizados para a quantificação de HPAs, em água de torneira, e classificação e caracterização das amostras de suco de uva e seus parâmetros de qualidade / This research work describes two studies of chemometric methods employed for the quantification of polycyclic aromatic hydrocarbons PAHs (naphthalene, fluorene, phenanthrene and fluoranthene) in tap water using molecular fluorescence technique, and the classification and characterization of grape juice and its quality parameters by near infrared spectroscopy. The goal of the first study is the combined application of the second-order chemometric methods (N-PLS, U-PLS, U-PLS/RBL, PARAFAC) and spectrofluorimetry technique for direct determination of HPAs in tap water, aiming to contribute for the growth of knowledge about the potential of these methodologies as viable alternatives to the traditional univariate chromatographic determination. The second study aimed at the classification and determination of grape juice quality parameters, as relative density and total soluble solids, were measured with the aid of near infrared spectroscopy and chemometric methods. Several chemometric methods, such as HCA, PLS-DA, SVM-DA, SIMCA, were investigated for the classification of grape juice samples as the same time first-order multivariate calibration methods, such as PLS, iPLS, SVM-LS, were used for prediction of quality parameters. The guiding principle for the development of the studies herein described was the need for analytical methodologies with cost, execution time, ease of operation, and residue output better or lower than present day methods employed for the quantification of PAHs in tap water and the classification and characterization of grape juice sample and its quality parameters

Fundação de Amparo à Pesquisa do Estado do Rio de Janeiro / Este trabalho de pesquisa descreve dois estudos de caso de métodos quimiométricos empregados para a quantificação de hidrocarbonetos policíclicos aromáticos HPAs (naftaleno, fluoreno, fenantreno e fluoranteno) em água potável usando espectroscopia de fluorescência molecular e a classificação e caracterização de sucos de uva e seus parâmetros de qualidade através de espectroscopia de infravermelho próximo. O objetivo do primeiro estudo é a aplicação combinada de métodos quimiométricos de segunda ordem (N-PLS, U-PLS, U-PLS/RBL e PARAFAC) e espectrofluorimetria para determinação direta de HPAs em água potável, visando contribuir para o conhecimento do potencial destas metodologias como alternativa viável para a determinação tradicional por cromatografia univariada. O segundo estudo de caso destinado à classificação e determinação de parâmetros de qualidade de sucos de uva, densidade relativa e teor de sólidos solúveis totais, foi medida por espectroscopia de infravermelho próximo e métodos quimiométricos. Diversos métodos quimiométricos, tais como HCA, PLS-DA, SVM-DA e SIMCA foram investigados para a classificação amostras de sucos de uva ao mesmo tempo que métodos de calibração multivariada de primeira ordem, tais como PLS, iPLS e SVM-LS foram usadas para a predição dos parâmetros de qualidade. O princípio orientador para o desenvolvimento dos estudos aqui descritos foi a necessidade de metodologias analíticas com custo, tempo de execução e facilidade de operação melhores e menor produção de resíduos do que os métodos atualmente utilizados para a quantificação de HPAs, em água de torneira, e classificação e caracterização das amostras de suco de uva e seus parâmetros de qualidade / This research work describes two studies of chemometric methods employed for the quantification of polycyclic aromatic hydrocarbons PAHs (naphthalene, fluorene, phenanthrene and fluoranthene) in tap water using molecular fluorescence technique, and the classification and characterization of grape juice and its quality parameters by near infrared spectroscopy. The goal of the first study is the combined application of the second-order chemometric methods (N-PLS, U-PLS, U-PLS/RBL, PARAFAC) and spectrofluorimetry technique for direct determination of HPAs in tap water, aiming to contribute for the growth of knowledge about the potential of these methodologies as viable alternatives to the traditional univariate chromatographic determination. The second study aimed at the classification and determination of grape juice quality parameters, as relative density and total soluble solids, were measured with the aid of near infrared spectroscopy and chemometric methods. Several chemometric methods, such as HCA, PLS-DA, SVM-DA, SIMCA, were investigated for the classification of grape juice samples as the same time first-order multivariate calibration methods, such as PLS, iPLS, SVM-LS, were used for prediction of quality parameters. The guiding principle for the development of the studies herein described was the need for analytical methodologies with cost, execution time, ease of operation, and residue output better or lower than present day methods employed for the quantification of PAHs in tap water and the classification and characterization of grape juice sample and its quality parameters

