Myeloarchitecture is a prominent feature that can identify the primary motor and sensory areas in the cerebral cortex and is increasingly imaged in magnetic resonance imaging (MRI) studies of cortical parcellation in humans. However, MRI studies of cortical myeloarchitecture are technically difficult for two reasons: the cortex is only a few millimeters thick, and intracortical contrast due to myelin is much smaller than the overall anatomical contrast between cortical tissue and underlying white matter that is typically utilized in imaging. The research in this thesis thus presents specific MRI protocols to visualize intracortical myelin, image processing protocols to delineate the heavily myelinated cortex from the adjacent typical cortex and the application of these techniques in the precentral motor cortex to study morphology of the highly myelinated dorso-medial part, consisting of Brodmann area (BA) 4 and part of BA 6. Optimization of the MRI protocols involved determining the sequence parameters for a T1-weighted MRI sequence to obtain maximal intracortical contrast at 0.7 mm isotropic resolution in imaging time of 15 min, based on T1 differences between cortex that is myelinated (GMm) or unmyelinated (GM). As part of the optimization, T1 values were measured in the following brain tissues: GM, GMm and white matter (WM). The optimization was carried out by simulating the MRI signal for a 3D, magnetization prepared, gradient echo sequence, using the measured T1 values in the analytical signal equations. It was found that lengthening the time delay at the end of each inner phase encoding loop increased the intracortical contrast. The optimization of MRI protocols also included implementing techniques to reduce radio frequency field (B1) inhomogeneities. It was found that dividing the optimized, T1-weighted MRI with a predominantly proton density weighted image resulted in a ratio image with significantly reduced B1 inhomogeneities. The goal of the image processing protocols developed in this thesis was to visualize the variation of intracortical myelin across the precentral motor cortex and to delineate its well-myelinated dorso-medial part. The myeloarchitectonic feature that was selected to visualize the variation in intracortical myelination was the thickness of GMm in the deeper parts of the cortex relative to the cortical thickness, referred to as the proportional myelinated thickness (p). To measure p, the following processing steps were performed. The ratio image was segmented into four tissues: GM, GMm, WM and cerebrospinal fluid (CSF) using fuzzy C-means clustering technique. Using a level set approach, thickness of the cortex was determined as the distance between the outer boundaries of GM and WM and thickness of GMm or myelinated thickness (m) was determined as the distance between the outer boundaries of GMm and WM. The proportional myelinated thickness p, was calculated as follows: p= m/t. The well-myelinated dorso-medial part of the precentral cortex, referred to as Mm, was distinguishable from the adjacent cortex when the proportional myelinated thickness was projected on the outer cortical surface. The optimized MRI and image processing techniques developed in this thesis were used to investigate cortical plasticity in amputees. Two morphological features of the myeloarchitecture over Mm, the mean proportional myelinated thickness and area, were measured in four lower limb amputees and four matched controls. A comparison of these morphological features showed no statistically significant difference (p < 0.05) between the two groups. / Thesis / Doctor of Philosophy (PhD)

The objective of this dissertation is to demonstrate different applications of ssNMR, with particular emphasis on uses in polymeric and biosciences. First, dynamics investigations on two polymers will be discussed: (1) disulfonated poly(arylene ether sulfone)s /poly(ethylene glycol) blends (BPS-20_PEG), which are under development as chlorine-resistant reverse osmosis (RO) membrane alternatives to aromatic polyamide (PA) technology, and (2) poly(arylene ether sulfone)s modified with 1,4-cyclohexyl ring units to improve processability. Simple cross-polarization magic-angle-spinning (CPMAS) experiments compared the chlorine tolerance of BPS-20_PEG and PA. Techniques capable of detecting motional geometries and rates on timescales from nanoseconds to seconds, including relaxation time measurements, were applied. Correlations were established between relaxation time and water permeability for the RO membranes, and between relaxation time and polydispersity in the 1,4- cyclohexyl ring modified polymer. Next, 31P and 2H static ssNMR experiments evidencing the formation of toroidal pores and thinned bilayers in oriented zwitterionic and anionic phospholipid bilayers, (biomembrane mimetic systems), by the antimicrobial peptides (AMPs) magainin-2 and aurein-3.3, will be mentioned. The toroidal pore geometries induced by magainin-2 were different than those produced by aurien-3.3. The most prominent features were observed in 2H spectra, implying greater interaction of the peptides with hydrophobic lipid acyl chains. Following this, a new two-dimensional homonuclear dipolar recoupling MAS experiment, capable of correlating long range 13C-13C spin pairs in a uniformly/ extensively 13C-labeled biomolecule, will be introduced. This technique was demonstrated on 13C-labeled versions of Glutamine and Glycine-Alanine-Leucine. Experiments involving the recoupling of all 13C-13C spin pairs, and experiments with selective recoupling using Gaussian or cosine-modulated Gaussian pulses, were demonstrated. Finally, work using static 1H- 13C CP ssNMR to selectively detect interfacial water around hydrophobic C60 will be recounted. This project exploited the distance limitation of CP, and 1H spin-lattice relaxation times, to separate the influence of bulk and interfacial water on the spectra. Results indicated that the tumbling of interfacial water is slowed by a factor of 105 compared to bulk water, providing it with a solid-like character, and allowing the hydration shell to be stable at temperatures above the freezing point of water. / Ph. D.

