Diffusion MRI is established as an essential tool for both clinicians as well as biomedical scientists. Its application plays an important role in diagnosis and management of acute stroke, tumors, trauma, and infectious disease, among myriad other applications. Furthermore, diffusion studies are crucial for understanding disease processes caused by developmental and neurodegenerative disorders. The latest developments in quantitative diffusion imaging have broadened the potential application of the technique for both clinical and research applications. However, ongoing research is critical in order to further improve the accuracy and reproducibility of quantitative diffusion MRI techniques. Correlation time diffusion (D-CT) is emerging as an alternative technique for obtaining diffusion qMRI data[1][2][3]. Using the D-CT technique, T1 relaxation data is analyzed, using a modified BPP relaxation theory, in order to calculate the correlation times of protons’ stochastic processes and relate these times to solution viscosity in order to calculate proton diffusion coefficients, ADCs. The purpose of our study was to compare age related changes, during childhood and early adulthood, of global brain diffusion coefficients obtained by correlation time technique to global brain diffusion coefficients obtained by a conventional pulsed field gradient technique. In our study, we used the data of 27 subjects (0.5-24 years old), who were scanned with Mixed-TSE and DW-SS-SE-EPI pulse sequences. Subsequently, we processed the resulting directly acquired images to generate T1, T2, PD, ADC maps as well as volumetric data. We used the student t-test and linear regression analysis to compare and interpret our data. Our results show a strong positive correlation between the volumetric data. Good correlation between ADC values was observed, with the widest discrepancy between DCT, DPFG (about 17%) observed in the youngest subjects, and the smallest discrepancy noted in the older subjects.

<p>This thesis presents the application of some of the NMR methods in studying host-guest complexes, mainly in solution. The general focus of the work is on investigating the reorientational dynamics of some small molecules that are bound inside cavities of larger moieties. In the current work, these moieties belong to two groups: cryptophanes and cyclodextrins. Depending on the structure of the cavities, properties of the guest molecules and the formed complexes vary. Chloroform and dichloromethane are in slow exchange between the cage-like cavity of the cryptophanes and the solvent, on the chemical shift time scale, whereas adamantanecarboxylic acid, quinuclidine and 1,7-heptanediol in complex with cyclodextrins are examples of fast exchange. Kinetics and thermodynamics of complexation are studied by measuring exchange rates and translational self-diffusion coefficients by means of 1-dimenssional exchange spectroscopy and pulsed-field gradient (PFG) NMR methods, respectively. The association constants, calculated using the above information give estimates of the thermodynamic stability of the complexes. Carbon-13 spin relaxation data were obtained using conventional relaxation experiments, such as inversion recovery and dynamic NOE, and in some cases HSQC-type (Hetereonuclear Single Quantum Correlation Spectroscopy) experiments. Motional parameters for the free and bound guest, and the host molecules were extracted using different motional models, such as Lipari-Szabo, axially symmetric rigid body, and Clore models. Comparing the overall correlation times and the order parameters of the free and bound guest with the overall correlation time of the host molecule one can estimate the degree of the motional restriction, brought by the complexation, and the coupling between the motion of the bound guest and the reorientation of the host molecule. In one case, the guest motions were also investigated inside the cavities of a solid host material.</p>

This thesis presents the application of some of the NMR methods in studying host-guest complexes, mainly in solution. The general focus of the work is on investigating the reorientational dynamics of some small molecules that are bound inside cavities of larger moieties. In the current work, these moieties belong to two groups: cryptophanes and cyclodextrins. Depending on the structure of the cavities, properties of the guest molecules and the formed complexes vary. Chloroform and dichloromethane are in slow exchange between the cage-like cavity of the cryptophanes and the solvent, on the chemical shift time scale, whereas adamantanecarboxylic acid, quinuclidine and 1,7-heptanediol in complex with cyclodextrins are examples of fast exchange. Kinetics and thermodynamics of complexation are studied by measuring exchange rates and translational self-diffusion coefficients by means of 1-dimenssional exchange spectroscopy and pulsed-field gradient (PFG) NMR methods, respectively. The association constants, calculated using the above information give estimates of the thermodynamic stability of the complexes. Carbon-13 spin relaxation data were obtained using conventional relaxation experiments, such as inversion recovery and dynamic NOE, and in some cases HSQC-type (Hetereonuclear Single Quantum Correlation Spectroscopy) experiments. Motional parameters for the free and bound guest, and the host molecules were extracted using different motional models, such as Lipari-Szabo, axially symmetric rigid body, and Clore models. Comparing the overall correlation times and the order parameters of the free and bound guest with the overall correlation time of the host molecule one can estimate the degree of the motional restriction, brought by the complexation, and the coupling between the motion of the bound guest and the reorientation of the host molecule. In one case, the guest motions were also investigated inside the cavities of a solid host material.