Made available in DSpace on 2016-08-19T12:56:34Z (GMT). No. of bitstreams: 1 Ariana Komura de Castro.pdf: 1539013 bytes, checksum: 9322eebdf7e436f3bca6297342a522b1 (MD5) Previous issue date: 2009-07-03 / The Hildebrand solubility parameter is used to express the compatibility of petroleum in mixtures, starting from the principle that, independently from the system composition, the asphaltenes always precipitate in a certain solubility parameter, known as the flocculation parameter, which estimated value is 16,35 (MPa)1/2. In this paper, it was tried to experimentally determine the flocculation parameter and the solubility parameters of some petroleum, through data of onset of precipitation of asphaltenes by adding n-alkenes. The experimental determinations of onset of precipitation were performed by optical microscopy and Near-Infrared spectroscopy (NIR), in order to be also evaluated the correlation between measures. The outcomes of onset of precipitation showed a reasonable correlation among techniques, but the data obtained by NIR were generally larger. Towards the flocculation parameter, the experimental data when adjusted to a linear behavior of first order ended up on inconsistent values compared with the ones in literature, what raised doubts about the basic hypothesis of compatibility model. However, it was possible the determination of solubility parameters for several petroleum and it was noticed that the data are used successfully in prediction of compatibility in mixtures, therefore, it was verified the need of the improvement of experimental methodology to the determination of onset of precipitation through Near-Infrared spectroscopy and clues indicate that the phenomena of asphaltenes precipitation may not be only molecular. / O parâmetro de solubilidade de Hildebrand é utilizado para expressar a compatibilidade de petróleos em misturas, partindo-se do princípio que, independentemente da composição do sistema, os asfaltenos precipitam sempre em um determinado parâmetro de solubilidade, conhecido como parâmetro de floculação, cujo valor estimado é 16,35 (MPa)1/2. Neste trabalho, tentou-se determinar experimentalmente o parâmetro de floculação e os parâmetros de solubilidade de alguns petróleos, através dos dados de início de precipitação dos asfaltenos pela adição de n-alcanos. As determinações experimentais de início de precipitação foram realizadas por microscopia ótica e espectroscopia de Infravermelho Próximo (NIR), a fim de que fosse avaliada também a correlação entre as medidas. Os resultados de início de precipitação indicaram uma correlação razoável entre as técnicas, mas os dados obtidos pelo NIR foram geralmente maiores. Em relação ao parâmetro de floculação, os dados experimentais quando ajustados a um comportamento linear de primeira ordem proporcionou valores inconsistentes comparados com o da literatura, o que coloca em dúvida a hipótese básica do modelo de compatibilidade. Entretanto, foi possível a determinação dos parâmetros de solubilidade para vários petróleos e foi observado que os dados são utilizados com sucesso na predição da compatibilidade em misturas, porém, verificou-se a necessidade do aperfeiçoamento da metodologia experimental para a determinação do início de precipitação através da espectroscopia de infravermelho próximo e indícios apontam que o fenômeno da precipitação dos asfaltenos possa não ser apenas molecular.

Orientador: Ronei Jesus Poppi / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-19T18:06:58Z (GMT). No. of bitstreams: 1 Alves_JulioCesarLaurentino_D.pdf: 19282542 bytes, checksum: 78d1bf16d9d133c488adb4bedf593b06 (MD5) Previous issue date: 2012 / Resumo: Modelos lineares de regressão e classificação por vezes proporcionam um desempenho insatisfatório no tratamento de dados de espectroscopia no infravermelho próximo de produtos derivados de petróleo. A máquina de vetores de suporte (SVM), baseada na teoria do aprendizado estatístico, possibilita o desenvolvimento de modelos de regressão e classificação não lineares que podem proporcionar uma melhor modelagem dos referidos dados, porém ainda é pouco explorada para resolução de problemas em química analítica. Nesse trabalho demonstra-se a utilização do SVM para o tratamento de dados de espectroscopia na região do infravermelho próximo de combustíveis e lubrificantes. O SVM foi utilizado para a solução de problemas de regressão e classificação e seus resultados comparados com os algoritmos de referência PLS e SIMCA. Foram abordados os seguintes problemas analíticos relacionados a controle de processos e controle de qualidade: (i) determinação de parâmetros de qualidade do óleo diesel utilizados para otimização do processo de mistura em linha na produção desse combustível; (ii) determinação de parâmetros de qualidade do óleo diesel que é carga do processo de HDT, para controle e otimização das condições de processo dessa unidade; (iii) determinação do teor de biodiesel na mistura com o óleo diesel; (iv) classificação das diferentes correntes que compõem o pool de óleo diesel na refinaria, permitindo a identificação de adulterações e controle de qualidade; (v) classificação de lubrificantes quanto ao teor de óleo naftênico e/ou presença de óleo vegetal. Demonstram-se o melhor desempenho do SVM em relação