In Alzheimer’s disease (AD), disturbances in the circadian rhythm and sleep-wake cycle are frequently observed. Both are controlled by the master clock: the suprachiasmatic nucleus (SCN), which was reported in postmortem studies of AD subjects to be compromised. However, the influence of age and gender on the biophysical integrity and subtle microstructural changes of SCN and mechanistic connections between SCN dysfunction and AD progression in vivo remain to be explored. In the present study, we utilized state-of-the-art in vivo magnetic resonance relaxation measurements in combination with immunohistochemistry to follow microstructural changes in SCN of the Tg2576 mouse model of AD. Longitudinal monitoring of in vivo T2 relaxation with age shows significant shortening of T2 values in the SCN of transgenic mice and more substantially in female transgenic than aged-matched controls. Multiexponential T2 analysis detected a unique long T2 component in SCN of transgenic mice which was absent in wild-type mice. Immunohistochemical examination revealed significantly elevated numbers of activated astrocytes and an increase in the astrocyte to neuron ratio in SCN of transgenic compared to wild-type mice. This increase was more substantial in female than in male transgenic mice. In addition, low GABA production in SCN of transgenic mice was detected. Our results offer a brief appraisal of SCN dysfunction in AD and demonstrate that inflammatory responses may be an underlying perpetrator for the changes in circadian rhythmicity and sleep disturbance in AD and could also be at the root of marked sex disparities observed in AD subjects.

This study seeks to evaluate the temperature effects on the electronic properties of thermoelectric materials, using first principles Density Functional Theory (DFT) calculations by incorporating the temperature effects on structural properties of the material. Using the electronic properties attained, the charge carrier scattering relaxation times were determined. The effect of interface between PbTe and SrTe on the charge carrier mobility was studied by finding out the relative alignment of energy bands at the semiconductor heterojunction. The crystal shape of the SrTe precipitates in the PbTe host matrix was evaluated from the interface energies using the Wulffman construction. We also attempted to develop a relation between the interface energies and electronic band alignment for different interface orientations. In this research, we incorporated the temperature effects on the structural properties of PbTe to get the temperature dependence of electronic properties like energy bandgap and effective masses of charge carriers. We used the values of bandgap and effective masses to determine the charge carrier scattering relaxation time at different temperatures which is used in evaluating the transport properties of thermoelectric materials like the Seebeck coefficient and electrical conductivity. / Master of Science

This work has been a study of systems, mostly of sulfa-drugs, showing polymorphic behaviour. Using different means as solid state NMR, X-ray analysis, and theoretical calculations, we have seen how it is possible to understand results obtained from the different techniques, proving how the study of polymorphic systems needs cooperative advice from the different techniques that are able to detect polymorphic differences. Within the sulfa-drugs I have been mostly concentrating on sulfanilamide, studying (^13)C and (^15)N solid state NMR spectra of the different polymorphs. The NMR parameters that have been most interesting to study, have been the relaxation times that have revealed complicated motion of the molecule despite it being a small molecule. In order to obtain detailed information from (^15)N spectra it has been necessary to enrich the samples and this has enabled a study of the shielding tensors of the nitrogens in the molecule. (^13)C spectra were also recorded of systems studied sulfathiazole solvates that proved to show some of the same solid state effects in the NMR spectra as sulfanilamide. Shielding calculations have proved to be still limited in order to obtain reliable information on the shielding of both and (^13)C (^15)N nuclei but considering hydrogen-bonded molecules, as opposed to isolated molecules, seemed to have improved the calculations quite a lot, so that some idea of intermolecular effects could be deducted. Exact positions of the hydrogen has proved to be essential as well in order to improve the calculations. Finally a case study for the REDOR pulse sequence has been carried out. Different attempts to understand the effects influencing this particular experiment have been carried out on 20% and 99% doubly enriched glycine, as well as on a particular sample, doubly enriched BRL55834, but the internuclear distances measured with this technique still displayed some uncertainties that made results not thoroughly reliable.