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O comportamento das formas de linha dos espectros de RMN estático em função da temperatura assim como os experimentos de PURE Exchange em uma dimensão (PUREX-1D) foram utilizados para elucidar detalhes da dinâmica molecular nos PnMA. Os experimentos PUREX-1D foram realizados na faixa de temperatura de Tg-145 o C a Tg. Nesta faixa de temperatura a dinâmica molecular dos PnMA acontece com tempos de correlação entre 500 micro e 10 milissegundos. Utilizando simulação espectral foi demonstrado que os espectros PUREX-1D dependem tanto do tempo de correlação quanto da geometria das reorientações moleculares. Este fato também foi usado para avaliar as características dos movimentos moleculares responsáveis pela reaxação estrutural beta nos PnMA. Foi observado que os pequenos ângulos de reorientação da cadeia principal associados com a relaxação estrutural beta aumentam com o aumento da temperatura e que os tempos de correlação do movimento podem apresentar uma larga distribuição. Análises das formas de linha obtidas através de experimentos de polarização cruzada (CP) em função da temperatura foram realizadas para se estudar o comportamento da dinâmica molecular responsável pela relaxações estruturais alfa e beta nos PnMA. Os experimentos CP foram realizados em uma faixa de temperaturas entre Tg-50 o C e Tg.+70 o C. Nesta faixa de temperatura as figuras de linha de RMN estática são altamente dependentes da temperatura, do tamanho e do volume do ramo lateral. A dinâmica molecular dos PnMA apresentou um movimento altamente anisotrópico sendo que a isotropização da conformação do espectro induzida pelos movimentos moleculares ocorreu apenas a temperaturas muito acima da Tg, contrariando o comportamento esperado para a maioria dos polímeros amorfos. / The behavior of the static NMR line shapes as a function of the temperature as well as one-dimensional Pure Exchange NMR experiments (PUREX-1D) were used to elucidate details of the molecular dynamics in PnMAs. The 1D-PUREX experiments were carried out in the temperature range of Tg-145 oC to Tg. In this range of temperature the molecular dynamics of PnMAs was found to occur with correlation times between 500m and 10ms. Using spectral simulations it was demonstrated that the 1D-PUREX spectra depend on both, the correlation time and geometry of the molecular reorientations. Hence this feature was used to evaluate the characteristics of the molecular motions responsible by the b structural relaxation of PnMAs. It was found that the small angles reorientation of main chain associated with the b-structural relaxation increases with the temperature and the correlation times present a possible broad distribution. Analysis of the NMR line shapes obtained in Cross Polarization (CP) experiments as a function of temperature was performed to study the behavior of the molecular dynamics responsible for the b and a structural relaxation. The CP experiments were performed in the temperature range of Tg-50 oC to Tg+70 oC. In this temperature range the static NMR line shapes are highly dependent on the temperature, size and bulk of the side-group. The dynamics of the PnMA presents a highly anisotropic motion and the isotropisation of conformation induced by the motion only occurs in temperatures well above Tg, contrary to the behavior of the most fragile amorphous polymers.