aos modelos desenvolvidos com os métodos quimiométricos de referência (métodos lineares). O desenvolvimento de métodos analíticos rápidos e de baixo custo para solução de problemas em controle de processos e controle de qualidade, com a utilização de modelos de regressão e classificação mais exatos, proporcionam o monitoramento da qualidade de forma mais eficaz e eficiente, contribuindo para o aumento das rentabilidades nas atividades econômicas de produção e comercialização dos derivados do petróleo estudados / Abstract: Linear regression and classification models can produce a poor performance in processing near-infrared spectroscopy data of petroleum products. Support vectors machine (SVM), based on statistical learning theory, provides the development of models for nonlinear regression and classification that can result in better modeling of these data but it is still little explored for solving problems in analytical chemistry. This work demonstrates the use of the SVM for treatment of near-infrared spectroscopy data of fuels and lubricants. The SVM was used to solve regression and classification problems and its results were compared with the reference algorithms PLS and SIMCA. The following analytical problems related to process control and quality control were studied: (i) quality parameters determination of diesel oil, used for optimization of in line blending process; (ii) quality parameters determination of diesel oil which is feed-stock of HDT unit for optimization of process control; (iii) quantification of biodiesel blended with diesel oil; (iv) classification of different streams that make up the pool of diesel oil in the refinery, enabling identification of adulteration and quality control; (v) classification of lubricants based on the content of naphthenic oil and/or the presence of vegetable oil. It is shown the best performance of the SVM compared to models developed with the reference algorithms. The development of fast and low cost analytical methods used in process control and quality control, with the use of more accurate regression and classification models, allows monitoring quality parameters in more effectiveness and efficient manner, making possible an increase in profitability of economic activities of production and business of petroleum derivatives studied / Doutorado / Quimica Analitica / Doutor em Ciências

Abstract Multimodal measurements are increasingly being employed in the study of human physiology. Brain studies in particular can draw advantage of simultaneous measurements using different modalities to analyse correlations, mechanisms and relationships of physiological signals and their dynamics in relation to brain functions. Moreover, multimodal measurements help to identify components of physiological dynamics generated specifically by the brain. This thesis summarizes the study, design and development of non-invasive medical instruments that can be utilized in conjunction with magnetic resonance imaging (MRI). A key challenge in the development of measurement methods is posed by the extraordinary requirements that the MRI environment poses - all materials need to be MR-compatible and the selected instruments and devices must not be affected by the strong magnetic field generated by the MRI scanner nor the MRI by the instruments placed within its scanning volume. The presented methods allow simultaneous continuous measurement of heart rate (HR) and metabolism from the brain cortex as well as pulse wave velocity (PWV) and blood pressure measurements in synchrony with electroencephalography (EEG) and MRI. Furthermore, the thesis explored the reliability and accuracy of the responses gathered by the developed instruments and, using new experimental methods, estimated the propagation of near-infrared light in the human brain. The goal of the novel multimodal measurement environment is to provide more extensive tools for medical researchers, neurologists in particular, to acquire accurate information on the function of the brain and the human body. Measurements have been performed on more than 70 persons using the presented multimodal setup to study such factors as the correlation between blood oxygen level-dependent (BOLD) data and low-frequency oscillations (LFOs) during the resting state. / Tiivistelmä Multimodaalisia kuvantamismenetelmiä käytetään enenevässä määrin ihmisen fysiologian ja elintoimintojen tutkimisessa. Erityisesti aivotutkimuksessa samanaikaisesti useammalla modaliteetilla mittaaminen mahdollistaa erilaisten fysiologisten mekanismien ja niiden korrelaatioiden tutkimisen kehon ja aivotoimintojen välillä. Lisäksi multimodaaliset mittaukset auttavat yksilöimään fysiologiset komponentit toisistaan ja identifioimaan aivojen tuottamia fysiologisia signaaleja. Tämä väitöskirja kokoaa tutkimustyön sekä laite- ja instrumentointisuunnittelun ja sen kehittämistyön ei-invasiivisesti toteutettujen lääketieteen mittausmenetelmien käyttämiseksi magneettikuvauksen aikana. Erityishaasteena työssä on ollut magneettikuvausympäristö, joka asettaa erityisvaatimuksia mm. mittalaitteissa käytettäville materiaaleille sekä laitteiden häiriönsiedolle magneettikuvauslaitteen aiheuttaman voimakkaan