Assisted reproductive technology (ART) has been rapidly expanding since the birth of Louise Brown, the first test tube baby, in 1978. Although an increasingly complex array of laboratory skills and procedures have been developed for infertility treatments, the success rate of ART remains low. In an attempt to make ART safer and more efficient, international medical practice is trending towards single embryo transfers and the use of innovative, sophisticated technologies to identify promising gametes and embryos with the highest potential to generate a pregnancy. Laser technology is increasingly being used to accomplish these aims. The application of lasers for ART has been successfully employed in clinical practice for some time now and is continually the subject of investigative research in order to generate new methods to improve operations. Moreover, lasers serve as a powerful tool at the forefront of investigative research in the reproductive sciences, assisting in broadening our understanding of reproductive and developmental biology. Nevertheless, there is a paucity of literature pertaining to the safe standardisation of such laser procedures with evidence at the molecular level. The primary aim of this thesis was to optimise applications of laser technology for clinical ART and research applications in the reproductive sciences. This thesis utilised the mouse embryo model to investigate potential deleterious effects of different laser treatment applications, both by the operator and hardware manufacturer. Safe and unsafe laser operator parameters were elucidated by assessing deleterious effects to the plasma membrane integrity, blastocyst survival rate, DNA fragmentation levels, and changes in gene expression of key developmental genes. The effect of altering the laser hardware to lower the power output was evaluated and it was determined that if a lower power laser is used to deliver a set amount of energy over a longer period of time, a smaller amount of damage is incurred. Work in this thesis also established a new method in which laser technology can be used as a research tool for the reproductive sciences, by creating a novel stimuli-responsive laser-activated nanoparticle delivery system with spatial control and increased efficiency in a mammalian cell model. The field of reproductive science continues to benefit greatly from laser application clinically to improve infertility treatments, and in research, to elucidate mechanisms underlying infertility, with a hope of increasing our understanding and eventually developing new treatment options.

FERNANDES, César Rodrigues. Espectroscopias Raman e infravermelho em cristais de aminoácidos : os casos da L-valina e do ácido L-glutâmico. 2015. 264 f. Tese (Doutorado em Física) - Programa de Pós-Graduação em Física, Departamento de Física, Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2015. / Submitted by Edvander Pires (edvanderpires@gmail.com) on 2015-04-09T21:07:04Z No. of bitstreams: 1 2015_tese_crfernandes.pdf: 8055322 bytes, checksum: 64f46f4716b7bda3f85f0cf3a7bab81d (MD5) / Approved for entry into archive by Edvander Pires(edvanderpires@gmail.com) on 2015-04-10T20:43:31Z (GMT) No. of bitstreams: 1 2015_tese_crfernandes.pdf: 8055322 bytes, checksum: 64f46f4716b7bda3f85f0cf3a7bab81d (MD5) / Made available in DSpace on 2015-04-10T20:43:31Z (GMT). No. of bitstreams: 1 2015_tese_crfernandes.pdf: 8055322 bytes, checksum: 64f46f4716b7bda3f85f0cf3a7bab81d (MD5) Previous issue date: 2015 / Estudar o comportamento dos aminoácidos quando sujeitos a condições extremas de temperatura é o objetivo principal dessa tese. Na L-valina (C_5 H_11 NO_2) foram realizados experimentos de absorção infravermelha, enquanto que experimentos de espalhamento Raman foram realizados nas fases α e β do ácido L-glutâmico (C_5 H_9 NO_4). Para a L-valina, o experimento de infravermelho foi realizado em duas regiões espectrais: na primeira o intervalo analisado foi de ~10 a ~700 cm-1 (englobando a região do infravermelho distante – FAR-IR); na segunda, o intervalo analisado foi de 370 a 4000 cm-1 (englobando a região conhecida como infravermelho médio: MID-IR). Nos experimentos Raman no