Since a decade, spintronics and related physics have attracted considerable attention due to the massive research conducted in these areas. The main reason for growing interest in these fields is the expectation to use the electrons spin instead of or in addition to the charge for the applications in spin-based electronics, quantum information, and quantum computation. A prime concern for these spins to be possible candidates for carrying information is the ability to coherently control them on the time scales much faster than the decoherence times. This thesis reports on the spin dynamics in two-dimensional electron gases hosted in artificially grown III-V semiconductor quantum wells. Here we present a series of experiments utilizing the techniques to optically control the spin polarization triggered by either optical or electrical methods i.e. well known pump-probe technique and current-induced spin polarization. We investigated the spin coherence in high mobility dense two-dimensional electron gas confined in GaAs/AlGaAs double and triple quantum wells, and, it\'s dephasing on the experimental parameters like applied magnetic field, optical power, pump-probe delay and excitation wavelength. We have also studied the large spin relaxation anisotropy and the influence of sample temperature on the long-lived spin coherence in triple quantum well structure. The anisotropy was studied as a function sample temperature, pump-probe delay time, and excitation power, where, the coherent spin dynamics was measured in a broad range of temperature from 5 K up to 250 K using time-resolved Kerr rotation and resonant spin amplification. Additionally, the influence of Al concentration on the spin dynamics of AlGaAs/AlAs QWs was studied. Where, the composition engineering in the studied structures allows tuning of the spin dephasing time and electron g-factor. Finally, we studied the macroscopic transverse drift of long current-induced spin coherence using non-local Kerr rotation measurements, based on the optical resonant amplification of the electrically-induced polarization. Significant spatial variation of the electron g-factor and the coherence times in the nanosecond scale transported away half-millimeter distances in a direction transverse to the applied electric field was observed. / Há uma década, a spintrônica e outras áreas relacionadas vêm atraindo considerável atenção, devido a enorme quantidade de pesquisa conduzidas por elas. A principal razão para o crescente interesse neste campo é a expectativa da aplicação do controle do spin do elétron no lugar ou em adição à carga, em dispositivos eletrônicos e informação e computação quânticas. A possibilidade destes spins carregarem informação depende, primeiramente, da habilidade de controlá-los coerentemente, em uma escala de tempo muito mais rápida do que o tempo de decoerência. Esta tese trata da dinâmica de spins em gases de elétrons bidimensionais, em poços quânticos de semicondutores III-V, crescidos artificialmente. Nós apresentamos uma série de experimentos, utilizando técnicas para o controle ótico da polarização de spin, desencadeadas por métodos óticos ou eletrônicos, ou seja, técnicas conhecidas de bombeio e prova e polarização de spin induzida por corrente. Nós investigamos a coerência de spin em gases bidimensionais, confinados em poços quânticos duplos e triplos de GaAs/AlGaAs e a dependência da defasagem com parâmetros experimentais, como campo magnético externo, potência ótica, tempo entre os pulsos de bombeio e prova e comprimento de onda da excitação. Também estudamos a grande anisotropia de relaxação de spin como função da temperatura da amostra, potência de excitação e defasagem entre bombeio e prova, medidos para uma vasta gama de temperatura, entre 5K e 250K, usando Rotação de Kerr com Resolução Temporal (TRKR) e Amplificação Ressonante de Spin (RSA). Além disso estudamos a influência da concentração de Al na dinâmica dos poços de AlGaAs/AlAs, para o qual a engenharia da composição da estrutura permite sintonizar o tempo de defasagem de spin e o fator $ g $ do elétron. Por fim, estudamos a deriva transversal macroscópica da longa coerência de spin induzida por corrente, através de medidas de Rotação de Kerr não-locais, baseadas na amplificação ressonante ótica da polarização eletricamente induzida. Observamos uma variação espacial significante do fator $ g $ e do tempo de vida da coerência, na escala de nanosegundos, deslocada distâncias de meio milímetro na direção transversa ao campo magnético aplicado.