magneettikentän takia. Kehitettävät mittausmenetelmät eivät myöskään saa aiheuttaa häiriöitä magneettikuvauslaitteen tuottamalle kuvainformaatiolle. Väitöskirjassa esitettävät mittausmenetelmät tekevät mahdolliseksi mitata magneettikuvausympäristössä ihmisen sydämen sykettä, veren virtauksen kulkunopeutta ja verenpaineen vaihteluja sekä aivokuoren metaboliaa - kaikki synkronissa aivosähkökäyrän mittaamisen ja magneettikuvantamisen kanssa. Lisäksi väitöskirjassa tutkitaan kehitettyjen mittausmenetelmien antamaa mittaustarkkuutta sekä arvioidaan lähi-infrapunavalon etenemistä ihmisen aivoissa uudenlaisella menetelmällä. Kehitetyllä multimodaalisella mittausympäristöllä on tavoitteena antaa lääketieteen alan tutkijoille, erityisesti neurologeille, käyttöön mittausmenetelmiä, joiden avulla voidaan tutkia ihmisen aivojen ja kehon välisiä toimintoja aiempaa kattavammin. Laitekokonaisuudella on tutkittu jo yli 70:tä henkilöä. Näissä mittauksissa on tutkittu mm. veren happitasojen hitaita vaihteluja ihmisen aivojen ollessa lepotilassa, ns. resting state -tilassa.

A l’échelle de l’agro-écosystème, la productivité primaire est sous la dépendance du recyclage des matières organiques du sol (MOS) par l’action des organismes indigènes décomposeurs, qui minéralisent les composés organiques libérant ainsi les nutriments nécessaires à la croissance végétale. A une échelle plus globale, le recyclage des MOS détermine les flux de carbone entre le sol et l’atmosphère, avec des conséquences majeures sur la qualité de l’environnement et les changements globaux. Malgré le rôle central des microorganismes indigènes dans ces processus, la composante microbienne est encore mal connue et souvent considérée comme une boîte noire en termes de diversité et de fonctionnalité. Par conséquent, pour mieux comprendre et prédire l’évolution des MOS et donc les flux de carbone (C) dans les agro-écosystèmes, il est nécessaire de mieux connaitre les populations et les mécanismes microbiens impliqués dans leur dégradation et transformation. Dans ce contexte, l’objectif de cette thèse était de progresser dans la connaissance de la réponse des communautés microbiennes telluriques à l’apport de résidus de culture. Cette réponse des communautés microbiennes a été abordée en termes de (i) succession des populations impliquées dans les processus de dégradation de ces MOF (matières organiques fraîches), (ii) lien avec leur fonction de dégradation et répercussion sur la dynamique des matières organiques, et (iii) rôle dans les processus de stockage/déstockage du carbone via les processus de « priming effect ». Différents paramètres pouvant moduler la dégradation des résidus et la dynamique des communautés ont été pris en compte : modalité d’apport des résidus (pratiques culturales), qualité biochimique des résidus (différentes espèces végétales), et température. La stratégie globale de recherche développée repose sur des expérimentations de terrain et au laboratoire impliquant différentes échelles spatiales (du microcosme de sol à la parcelle agronomique) et temporelles (du temps de génération microbien aux cycles culturaux). La réponse des communautés microbiennes à l’apport de résidus a été évaluée par l’utilisation de méthodes moléculaires permettant de caractériser sans a priori la diversité des microorganismes du sol (empreintes moléculaires, clonage/séquençage, séquençage haut débit). En parallèle, un suivi quantitatif et qualitatif de la matière organique du sol, par des méthodes de biochimie ou de spectroscopie, a été réalisé afin d’établir le lien entre la dynamique des communautés microbiennes et le devenir de la matière organique dans le sol. Les deux premiers chapitres du manuscrit portent sur des expérimentations réalisées au terrain (conditions naturelles) afin d’évaluer l’influence de la localisation des résidus (résidus de blé incorporés vs. laissés en surface ; site expérimentale INRA Mons) d’une part et d’autre part de la qualité biochimique des résidus (résidus de blé, colza et luzerne incorporés, site expérimentale INRA Epoisses) sur la dynamique des communautés microbiennes du sol. Les résultats obtenus mettent en évidence une forte influence de la localisation comme de la qualité biochimique des résidus sur les successions de populations microbiennes induites suite à l’apport. Des populations/groupes microbiens stimulés spécifiquement dans chaque modalité ont été identifiés. Les résultats de diversité ont été mis en regard des dynamiques de décomposition des résidus, afin de faire le lien entre les successions de populations et l’évolution des ressources trophiques. La troisième partie du travail correspond à une expérimentation en conditions contrôlées (microcosmes de sol) nous permettant de coupler des outils moléculaires et isotopiques (ADN-SIP) pour cibler spécifiquement les populations microbiennes activement impliquées dans la dégradation des résidus de culture - etc / The effect of the location of wheat residues (soil surface vs. incorporated in soil) on their decomposition and on soil bacterial communities was investigated by the means of a field experiment. Bacterial-Automated Ribosomal Intergenic Spacer Analysis (B-ARISA) of DNA extracts from