ácido L-glutâmico, o intervalo espectral entre ~15 e ~4000 cm-1 foi estudado. Nos experimentos de infravermelho, o parâmetro termodinâmico temperatura assumiu valores de 100 K até 300 K espaçados por 20 K. Nos experimentos Raman conseguiu-se um espaçamento de 50 K com a temperatura variando de 18 a 300 K, tanto para a fase α como para a fase β. Na fase β, diversas geometrias de espalhamento foram utilizadas, enquanto que para a fase α somente uma geometria de espalhamento foi analisada. Da análise dos espectros da L-valina foram observados surgimentos e desaparecimentos de modos na região do infravermelho distante (FAR-IR). Um modo de rede localizado em 103 cm^(-1), desdobra-se em dois modos de maneira rápida, e diferente do que seria esperado pela evolução espectral ω x T. Situação inversa, ocorre quando dois modos colapsam em 163 cm^(-1) e, interessantemente, à mesma temperatura que no desdobramento: ~120K. Nas mesmas condições outros dois modos, em ~211 cm^(-1) e em ~216 cm^(-1) se reduzem a um único modo em ~214 cm^(-1). Um pico em ~190 cm-1 desaparece no intervalo 100-120 K. Nesse intervalo também podemos verificar grandes desvios da linearidade das frequências dos modos em 147 cm^(-1), 196 cm^(-1), 225 cm^(-1) e 305 cm^(-1). Mais ainda, os modos vibracionais em 154cm^(-1) e 214 cm^(-1) apresentam descontinuidade (nesse caso, verificadas entre 120 e 160 K). Isso sugere não se tratar de simples mudanças conformacionais, posto que tais ocorrências (desdobramentos, desaparecimentos e fortes não linearidades dos modos) se dão num intervalo particular de temperatura. Pode-se concluir daí que o cristal sofre uma transição de fase estrutural a partir de 120 K, se completando a 100 K. Observe-se que para a região MID, a L-valina não apresenta alterações espectrais significativas: as frequências dos modos no geral são lineares, constantes e sem descontinuidades. As medidas Raman na forma β do ácido L-glutâmico resultaram num número constante de modos de vibração na região dos modos da rede durante todo o resfriamento, o que foi interpretado como estabilidade do material. Entretanto, houve colapso (eg.:~500 cm-1, 200 K, Z(XX)Z; três bandas tornaram-se duas) e surgimento (eg.: ~930 cm-1, 120 K, Z(XX)Z; uma banda torna-se duas) de bandas em outras regiões do espectro. Tais ocorrências foram interpretadas como alteração do ambiente da molécula (~930 cm-1), efeito de “aliasing” dificultando o ajuste por lorentzianas (eg.: ~1070 cm-1), e mudança de conformação. Por não estarem associados a levantamentos nem incrementos de degenerescência, tais comportamentos sugerem estabilidade do ácido L-glutâmico na forma β. Os espectros Raman obtidos para a fase α do ácido L-glutâmico se apresentaram completamente regulares: modos lineares, sem descontinuidades nas frequências nem mudança no número de modos. A partir de todos os resultados obtidos, procurou-se entender que fatores determinam a estabilidade de um cristal de aminoácido. A análise do comportamento desta família de materiais mostra três “níveis” de estabilidade (i) estáveis (e.g.: ácido L-glutâmico e L-isoleucina), (ii) microtransições conformacionais (complexo comportamento vibracional, e.g.: L-alanina) e (iii) cristais que sofrem transição de fase estrutural (e.g.: L-valina e L-leucina). Fatores como ordenamento de cadeias laterais, forças de van der Waals e comprimento médio das ligações de hidrogênio (d ̅_LH) podem influenciar na estabilidade destas estruturas cristalinas. Entretanto, observando somente os comprimentos médios das ligações de hidrogênio (d ̅_LH) foi possível inferir uma relação entre esse valor e a estabilidade: L-valina e taurina sofrem transição (〖d ̅_LH〗_(L-val)=2.92 Å, 〖d ̅_LH〗_tau=2.90 Å), L-alanina ⇒ micro-transição conformacional (〖d ̅_LH〗_(L-ala)=2.83 Å) e ácido L-glutâmico estável (〖d ̅_LH〗_(L-glu(α))=2.771 Å, 〖d ̅_LH〗_(L-glu(β))=2.798 Å). Nota-se que: 〖d ̅_LH〗_(L-glu(α,β))<〖d ̅_LH〗_(L-ala)<〖d ̅_LH〗_(L-val),〖d ̅_LH〗_tau. A L-treonina constitui exceção, pois é estável embora possua 〖d ̅_LH〗_(L-treo)=2.86 Å. Outras técnicas experimentais (e.g.: difração e espalhamento de nêutrons) são sugeridas para serem utilizadas futuramente na abordagem deste problema.

