A series of studies are presented in which fluorine tagging reagents are used to analyze complex mixtures for compounds containing active hydrogen functional groups (e.g., hydroxyl, amine, thiol, and carboxylic groups). The existence of these derivatized functional groups is determined by utilizing a number of solution and solid-state nuclear magnetic resonance (NMR) techniques. In solution NMR studies p-fluorobenzoyl chloride was the fluorine tagging reagent of choice because of a large ¹⁹F chemical shift range for the different derivatized substrates (~10 ppm) and generally good reaction yields. Various classes of sterol and amino acid p-fluorobenzoyl derivatives were characterized on the basis of their ¹⁹F NMR isotropic chemical shifts. The presence (or absence) of hydroxyl, amine, and carboxylic acid functional groups in coal extract and pyrolysis products was also determined. The versatility of the p-fluorobenzoyl chloride as the fluorine tagging reagent in ¹⁹F NMR was enhanced by: a) enriching the carbonyl carbon of the acid chloride with labeled ¹³C isotope, thus synthesizing a dual ¹⁹F and ¹³C NMR sensitive reagent and b) using the reagent in conjunction with LC-NMR. The extension to either technique added another dimension to the NMR spectral data obtained from the p-fluorobenzoyl tagging reagent in solution NMR. Finally, preliminary data is presented illustrating how fluorine tagging reagents may be used to study functional groups (and atoms present in the immediate proximity of the group) existing on solid material utilizing solid-state NMR. Functional groups on the solid material are tagged with a fluorinated reagent. The sample is then analyzed using solid-state NMR with cross-polarization (CP), magic angle spinning (MAS), and high-power proton decoupling. The ¹⁹F dipolar coupling interactions, created by the presence of the fluorine tag, attenuate signals for these nuclei in the immediate proximity of the tagged site. A series of 1-adamantanol, steroid, and silica gel fluorinated derivatives show that the effects of the ¹⁹F dipolar interactions were modulated by complex anisotropic molecular motions (i.e., solid system with little motion, exhibiting greater signal attenuations due to ¹⁹F dipolar coupling). / Ph. D. / incomplete_metadata

The limitations of previous dynamic nuclear polarization (DNP) experiments have been avoided by a transfer DNP approach whereby the nuclear spins are polarized by DNP at low magnetic field (0.33 T) and then quickly transferred to a high monitoring field (4.7 T). This approach provides an order of magnitude improvement in sensitivity when compared to the usual low field DNP experiment. Also high resolution spectra commonly obtainable at high magnetic fields are now possible for the DNP enhanced signals. Using this method, we have observed large ¹H, ²D, ¹³C, ²⁹Si, and ¹⁵N scalar and dipolar enhancements (2-60 times of signal strength at 4.7 T NMR). Among the results, ¹⁵N and ²⁹Si liquid DNP enhancements are the first to be reported. The selective ¹³C and ¹H DNP enhancements at 0.33 T for different nuclei on the same molecule were observed. A mathematical model describing the low to high magnetic field transfer DNP experiments has also been developed. In ¹³C DNP, we find that the three-spin effect can significantly degrade the dipolar dominated enhancements unless high radical concentrations are used. The scalar dominated ¹³C DNP enhancements can be very large. In addition, the nitroxide radical (TEMPO) used in the present study can induce large scalar enhancements at carbon or nitrogen atoms which have weakly acidic hydrogens. These results indicate DNP can be a very sensitive probe to study weak intermolecular interactions (e.g., hydrogen bonding). / Ph. D.