residues, detritusphere (soil adjacent to residues), and bulk soil evidenced that residues constitute the zone of maximal changes in bacterial composition. However, the location of the residues influenced greatly their decomposition and the dynamics of the colonizing bacterial communities. Sequencing of 16S rRNA gene in DNA extracts from the residues at the early, middle, and late stages of degradation confirmed the difference of composition of the bacterial community according to the location. Bacteria belonging to the -subgroup of proteobacteria were stimulated when residues were incorporated whereas the -subgroup was stimulated when residues were left at the soil surface. Moreover, Actinobacteria were more represented when residues were left at the soil surface. According to the ecological attributes of the populations identified, our results suggested that climatic fluctuations at the soil surface select populations harboring enhanced catabolic and/or survival capacities whereas residues characteristics likely constitute the main determinant of the composition of the bacterial community colonizing incorporated residues. Microbial communities are of major importance in the decomposition of soil organic matter. However, the identities and dynamics of the populations involved are still poorly documented. We investigated, in a eleven-month field experiment, how the initial biochemical quality of crop residues could lead to specific decomposition patterns, linking biochemical changes undergone by the crop residues to the respiration, biomass and genetic structure of the soil microbial communities. Wheat, alfalfa and rape residues were incorporated into the 0-15 cm layer of the soil of field plots by tilling. Biochemical changes in the residues occurring during degradation were assessed by near infrared spectroscopy (NIRS). Qualitative modifications in the genetic structure of the bacterial communities were determined by Bacterial-Automated Ribosomal Intergenic Spacer Analysis (B-ARISA). Bacterial diversity in the three crop residues at early and late stages of decomposition process was further analyzed from a molecular inventory of the 16S rDNA. The decomposition of plant residues in croplands was shown to involve specific biochemical characteristics and microbial communities dynamics which were clearly related to the quality of the organic inputs. Decay stage and seasonal shifts occurred by replacement of copiotrophic populations/bacterial groups such as proteobacteria successful on younger residues with those successful on more extensively decayed material such as Actinobacteria. However, relative abundance of proteobacteria depended greatly on the composition of the residues, with a gradient observed from alfalfa to wheat, suggesting that this bacterial group may represent a good indicator of crop residues degradability and modifications during the decomposition process...

The present thesis proposes new methods for obtaining objective and accurate diagnoses in modern healthcare. Non-invasive techniques have been used to examine or diagnose three different medical conditions, namely neuropathy among diabetics, radiotherapy induced erythema (skin redness) among breast cancer patients and diagnoses of cutaneous malignant melanoma. The techniques used were Near-InfraRed spectroscopy (NIR), Multi Frequency Bio Impedance Analysis of whole body (MFBIA-body), Laser Doppler Imaging (LDI) and Digital Colour Photography (DCP). The neuropathy for diabetics was studied in papers I and II. The first study was performed on diabetics and control subjects of both genders. A separation was seen between males and females and therefore the data had to be divided in order to obtain good models. NIR spectroscopy was shown to be a viable technique for measuring neuropathy once the division according to gender was made. The second study on diabetics, where MFBIA-body was added to the analysis, was performed on males exclusively. Principal component analysis showed that healthy reference subjects tend to separate from diabetics. Also, diabetics with severe neuropathy separate from persons less affected. The preliminary study presented in paper III was performed on breast cancer patients in order to investigate if NIR, LDI and DCP were able to detect radiotherapy induced erythema. The promising results in the preliminary study motivated a new and larger study. This study, presented in papers IV and V, intended to investigate the measurement techniques further but also to examine the effect that two different skin lotions, Essex and Aloe vera have on the development of erythema. The Wilcoxon signed rank sum test showed that DCP and NIR could detect erythema, which is developed during one week of radiation treatment. LDI was able to detect erythema developed during two weeks of treatment. None of the techniques could detect any differences between the two lotions regarding the development of erythema. The use of NIR to diagnose cutaneous malignant melanoma is presented as unpublished results in this thesis. This study gave promising but inconclusive results. NIR could be of interest for future development of instrumentation for diagnosis of skin cancer.