High combustion temperatures are required in gas-turbine engines to achieve high cycle efficiencies. With increasing temperature, however, the life span of the turbine components are reduced. The ability to accurately predict engine component temperature as a function of combustion temperature is required to strike this balance correctly. An experimental heat transfer measurement technique is developed in this thesis, which builds on a large body of existing literature. The technique enables a detailed quantification of turbine heat transfer on test rigs which closely represent gas-turbine engine configurations. Fundamental improvements are made to existing methods, in the definition of the ‘semi- infinite limit’ for transient measurement techniques, in Infra-red camera calibration, and in thermal effusivity measurement. The improvements were developed from first principles, verified experimentally, and have been used on a world leading heat transfer rig (the FACTOR combustor-turbine interaction rig, run on the NG-Turb facility at DLR Göttingen). It was found that optimisation of a number of measurement parameters was required to minimise the measurement uncertainty. It is shown that the optimum measurement parameters are dependant, and sensitive to the specific configuration of the test rig. An experimental procedure was developed and tested, which has been ‘tuned’ for measurements on the FACTOR test rig. Despite the challenging measurement environment on the FACTOR rig, it was found that state-of-the-art heat transfer measurement uncertainties of approximately 5%, could nevertheless still be achieved, by using the new methods. General principles and rules are established which can be used to guide the design of future heat transfer measurements, with the aim of minimising measurement uncertainty.

Made available in DSpace on 2014-06-11T19:25:33Z (GMT). No. of bitstreams: 0 Previous issue date: 2007-05-22Bitstream added on 2014-06-13T19:12:25Z : No. of bitstreams: 1 menegazzo_lm_me_ilha.pdf: 652340 bytes, checksum: 7cd3c65c7db0577bbe66236ac50269ff (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Este trabalho propõe o estudo do grau de conversão e de dureza de três resinas fotoativadas Fill Magic, TPH Spectrum e Te-Econom, em função do tempo de exposição e do tipo de fonte de luz. Foram utilizadas quatro fontes diferentes, sendo duas halógenas e duas baseadas em LED. O grau de conversão foi avaliado de espectros de absorção no infravermelho próximo e a dureza através de testes Vickers. Cinco amostras de 10 mm de diâmetro e 2 mm de espessura foram preparadas para cada tempo de exposição e tipo de fonte. Após exposição à luz, todas as amostras foram mantidas durante 7 dias em ambiente escuro antes de serem utilizadas para obtenção de espectros e serem submetidas ao teste de dureza. Os espectros foram obtidos em um espectrômetro Nexus 670 da Nicolet e a microdureza Vickers foi obtida com um microdurômetro HMV - 2T da Shimadzu. Os resultados mostraram que o grau de conversão aumenta com o tempo de exposição para fontes com densidade de potência menor que 233 mW/cm2. Não foi observada diferença significativa no grau de conversão nas amostras irradiadas com fontes halógena e LED, ambas com densidade de potência maior que 233 mW/cm2. Não foi possível estabelecer uma relação entre dureza e o tempo de exposição ou a densidade de potência. Entre as resinas, a FM é a que apresentou melhores valores de grau de conversão e a Te-Econom de dureza. / The aim of this study was to evaluate the degree of conversion and hardness of three photo-activated composites (Fill Magic, TPH Spectrum and Te-Econom) as a function of exposure time and type of light source. As visible light source were utilized four different units, two halogen and two light-emitting diodes (LED). The conversion degree was evaluated by near-infrared spectroscopy and the hardness by Vickers tests. Five samples of 10 mm diameter and 2 mm thickness were prepared for each exposure time and light source. The spectra were obtained in a Nexus 670 Nicolet spectrometer and the hardness in a HMV - 2T micro hardness tester (Shimadzu). These measurements were performed after 7 days dark storage. The results showed that the degree of conversion increases with the exposure time for the light units with power density smaller than 233 mW/cm2. No significant differences were observed in degree of conversion in samples irradiated with halogen and LED units, both with power density larger than 233 mW/cm2. There is not correlation between the conversion degree and the micro hardness for all studied composites. The highest values for conversion degree and hardness were obtained with the Fill Magic and Te-Econom composites, respectively.

