Thesis (Ph.D.)--Memorial University of Newfoundland, 2004. / Bibliography: leaves 157-167.

Thesis (Ph. D.)--University of Canterbury, 2006. / Typescript (photocopy). "20-July-2006." Includes bibliographical references. Also available via the World Wide Web.

Thesis (Ph. D.)--University of Washington, 2006. / Vita. Includes bibliographical references (leaves 159-176).

Thesis (Ph. D.)--University of Washington, 2007. / Vita. Includes bibliographical references (leaves 167-181).

Changes in the metabolic state of the brain can occur, for example, as a result of neuronal activity or in pathologies such as cancer. In these cases, an altered energy demand can lead to changes in neurochemical concentrations detectable using proton magnetic resonance spectroscopy (¹H-MRS). This thesis explores in vivo ¹H-MRS methods for detection of such changes in the healthy and diseased brain. Specifically, this thesis aims to develop methods with semi-LASER localisation, thereby minimising the negative effects of chemical shift displacement and field inhomogeneity on spectral acquisition. Firstly, a Hadamard-encoded semi-LASER method for simultaneous measurement from two regions was developed at 7 T. Slice profiles, with low chemical shift displacement and small amounts of signal overlap, were revealed in phantom and in vivo. This was then implemented in a study of neurochemical change during positive and negative blood oxygen level-dependent (BOLD) responses. Negative BOLD responses are thought to reflect regions of neuronal suppression. A small decrease in ascorbate, as well as the T2*-induced linebroadening of several spectra, were observed in these regions. Furthermore, increases in glutamate and lactate were detected in positive BOLD regions. These findings suggested that negative BOLD may not be generated by an increase in local GABA concentration. Secondly, an optimised semi-LASER sequence (TE = 110 ms) at 3 T was shown to improve localisation of the oncometabolite 2-hydroxyglutarate (2-HG) - a product of IDH-mutation found in the majority of gliomas. This resulted in improved detection of 2-HG in patients compared to an existing technique. The method was also compared to 7 T, where benefits of an increased spectral resolution resulted in significantly better detection of 2-HG along with associated metabolites. This thesis highlights the importance of robust localisation for performing sensitive in vivo ¹H-MRS neurochemical measurement in the human brain.

Tridentate benzimidazole-based ligands, bis((1H-benzimidazol-2-yl)methyl)sulfide (BNSN) and bis((1H-benzimidazol-2-yl)methyl)amine (BNNN), along with dinonylnaphthalene sulfonic acid (DNNSA) as a synergist, were investigated as potential selective extractants for Ni2+ from base metals in a solvent extraction system using 2-octanol/Shellsol 2325 (8:2) as diluent and modifier. However, extraction studies show a lack of pH-metric separation of the later 3d metal ions with bis((1-octylbenzimidazol-2-yl)methyl)sulfide (BONSN) and bis((1- decylbenzimidazol-2-yl)methyl)amine (BDNNN) as extractants, but extractions occurred in the low pH range with an opportunity for back extraction. This investigation suggested that tridentate ligands (at least those of the nature investigated here) are not feasible extractants for separation of base metal ions due to their lack of stereochemical “tailor-making.”

A 10.6 ym C02 laser operating a power range S P 200 watts was used to pump some select vibrational transitions in the NO2 molecule while monitoring the rotational transitions (91/9—'100/10), (232f 22 ~~"*242,23> ' (402,38 "393,37) in the (0, 0, 0) vibrational level and the (8q,8—*"^1,7) rotational transition in the (0, 1, 0) vibrational level. These rotational transitions were monitored by microwave probing to determine how the population of states in the rotational manifolds were being altered by the laser. Coincidences between some components of the V3-V2 band of N02 and the C02 infrared laser lines in the 10 um region appeared to be responsible for the strong interaction between the continuous laser beams and the molecular states.