Orientador: Rickson Coelho Mesquita / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-30T22:43:33Z (GMT). No. of bitstreams: 1 QuirogaSoto_AndresFabian_M.pdf: 7858431 bytes, checksum: cab3b799ea039aaac9d7d8039a9590ed (MD5) Previous issue date: 2016 / Resumo: A espectroscopia óptica de difusão DOS é uma técnica que usa luz no regime do infravermelho próximo (NIR) para extração de informações fisiológicas em tecidos biológicos de forma não invasiva, tais como as concentrações de oxi-hemoglobina (HbO) , desoxi-hemoglobina (Hb) e a saturação de oxigênio no tecido (StO_2). Esta técnica baseia-se no fato de que a luz do infravermelho próximo se propaga difusivamente no tecido biológico, conseguindo se aprofundar alguns centímetros e voltar na superfície de incidência, e sofrendo alterações ao atravessar o meio devido à absorção e ao espalhamento do tecido. Este enfoque utiliza a equação de difusão para o modelamento da luz e suas soluções para conseguir as propriedades ópticas absolutas, que permite inferir as informações fisiológicas do tecido. A técnica experimental DOS utiliza fontes que emitem pulsos ultracurtos (Time Domain DOS) ou intensidades moduladas (Frequency Domain DOS) para extrair tais informações. No entanto, a implementação destas técnicas requerem uma eletrônica avançada, tornando a construção complicada ou a aquisição custosa. Por outro lado, os equipamentos que usam fontes contínuas medem apenas variações relativas dos coeficientes de absorção do tecido. Neste trabalho, estudou-se uma nova metodologia a partir da espectroscopia óptica de difusão usando fontes de onda contínua para vários comprimentos de ondas (CW-DOS) a fim de extrair os valores absolutos de absorção e espalhamento do tecido. A metodologia foi validada com dados ópticos em phantoms e camundongos, conseguindo inferir as propriedades ópticas absolutas para cada estágio. Os resultados refletem que a metodologia é uma boa alternativa para extração de informação fisiológica de forma simples e confiável, e que serve como base para a construção de novos equipamentos de DOS / Abstract: Diffuse Optical Spectroscopy (DOS) is a technique that employs near infrared (NIR) light to noninvasively extract physiological information from biological tissue, such as microvascular oxy-hemoglobin (HbO) and deoxy-hemoglobin (Hb) concentrations, and tissue oxygen saturation (StO_2). DOS is based on the fact that NIR light diffuses through deep tissue and interacts with tissue cells and molecules before returning to the surface. Therefore, the tissue composition can be estimated by the absorption and scattering coefficients, which can be monitored by the intensity detected of scattered light. DOS uses the diffusion equation for modeling light propagation, and its solutions to estimate the absolute optical properties. Typical experimental methods in DOS employ ultrashort-pulsed light sources (Time Domain DOS) or intensity modulated light sources (Frequency Domain DOS) to extract such information. However, the implementation of these techniques requires advanced electronics, which makes its use complicated and/or expensive. Instruments that use continuous-wave (CW- DOS) light sources are limited to estimate relative changes of the absorption coefficient, only. In this dissertation, we analyze a methodology based on continuous-wave diffuse optical spectroscopy with several wavelengths to estimate the absolute values of absorption and scattering coefficients of biological tissue. The methodology was validated in optical phantoms and in mice. Our results suggest that the methodology can be a good approach for estimating physiological information in a simple and reliable way, and it can be used as the basis for the construction of new DOS equipments / Mestrado / Física / Mestre em Física / 1373920/2014 / CAPES

Le taux de survie des patients souffrant d’un arrêt cardiaque extrahospitalier est inférieur à 10% même avec les meilleures pratiques en réanimation. Une nouvelle technique de réanimation, soit la réanimation par circulation extracorporelle, a été mise à l’essai et s’avère prometteuse pour améliorer le pronostic chez cette population. Par contre, des réponses à plusieurs enjeux doivent être obtenues avant de tester de façon prospective les avantages de cette technique, notamment quant aux impacts collatéraux sur les pratiques de réanimation préhospitalière qu’elle impliquerait, à la sélection des patients et aux potentielles stratégies de monitorage à utiliser chez ces patients. Cette thèse vise à répondre à ces questions avant d’éventuellement démontrer la valeur ajoutée de cette technique de réanimation et ainsi améliorer la survie pour ces patients. Le premier volet présente les résultats de trois études de cohorte explorant les impacts