Incineration of waste materials has become a common way to handle a worldwide increase of produced waste materials. The problem with waste as fuel is that the material is not homogeneous and include a mixture of fossils and renewables. The fossil part ends up in an emission of fossil carbon dioxide in a combustion process, which is included in the emissions trading system. However, since waste material varies a lot in composition depending on the time of the year, origins, etc. it is preferable to have a method for real-time measurement of the fossil share of combusted waste. No real-time measurement technologies are available today which is the reason to investigate if near-infrared (NIR) spectroscopy could be a potential solution. An artificial mixture of refused derived fuel has been used to investigate the possibilities of NIR for prediction of the fossil share in waste material. The fossil share is assumed to be equal to the content of plastic material with an origin of oil products. Mixtures with different plastic content are scanned by the NIR instrument to obtain individual absorption spectra. A Partial least square (PLS) regression model is created on measured spectra and known content of plastics. The best model for the prediction on new spectral data using one of four measured replicates is a PLS model preprocessed with Savitzky-Golay smoothing that gives an R-square value of 0,782. If the prediction is done, depending on a delimitated wavenumber interval and an average of all four replicates is the best model instead of a PLS model pre-processed with standard normal variate without seven outliers that have an R-square value of 0,81. R-square value is the coefficient of determination which has been used to figure out the best model. An R-square value above 0,65 are recommended for process modelling, where 1 is the highest possible value.

Orientador: João Carlos Silos Moraes / Banca: Marco Antonio Utrera Martines / Banca: Paulo Henrique dos Santos / Resumo: Este trabalho propõe o estudo do grau de conversão e de dureza de três resinas fotoativadas Fill Magic, TPH Spectrum e Te-Econom, em função do tempo de exposição e do tipo de fonte de luz. Foram utilizadas quatro fontes diferentes, sendo duas halógenas e duas baseadas em LED. O grau de conversão foi avaliado de espectros de absorção no infravermelho próximo e a dureza através de testes Vickers. Cinco amostras de 10 mm de diâmetro e 2 mm de espessura foram preparadas para cada tempo de exposição e tipo de fonte. Após exposição à luz, todas as amostras foram mantidas durante 7 dias em ambiente escuro antes de serem utilizadas para obtenção de espectros e serem submetidas ao teste de dureza. Os espectros foram obtidos em um espectrômetro Nexus 670 da Nicolet e a microdureza Vickers foi obtida com um microdurômetro HMV - 2T da Shimadzu. Os resultados mostraram que o grau de conversão aumenta com o tempo de exposição para fontes com densidade de potência menor que 233 mW/cm2. Não foi observada diferença significativa no grau de conversão nas amostras irradiadas com fontes halógena e LED, ambas com densidade de potência maior que 233 mW/cm2. Não foi possível estabelecer uma relação entre dureza e o tempo de exposição ou a densidade de potência. Entre as resinas, a FM é a que apresentou melhores valores de grau de conversão e a Te-Econom de dureza. / Abstract: The aim of this study was to evaluate the degree of conversion and hardness of three photo-activated composites (Fill Magic, TPH Spectrum and Te-Econom) as a function of exposure time and type of light source. As visible light source were utilized four different units, two halogen and two light-emitting diodes (LED). The conversion degree was evaluated by near-infrared spectroscopy and the hardness by Vickers tests. Five samples of 10 mm diameter and 2 mm thickness were prepared for each exposure time and light source. The spectra were obtained in a Nexus 670 Nicolet spectrometer and the hardness in a HMV - 2T micro hardness tester (Shimadzu). These measurements were performed after 7 days dark storage. The results showed that the degree of conversion increases with the exposure time for the light units with power density smaller than 233 mW/cm2. No significant differences were observed in degree of conversion in samples irradiated with halogen and LED units, both with power density larger than 233 mW/cm2. There is not correlation between the conversion degree and the micro hardness for all studied composites. The highest values for conversion degree and hardness were obtained with the Fill Magic and Te-Econom composites, respectively. / Mestre