In this study the applicability of Carbon-13 NMR and XPS to the detection of chemical changes in a solid composite rocket propellant was studied. Storage at elevated temperatures was used to simulate the propellant ageing process. In the XPS analysis, changes in the sources for the N(1s) and Cl(2p) photopeaks were investigated. The propellant loses "organic" nitrogen as it ages. Changes in the amount of Cl⁻ present are in doubt due to instrumental considerations. Carbon-13 NMR analysis showed that with increasing age of a sample there is a corresponding loss of vinylic groups from the binder. This loss of vinylic character is preferential in the order pendant>>cis>trans. Due to the long scan times involved this method is of limited utility for ageing analysis. / Master of Science

In this thesis, I traced the development of Nuclear Magnetic Resonance (NMR) Spectroscopy through the pages of the Journal of Organic Chemistry (JOC) from the year 1956 to 1969 to understand how organic chemists and Varian Associates?the makers of the first commercial NMR spectrometers?negotiated the identity of the NMR spectrometer. The work of the organic chemists was examined through their publications in the JOC. Examining the abstracts from the JOC between the years 1956 and 1969 developed an understanding of the ways in which organic chemists used the instrument. To understand the role Varian Associates played in the development of NMR, I examined the company?s advertisements in the JOC. I traced the changes in advertising style and format in order to see how Varian Associates expected their instruments to be used. I drew three conclusions from this work: 1) organic chemists and Varian Associates together determined what an NMR spectrometer was and how it could be used; 2) the identity of the instrument was negotiated by these two groups, and the novel use of the instrument by the organic chemists and new schemes in advertising on the part of Varian Associates were attempts to shift this identity; 3) NMR spectroscopy was a domain of knowledge that was embodied in the NMR spectrometer, and that could only be accessed through the instrument. / Master of Science

Traumatic brain injury (TBI) continues to be a widespread problem in the United States with approximately 1.7 million occurrences annually [1]. Current automotive crash test standards use the Head Injury Criterion (HIC) [2] to assess head injury potential, but this metric does not relate an impact to underlying damage. For an injury metric to effectively predict TBI, it is crucial to relate level of impact to resulting injury. The research presented in this dissertation explains the development and repeatability of two novel injury devices, impact response characterization over the course of 24 hours in the Gottingen minipig and the relationships between metabolite changes, underlying disruption, and impact kinematics, and the characterization of impact response over the course of 72 hours. The translation-input and combined translation and rotation-input injury devices were shown to be repeatable, minimizing the number of animals needed for testing. Impact response over the course of 24 hours showed axonal disruption through immunostaining and proton magnetic resonance spectroscopy. The translation-input injury group metabolite analyses revealed the initial stages of glutamate excitotoxicity while the combined-input injury group showed a clear pathway for glutamate excitotoxicity. Numerous correlative relationships and potential underlying disruption predictors were found between metabolites, immunostaining, and kinematics. The most promising predictor combination for the translation-input injury device was N-acetylaspartylglutamate/Scyllo at 24 hours compared to 1 hour and linear speed for predicting underlying light neurofilament disruption. For the combined-input injury device, the strongest predictor combination was Glutamine/N-acetylaspartylglutamate at 24 hours compared to baseline and angular acceleration for predicting underlying light neurofilament disruption. Statistically significant predictors were found between Glutamate+Glutamine/Total Creatine at 24 hours compared to baseline and all kinematics and injury metrics with an angular component for predicting heavy neurofilament disruption. Analyses over the course of 72 hours revealed persistent axonal disruption and metabolite perturbations. Overall, this dissertation and the complementary parts of this project have many societal implications. Due to the high incidence of traumatic brain injury, there is a need for prevention, mitigation, and treatment strategies. Developing a new injury metric will help improve prevention strategies, especially in the automotive, sporting, and military environments. 1 Faul, M., Xu, L., Wald, M. M., and Coronado, V. G. (2010). Traumatic Brain Injury in the United States. Atlanta, GA: Centers for Disease Control and Prevention, National Center for Injury Prevention and Control. 2 Versace, J. (1971). A Review of the Severity Index. SAE Technical Paper. No. 710881 / Ph. D.