qu’aurait l’incorporation de la réanimation par circulation extracorporelle sur les protocoles de soins. Les résultats d’une première étude de cohorte ont démontré que la durée des manœuvres de réanimation avancées pratiquées en préhospitalier pourrait être réduite pour permettre un départ plus rapide vers un centre hospitalier pouvant initier la réanimation par circulation extracorporelle puisqu’il n’y avait pas d’association positive entre la durée de ces manœuvres et la survie chez ces patients. Les résultats d’une deuxième étude ont démontré que de rediriger les patients en arrêt cardiaque vers les centres hospitaliers pouvant pratiquer la réanimation par circulation extracorporelle pourrait augmenter leur taux de survie. Ce bénéfice potentiel subsistait jusqu’à un ajout de 14 minutes de la durée du trajet par ambulance dû à la redirection. Troisièmement, la modification de ces deux protocoles de soins permettrait à potentiellement trois fois plus de patients de bénéficier d’une réanimation par circulation extracorporelle. Le second volet présente les résultats de deux études visant à optimiser la sélection des patients pour une réanimation par circulation extracorporelle. Les résultats d’une première étude de cohorte descriptive ont démontré que les patients nécessitant plus de 10 défibrillations conservaient un pronostic de survie adéquat, et ainsi devraient demeurer éligible à une réanimation par circulation extracorporelle. Dans une deuxième étude de cohorte, nous avons étudié l’impact pronostique d’une conversion de rythme pendant la réanimation et avons démontré que le rythme initial était un meilleur marqueur de pronostic que la conversion du rythme. Ainsi, les patients ayant une conversion d’un rythme non-défibrillable à un rythme défibrillable ne devraient pas être retenus en première intention pour une réanimation par circulation extracorporelle, contrairement à ceux dont le rythme initial était déjà défibrillable. Les études du troisième volet visaient à explorer l’usage d’une technologie de monitorage de l’oxymétrie tissulaire, la spectroscopie proche-infrarouge, en raison de son potentiel pour mesurer en continu le degré d’oxygénation des candidats à une réanimation par circulation extracorporelle. Une revue systématique de la littérature a démontré l’utilité pronostique de cette technologie pour les patients en arrêt cardiaque. Ensuite, nous avons décrit à l’aide d’une cohorte prospective les propriétés métrologiques de deux appareils et les facteurs associés permettant d’optimiser leur utilité dans le contexte de patients en arrêt cardiaque. Les connaissances développées par l’entremise des études composant la présente thèse ont déjà été intégrées aux protocoles de prise en charge des patients souffrant d’un arrêt cardiaque extrahospitalier ce qui jette des bases solides pour poursuivre des recherches pour ultimement améliorer leur pronostic. / Despite advances in medical care, survival amongst out of hospital cardiac arrest patients remains low, with only 10% of patients surviving. The use of extracorporeal cardiopulmonary resuscitation, a novel resuscitation procedure, has recently garnered interest and showed promise to improve resuscitation outcomes. However, questions remain to be answered before this technology can be prospectively evaluated, notably regarding the collateral impacts of its implementation, appropriate patient selection and the monitoring strategies to use for these patients. The main objective of this thesis is to answer these questions to eventually improve the outcome of patients suffering from an out-of-hospital cardiac arrest. In the first part, the results of three cohort studies exploring the potential impact of the implementation of extracorporeal resuscitation on prehospital resuscitation protocols are presented. A first cohort study showed that the duration of prehospital advanced cardiac life support could be reduced to allow for an earlier transport to an extracorporeal resuscitation centre. A second cohort study showed that patients being transported to specialized resuscitation centres might have increased survival. This increase in survival would remain despite an additional 14 minutes of prehospital transport time due to the redirection. A third study showed that prehospital redirection could triple the number of patients who could benefit from extracorporeal resuscitation. In the second part, the results of two studies aiming to improve the selection of adequate patients for extracorporeal resuscitation are presented. A first cohort study showed that patients requiring more than 10 defibrillations still had an adequate chance at survival and should remain eligible for an extracorporeal resuscitation. A second cohort study showed that the