A carne bovina é considerada um alimento altamente nutritivo, sendo uma fonte de proteínas e vitaminas, além de minerais tal como ferro e zinco. Por outro lado, a carne vermelha atualmente tem sido associada a doenças cardiovasculares e ao câncer. No entanto, essa associação vem sendo contestada, pois a carne de ruminantes bem como o leite são fontes naturais do ácido linoléico conjugado (CLA, do inglês \"conjugated linoleic acid\"), o qual possui várias propriedades benéficas, como atividade anticarcinogênica, redução de gordura corporal, entre outras. Essas propriedades têm sido observadas em estudos com animais modelos, mas também pesquisas apontam tais benefícios para os humanos. Vários estudos têm sido realizados para aumentar a produção de CLA pelos ruminantes no Brasil. Nesse contexto, se faz necessário o desenvolvimento de métodos rápidos e eficazes para a determinação de CLA em carnes de ruminantes e no leite, pois o método atual é baseado na análise dos ésteres metílicos dos ácidos graxos por cromatografia gasosa, que envolve várias etapas, sendo um método laborioso. Assim, o principal objetivo deste trabalho foi o desenvolvimento de uma metodologia rápida, baseada na técnica de ressonância magnética nuclear de hidrogênio (RMN de 1H) para a determinação do teor do CLA na gordura de carne bovina. Para isso foi avaliada a influência dos principais parâmetros experimentais de RMN de 1H, como a largura do pulso de radiofrequência, o tempo de repetição, método de excitação seletiva, entre outros parâmetros que podem interferir na razão sinal/ruído e na reprodutibilidade das medidas. Os resultados mostraram que a utilização da RMN de 1H para a determinação do teor de CLA em carne bovina, além de ser coerente com os dados obtidos por cromatografia gasosa, representa uma abordagem mais rápida e simples para a determinação do teor de CLA em carne bovina. / Beef is considered a very nutritive food, since it is a source of proteins and vitamins, besides minerals such as iron and zinc, on the other hand it has been associated to heart diseases and cancer. However, this association has been contested because ruminant meat as well as milk, is a natural source of conjugated linoleic acid (CLA), that has several benefic properties such as anticarcinogenic activity, reduction of body fat and others. These properties have been observed in studies with animals and can be extended to humans. Several studies have been done to increase the concentration of CLA in Brazilian ruminant meat. In this context, it is necessary to develop fast and effective analytical methods to determine CLA in ruminant meat and milk, because the current method, based on the analysis of fatty acid methyl esters by gas chromatography (GC), involves several stages, being laborious. Thus, the main purpose of this work was the development of a fast methodology, based on hydrogen nuclear magnetic resonance technique (1H NMR) to determine CLA content in beef fat. In consequence, it was evaluated the influence of main experimental parameters from 1H NMR, such as radiofrequency pulse width, repetition time, method of selective excitation, between others that may interfere in signal-to-noise ratio and reproducibility. The results indicated that the use of 1H NMR spectroscopy to determine CLA content in beef have high correlation to data obtained by gas chromatography, representing a much faster and simpler methodology to determine CLA content in beef.

Contributions to the second order collision efficiency function S ⁽²⁾ (b), used in semiclassical perturbation approaches to pressure broadening of microwave and infrared spectra, due to several leading terms, dipole and quadrupole components, in the expansion of the intermolecular interaction energy are derived by method of irreducible spherical tensor operators for molecules of arbitrary symmetry. Results are given explicitly in terms of dipole and quadrupole line strengths. General expressions for dipole moment line strength in the asymmetric rotor basis as well as quadrupole moment line strength for the special case of molecules with two independent quadrupole moment components are derived. Computer programs for calculating linewidth parameters in the rotational spectrum of ¹⁴NO₂ based on Anderson and Murphy and Boggs theories are presented.

Abstract Xenon atoms and sulfur hexafluoride (SF6) molecules can be dissolved in liquids and liquid crystals or adsorbed in porous materials. Nuclear magnetic resonance (NMR) spectra of 129Xe or 19F nuclei reveal information about their surroundings. This means that xenon atoms and SF6 molecules can be used as probes to indirectly study materials by NMR spectroscopy. The change in the spectra arises from a NMR interaction called shielding. Especially in the case of xenon, shielding reveals even the slightest changes, for example, in the density of a liquid it is dissolved in. Because a change in temperature leads to a change in the density of the liquid as well, temperature change is observed as a shift of the resonance line in the 129Xe NMR spectrum. This property can be utilized in the accurate determination of the sample temperature. Self-diffusion measurements of the gases provide additional information on a larger scale rather than just the immediate surroundings of atoms or molecules. Various liquid crystals were studied using xenon and SF6 as probes proving their applicability. It is often considered that the signal observed in NMR experiments is very weak and limits the full potential of the method. This is true especially with the samples in gaseous form. The Spin-Exchange Optical Pumping (SEOP) hyperpolarization method solves this problem in the case of xenon. A 129Xe NMR signal can be enhanced by a factor of 104–105 by SEOP and this opens access to techniques that are not otherwise possible. The remote detection technique, which separates the encoding and detection steps of the typical NMR experiment both temporally and spatially, is one of these techniques. The potential of the combination of SEOP and remote detection techniques was shown in studies of thermally modified Pinus Sylvestris.