L’évolution des techniques altimétriques de la bande Ku Nadir vers la bande Ka et l’interféro-métrie large fauchée proche Nadir dans le contexte de la mission SWOT (« Surface Water Ocean Topography », CNES/NASA) soulève de nouvelles questions scientifiques quant à la validité des modèles de rétrodiffusion des surfaces d’eau dans cette bande de fréquence et les erreurs sur les estimations de hauteurs d’eau dues aux mouvements de ces surfaces au cours du temps. Un modèle de rétrodiffusion (GO4) adapté à la configuration SWOT est présenté. Il conserve la précision du modèle de référence de l’Optique Physique tout en gardant la simplicité du modèle plus couramment employé de l’Optique Géométrique. En plus du paramètre classique de pente, il introduit un paramètre supplémentaire, dit de « courbure effective » (msc). Le modèle permet l’inversion des paramètres de pente et de courbure de la surface sous certaines conditions déve-loppées dans ce manuscrit. La validité des modèles conjoints de rétrodiffusion en bande Ka et de surface d’eau a été vérifiée sur des mesures radar effectuées en soufflerie dans un environnement contrôlé. Dans une dernière partie, les propriétés temporelles du signal rétrodiffusé ont été étudiées, en particulier le temps de corrélation et le décalage Doppler induit par le mouvement des vagues. Nous étudions l’influence de ces quantités sur les performances de la synthèse SAR non focalisée du système SWOT. / The evolution of the altimetric techniques from Ku-band to Ka-band and the wide swath al-timetry in the context of the SWOT mission (« Surface Water Ocean Topography », CNES/NASA) raises new scientific questions about the validity of the backscattering models from water sur-faces in such a frequency band and errors in estimating water heights from time-evolving water surfaces. A backscattering model (GO4) adapted to the SWOT configuration is introduced. It preserves the accuracy of the referencial Physical Optics model while maintaining the simplicity of the clas-sical Optical Geometrics model. In addition to the classical slope parameter, it introduces another parameter called as « effective curvature » (msc). This model allows the inverson of the surface slope and curvature parameters under certain conditions which are developped in this manus-cript. The joint validity of the backscattering models in Ka-band and from water surfaces is che-cked from controlled wind-wave tank radar measurements . In a last part, the temporal properties of the backscattered signal is studied, in particular the correlation time and the Doppler shift induced by waves motion. Influence of the latters on the non focused SAR synthesis is studied in the context of the SWOT system.

O comportamento das formas de linha dos espectros de RMN estático em função da temperatura assim como os experimentos de PURE Exchange em uma dimensão (PUREX-1D) foram utilizados para elucidar detalhes da dinâmica molecular nos PnMA. Os experimentos PUREX-1D foram realizados na faixa de temperatura de Tg-145 o C a Tg. Nesta faixa de temperatura a dinâmica molecular dos PnMA acontece com tempos de correlação entre 500 micro e 10 milissegundos. Utilizando simulação espectral foi demonstrado que os espectros PUREX-1D dependem tanto do tempo de correlação quanto da geometria das reorientações moleculares. Este fato também foi usado para avaliar as características dos movimentos moleculares responsáveis pela reaxação estrutural beta nos PnMA. Foi observado que os pequenos ângulos de reorientação da cadeia principal associados com a relaxação estrutural beta aumentam com o aumento da temperatura e que os tempos de correlação do movimento podem apresentar uma larga distribuição. Análises das formas de linha obtidas através de experimentos de polarização cruzada (CP) em função da temperatura foram realizadas para se estudar o comportamento da dinâmica molecular responsável pela relaxações estruturais alfa e beta nos PnMA. Os experimentos CP foram realizados em uma faixa de temperaturas entre Tg-50 o C e Tg.+70 o C. Nesta faixa de temperatura as figuras de linha de RMN estática são altamente dependentes da temperatura, do tamanho e do volume do ramo lateral. A dinâmica molecular dos PnMA apresentou um movimento altamente anisotrópico sendo que a isotropização da conformação do espectro induzida pelos movimentos moleculares ocorreu apenas a temperaturas muito acima da Tg, contrariando o comportamento esperado para a maioria dos polímeros amorfos. / The behavior of the static NMR line shapes as a function of the temperature as well as one-dimensional Pure Exchange NMR experiments (PUREX-1D) were used to elucidate details of the molecular dynamics in PnMAs. The 1D-PUREX experiments were carried out in the temperature range of Tg-145 oC to Tg. In this range of temperature the molecular dynamics of PnMAs was found to occur with correlation times between 500m and 10ms. Using spectral simulations it was demonstrated that the 1D-PUREX spectra depend on both, the correlation time and geometry of the molecular reorientations. Hence this feature was used to evaluate the characteristics of the molecular motions responsible by the b structural relaxation of PnMAs. It was found that the small angles reorientation of main chain associated with the b-structural relaxation increases with the temperature and the correlation times present a possible broad distribution. Analysis of the NMR line shapes obtained in Cross Polarization (CP) experiments as a function of temperature was performed to study the behavior of the molecular dynamics responsible for the b and a structural relaxation. The CP experiments were performed in the temperature range of Tg-50 oC to Tg+70 oC. In this temperature range the static NMR line shapes are highly dependent on the temperature, size and bulk of the side-group. The dynamics of the PnMA presents a highly anisotropic motion and the isotropisation of conformation induced by the motion only occurs in temperatures well above Tg, contrary to the behavior of the most fragile amorphous polymers.