FundaÃÃo Cearense de Apoio ao Desenvolvimento Cientifico e TecnolÃgico / A composiÃÃo quÃmica de oito marcas comerciais de cones de guta-percha foi determinada e seus resultados correlacionados com a capacidade de selamento apical. As marcas investigadas foram: (AnalyticÃ, DenstplyÃ, DiadentÃ, MetaÃ, ObturaÃ,OdusÃ, Tanarià e UltimateÃ). Os componentes dos cones de guta-percha (ZnO, BaSO4, guta-percha e ceras ou resinas) foram inicialmente obtidas pelo mÃtodo de Friedman at al 38. A composiÃÃo dos cones foi obtida por anÃlise gravimÃtrica, microanÃlise de energia dispersiva de raios-X, difraÃÃo de raios-X e anÃlise elementar. O polÃmero guta-percha foi caracterizado por analise tÃrmica (TGA e DSC), viscosidade intrÃnseca, cromatografia de permeaÃÃo em gel, infravermelho e ressonÃncia magnÃtica nuclear. O mÃtodo descrito por Friedman et al 38 foi apropriado para quantificar os componentes do cone como a guta-percha e ceras/resinas, mas superestimou a quantidade de sulfato de bÃrio e Ãxido de zinco. Um aumento na mÃdia de sulfato de bÃrio de 3,5% em relaÃÃo ao valor correto de sulfato de bÃrio e de 43,6% em relaÃÃo a massa do cone foi observado. Os cones de guta-percha contem em torno de 14,5 a 20,4% de guta-percha e de 62,8 a 84,3% de Ãxido de zinco. Sulfato de bÃrio nÃo foi determinado em trÃs dessas marcas (DentsplyÃ, Odusà e TanariÃ). As anÃlises de TGA mostraram que os resÃduos inorgÃnicos obtidos por essa tÃcnica à similar aos resÃduos inorgÃnicos observados na anÃlise gravimÃtrica. As fases cristalinas do polÃmero guta-percha foram identificadas por DSC. As marcas AnalyticÃ, DiadentÃ, MetaÃ, ObturaÃ, Odusà e Tanarià apresentaram picos endotÃrmicos caracterÃsticos da b guta-percha. Nas duas outras marcas o polÃmero esta presente na fase a. A determinaÃÃo da massa molar por anÃlise viscosimÃtrica mostrou valores similares para sete marcas variando de 1,0 x 105 a 1,6 x 105 g/mol, entretanto o polÃmero presente na marca Tanarià apresenta uma menor massa molar (5,6 x 104 g/mol). Resultado similar foi obtido por GPC. / The chemical composition of eight commercially available of gutta-percha cones brands was determined and the results correlated with the apical seal ability. These brands were: (AnalyticÃ, DentsplyÃ, DiadentÃ, MetaÃ, ObturaÃ, OdusÃ, Tanarià and UltimateÃ). The gutta-percha cones components (ZnO, BaSO4, gutta-percha, wax and resins) were initially obtained by Frideman et al 38 method. The composition of cones was obtained by gravimetric analysis, energy-dispersive X-ray microanalysis, X-ray diffraction and elemental analysis. The gutta-percha polymer was characterized by thermal analysis (TGA and DSC), intrinsic viscosity, gel permeation chromatography, infrared and nuclear magnetic resonance. The method described by Friedman et al 38 was appropriated to quantify gutta-percha and resin/wax components of cones, but led to overestimation of barium sulphate and zinc oxide. An average increase in the amount of barium sulfate of 3.5% in relation to the corrected BaSO4 mass value and of 43.6% in relation to cone mass was observed. Gutta-percha content range from 14.5 to 20.4% and zinc oxide from 62.8 to 84.3%. Barium sulphate was not detected in three of these brands (DentsplyÃ, Odusà and TanariÃ). TGA analysis shows that the inorganic residue obtained in this technique is similar of the inorganic residues observed in the gravimetric analysis. Crystal phases of gutta-percha polymer were identified by DSC. AnalyticÃ, DiadentÃ, MetaÃ, ObturaÃ, Odusà and Tanarià brands presents endothermic peak characteristic of b-guttapercha. In the other two brands the polymer is present in the a-phase. Molar mass determination by viscometric analysis shows similar values of seven brands in the average of 1.0 x 105 to 1.6 x 105 g/mol, however the polymer present in the Tanarià brand has lower molar mass (5.6 x 104 g/mol). Similar results were obtained by GPC. 11 The polymer present in the eight brands were analysed by IV and NMR, transpolyisoprene was identified as the main polymer component in the gutta-percha cones. The infiltration results of five brands (DentsplyÃ, TanariÃ, ObturaÃ, Odusà and Analyticà ) indicates that the small amount of gutta percha and also the presence of the a-phase in the Dentsplyà brand may be responsible for the high infiltration observed. A poor sealing ability was observed for brands with gutta-percha content lower than 16%.