initial rhythm was a much better prognosticating factor than subsequent rhythms. Patients with an initial non- shockable rhythm who experience a conversion to a shockable rhythm should not be considered first-line candidates for extracorporeal resuscitation. In the third part, three studies exploring the potential uses of near-infrared spectroscopy for the monitoring of extracorporeal resuscitation patients are presented. A systematic review was first performed and showed the prognosticating ability of this technology for patients suffering from a cardiac arrest. Then, using a prospective cohort, the metrological properties and their determinants of two frequently used near-infrared spectroscopy devices were described, in order to optimize their uses in the context of cardiac arrest. The knowledge acquired by the studies comprised in this thesis has already been integrated in protocols guiding the care for patients suffering from an out-of-hospital cardiac arrest and has laid the foundation for the prospective evaluation of extracorporeal resuscitation for this population, which will hopefully ultimately lead to improvement in their prognosis.

Les patients coronariens (PC) sont plus à risque de présenter des déficits cognitifs et certains types démence. Les fonctions cognitives des PC ont été étudiées au repos, mais jamais au cours d’une séance d’exercice aigu. L’exercice aigu à haute intensité peut affecter négativement la performance cognitive chez des personnes saines. Bien que les PC soient plus à risque de dysfonctions cérébrales et cardiovasculaires, cette relation n’a jamais été étudiée au sein de cette population clinique et peut permettre de mieux comprendre l’axe coeur-cerveau. Il était postulé que la performance cognitive sera affectée par l’exercice à haute intensité due à une diminution de l’apport en oxygène seulement chez les patients coronariens. Trente-huit PC et 16 participants sains ont été recrutés. Les participants ont complété les mesures suivantes : (1) des tests neuropsychologiques et une familiarisation à la tâche de Stroop modifiée informatisée (2) un test mesurant la consommation d’oxygène jusqu’au pic de l’effort (VO2pic) et (3) la tâche de Stroop à 30% et 70% de leur puissance maximale atteinte au VO2pic tout en pédalant sur un ergomètre. L’oxygénation cérébrale a été mesurée grâce à la spectroscopie proche infrarouge. Les résultats ont démontré que la performance cognitive est restée stable entre les deux intensités pour les deux groupes. Chez les PC, le volume sanguin cérébral était affecté négativement par l’effort physique à haute intensité comparativement à l’intensité modérée et aux participants sains. La maladie coronarienne affecte négativement l’oxygénation cérébrale pendant un effort à haute intensité. D’autres études sont nécessaires afin de déterminer si un test cognitif administré pendant un effort physique pourrait permettre d’identifier les patients coronariens à risque de déclin cognitif. / Coronary heart disease (CHD) patients are at higher risk for developing cognitive deficits and certain types of dementia. The cognitive functions of coronary patients have been studied at rest, but never during an acute exercise session. Acute high intensity exercise negatively affects cognitive performance in healthy people. Although coronary patients are at higher risk of cerebral and cardiovascular dysfunction, this relationship has never been studied in this clinical population and could help better understanding of the heart-brain axis. The aim of this study was to measure the effects of an acute exercise at two different intensities on cognitive performance and cerebrovascular response in CHD patients. It was hypothesized that higher exercise intensity will impair executive performance and cerebrovascular response only in CHD patients. Thirty-eight CHD patients and 16 healthy controls completed neuropsychological assessments, maximal cardiopulmonary exercise testing and two exercise bouts at 30% and 70% of their individualized maximum capacity on an ergocycle while performing a cognitive test including non-executive and executive conditions. Cerebral oxygenation and perfusion were measured during both intensities in all participants with near-infrared spectroscopy. The results demonstrated that the cognitive performance remained stable between the two intensities for both groups. In CHD patients only, cerebral blood volume was negatively affected by high intensity exercise compared with moderate intensity. Coronary heart disease negatively affects cerebral oxygenation during high intensity exercise. Further studies are needed to determine whether a cognitive test administered during physical exertion could identify coronary patients at risk of cognitive decline.