Ce travail avait pour objectif principal l’étude par spectroscopie vibrationnelle Raman et IR, couplée à l’analyse statistique de type ACP, la détection des changements moléculaires induits par différentesclasses d’antibiotiques (ampicilline, céfotaxime,tétracycline et ciprofloxacine) vis-à-vis de deux bactéries modèles (E. coli et V. parahaemolyticus). Dans le cas d’E. coli, l’ampicilline et le céfotaxime ont provoqué une baisse des bandes protéiques en Raman et IR, une augmentation des carbohydrates en IR.L’addition de la tétracycline a entraîné une augmentation des acides nucléiques, une forte baisse de la phénylalanine en Raman, une diminution des bandes protéiques et une augmentation de l’ADN en Raman et IR. Concernant la ciprofloxacine, une augmentation des acides nucléiques en Raman, une augmentation des bandes protéiques et de l’ADN en IR ont été observées. Chez V. parahaemolyticus, le céfotaxime a provoqué une baisse des protéines en Raman et Infra-rouge, une augmentation des polysaccharides en Infra-rouge. L’addition de la tétracycline a entraîné une baisse de la phénylalanine en Raman, une baisse des protéines en Raman et Infra-rouge, une augmentation des polysaccharides en Infra-rouge. Concernant la ciprofloxacine, une augmentation des polysaccharides et une diminution des bandes protéiques en Raman et IR ont été détectées. Une nette discrimination entre les échantillons traités aux antibiotiques et le témoin a été enregistrée chez E. coli et V. parahaemolyticus. Pour cette dernière, le profil de résistance à l’ampicilline a aussi été observé. Ce travail jette les bases d’une compréhension des mécanismes d’antibio-résistance dans les systèmes bactériens. / The present study aimed to explore Raman and IR in combination with PCA to detect molecularchanges induced by different classes of antibiotics(ampicillin, cefotaxime, tetracycline and ciprofloxacin) against two bacterial models (E.coli and V. parahaemolyticus) In E. coli,ampicillin and cefotaxime treatments led to a decrease of protein bands in both Raman and IR,an increase of carbohydrates in IR. Tetracycline addition caused an increase of nucleic acids, a sharp decrease of phenylalanine in Raman, a decrease of protein bands and an increase of DNA in both Raman and IR. For ciprofloxacin, an increase of nuleic acids in Raman, an increase of protein bands and DNA in IR were observed. In V. parahaemolyticus, cefotaxime resulted in a decrease of protein bands in both Raman and IR,an increase of polysaccharides in IR. Tetracycline increase of polysaccharides and a decrease of proteins in both Raman and Infra-red were noticed. Clear discrimination of antibiotic-treated samples compared to the control was recorded for the three antibiotic classes in both E. coli and V. parahaemolyticus. For the latter, resistance pattern has also been observed for ampicillin. This work lays the foundations for an understanding of the mechanisms of antibiotic resistance in the bacterial systems.

Implication de l’oxygénation cérébrale dans les limitations à l’exercice musculaire des personnes non-entraînées et sportifs d’endurance. L’objectif général de ce travail était de déterminer si l’oxygénation cérébrale était un facteur de la limitation à l’exercice de type aérobie. Dans un premier temps, nous nous sommes attachés à étudier le rôle de l’oxygénation cérébrale mesurée par la Spectroscopie dans le proche Infra-Rouge (NIRS) dans la limitation de l’exercice progressif maximal en rampe. Nous avons montré l’existence d’un seuil de déclin de l’oxygénation cérébrale associé au point de compensation respiratoire (RCP). L’amélioration de la performance avec une supplémentation d’O2 était liée au décalage de ce seuil à de plus hautes intensités d’exercice chez des sujets actifs (étude 1). Dans un second temps, nous avons montré que ce seuil de déclin de l’oxygénation, retrouvé aussi chez des sportifs entraînés en endurance apparaîssait à de plus hautes intensités d’exercice que chez des sujets non-entraînés (étude 2). Enfin, nous avons déterminé l’impact de l’hypoxémie artérielle induite par l’exercice (HIE) des sportifs d’endurance sur l’oxygénation cérébrale au cours d’un exercice maximal en rampe et d’un exercice de temps limite à charge constante. Nous avons ainsi montré que l’oxygénation cérébrale était augmentée avec la HIE suggérant un effet compensatoire à l’hypoxémie artérielle au cours de l’exercice progressif maximal en rampe. Ceci, n’existait pas au cours de l’exercice de temps limite ne supportant pas l’implication de l’oxygénation cérébrale dans ce type d’exercice (étude 3). Ces travaux ont donc mis en évidence l’implication de l’oxygénation cérébrale dans la limitation de l’exercice maximal en rampe chez des sujets actifs et des sportifs entraînés en endurance présentant ou pas une HIE. Toutefois, elle ne semble pas être un facteur majeur de limitation de l’exercice de temps limite. / Involvement of cerebral oxygenation in muscular exercice limitation in untrained and trained endurance men. A decrease in oxygen availability in the brain could be a physiological mechanism limiting aerobic fitness. We first studied the role of cerebral oxygenation measured by Near Infra-Red Spectroscopy (NIRS ) in maximal cycle ramp exercise limitation. We showed a cerebral oxygenation threshold decline associated with respiratory compensation point (RCP). This threshold appeared for higher exercise intensities -related to performance improvement with hyperoxia in untrained endurance men (study 1). Secondly , we showed that the cerebral oxygenation threshold in athletes occurred for higher sub-maximal exercise intensities than untrained (study 2). Finally , we determined the involvement of exercise-induced arterial hypoxemia (EIH) in endurance athletes on cerebral oxygenation during maximal cycle ramp exercice and exercice time to exhaustion. We showed that cerebral oxygenation was improved by EIH suggesting a compensatory effect of EIH during the maximal cycle ramp. This did not occur during exercise time to exhaustion, and does not support the involvment of cerebral oxygenation in this type of exercise (study 3). This work has therefore highlighted the involvement of cerebral oxygenation in maximal cycle ramp exercice limitation in untrained and trained endurance men with or without EIH. However, it was unlikely been the major factor limiting the exercise time to exhaustion.

Les cellules photoacoustiques sont des capteurs optiques qui utilisent l'absorption des photons par des molécules de gaz pour générer une onde de pression proportionnelle à leur concentration. Le signal photoacoustique est également inversement proportionnel au volume de la cellule. La miniaturisation de la cuve permet donc l’amélioration des performances du capteur. Le travail de cette thèse consiste en la conception, la réalisation et la caractérisation de cellules photoacoustiques résonantes différentielles d’Helmholtz (DHR) miniaturisées. Dans un premier temps, des simulations par la méthode des éléments finis de cellules à l'échelle millimétrique ont permis de montrer que la miniaturisation de ce type de résonateur est une voie prometteuse. Aussi, la réalisation ambitieuse d’une cellule DHR sur silicium a été engagée en utilisant les techniques de la microélectronique. Cependant, cette voie de miniaturisation extrême s'est heurtée à des difficultés de réalisation, qui n'ont pas permis d'obtenir des dispositifs fonctionnels. Une alternative de miniaturisation, à l'échelle centimétrique, utilisant des microphones MEMS du commerce, a donc été engagée. Trois cellules fabriquées par différentes méthodes ont été réalisées et testées pour la détection de méthane. La dernière génération a permis la détection d'environ 100 ppb de méthane avec un laser à cascade interbande commercial à 3,357 µm de longueur d’onde. Pour préparer la prochaine génération de cellules, l'optimisation de la géométrie a été effectuée par simulation. Cette optimisation permet d'envisager une augmentation de 43 % du signal par rapport à la cellule la plus performante. / Photoacoustic cells are optical sensors based on the absorption of photons by gas molecules. The pressure wave created by gas relaxation is proportional to the trace gas concentration. Furthermore the photoacoustic signal is inversely proportional to the cell volume. Thus cell miniaturization enables performances improvements. This work consists in designing, realizing and characterizing miniaturized photoacoustic cells, based on the differential Helmholtz resonator (DHR) principle. In a first phase, modeling by the finite element method of millimeter scale cells has shown that the miniaturization of this type of resonator should effectively improve the detection limit. Thus, the ambitious realization of a DHR cell on silicon by the use of microelectronic techniques has been attempted. However, this extreme miniaturization direction encountered design and fabrication difficulties which made the produced devices unusable. To overcome these difficulties, a miniaturization alternative, at the centimeter scale, using commercial MEMS microphones, has been carried out. Three cells have been built by different methods and have been tested for methane detection. The last cell generation can detect around 100 ppb of methane with a commercial interband cascade laser at 3.357 µm of wavelength. Finally, to anticipate the next cell generation fabrication, a geometry optimization has been performed by simulation. This optimization shows that a 43 % signal improvement, compared to the most performant cell already built.