A lo largo de la última década hemos asistido a un desarrollo sin precedentes de las tecnologías de la salud. Los avances en la informatización, la creación de redes, las técnicas de imagen, la robótica, las micro/nano tecnologías, y la genómica, han contribuido a aumentar significativamente la cantidad y diversidad de información al alcance del personal clínico para el diagnóstico, pronóstico, tratamiento y seguimiento de los pacientes. Este aumento en la cantidad y diversidad de datos clínicos requiere del continuo desarrollo de técnicas y metodologías capaces de integrar estos datos, procesarlos, y dar soporte en su interpretación de una forma robusta y eficiente. En este contexto, esta Tesis se focaliza en el análisis y procesado de señales biomédicas y su uso en problemas de clasificación automática. Es decir, se focaliza en: el diseño e integración de algoritmos para el procesado automático de señales biomédicas, el desarrollo de nuevos métodos de extracción de características para señales, la evaluación de compatibilidad entre señales biomédicas, y el diseño de modelos de clasificación para problemas clínicos específicos. En la mayoría de casos contenidos en esta Tesis, estos problemas se sitúan en el ámbito de los sistemas de apoyo a la decisión clínica, es decir, de sistemas computacionales que proporcionan conocimiento experto para la decisión en el diagnóstico, pronóstico y tratamiento de los pacientes. Una de las principales contribuciones de esta tesis consiste en la evaluación de la compatibilidad entre espectros de resonancia magnética (ERM) obtenidos mediante dos tecnologías de escáneres de resonancia magnética coexistentes en la actualidad (escáneres de 1.5T y de 3T). Esta compatibilidad se evalúa en el contexto de clasificación automática de tumores cerebrales. Los resultados obtenidos en este trabajo sugieren que los clasificadores existentes basados en datos de ERM de 1.5T pueden ser aplicables a casos obtenidos con la nueva tecnolog / Fuster García, E. (2012). Biomedical signal analysis in automatic classification problems [Tesis doctoral]. Editorial Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/17176

Nuclear Magnetic Resonance (NMR) and computational methods increasingly play a predominant and indispensable role in modern chemical research. The insights into the local nuclear environment that NMR can provide is unique information which allows the structural characterization of novel materials, as well as the understanding and explanation of their relevant properties on an atomic scale. Computational methods, on the other hand, can be used to support experimental findings, providing a rigorous theoretical basis. Furthermore, when more complex chemical systems are considered, calculations can prove to be invaluable for the interpretation of experimental data and often allow an otherwise impossible spectral assignment. This thesis presents a series of studies in which NMR spectroscopy, in combination with computational methods, is utilized to investigate a variety of chemical systems both in solution and the solid state. An overview of the thesis and experimental and computational details are given in Chapter 1. In Chapter 2, the quantum mechanical basis necessary for the description of the NMR phenomenon is presented. Chapter 3 explores the main experimental techniques employed routinely for the acquisition of NMR spectra in both solution and the solid state. Chapter 4 describes the main features of density functional theory (DFT) and its implementation in computational methods for the calculation of relevant NMR parameters. Chapter 5 reports an experimental solution-phase NMR study and a parallel computational investigation of the poly(CTFE-co-EVE) fluoropolymer. In Chapter 6, the combination of [superscript(14/15)]N solution-phase NMR techniques and DFT methods for the study of alkylammonium cationic templates used in the synthesis of microporous materials is presented. The characterization of a boroxoaromatic compound in the solid state and the study of its reactivity are described in Chapter 7. In Chapter 8, two experimental NMR methods for the study of the anisotropic chemical shift interaction in the solid state are compared and used to characterize a range of materials. Cross-polarization and nutation of quadrupolar nuclei are computationally investigated under both static and spinning conditions in Chapter 9. A general conclusion and a summary are given in Chapter 10.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2009. / Please refer to full text for abstract. Abstract contains special characters.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2005. / This thesis begins with the description of the preparation of thirteen dithioesters (of the form Z- (C=S)-S-R) which were characterized via Fourier-transform infrared spectroscopy (FT-IR), nuclear magnetic resonance spectroscopy (NMR) and ultraviolet spectroscopy (UV). The dithioesters were then used as reversible addition-fragmentation chain transfer (RAFT) mediating agents in the bulk polymerization of styrene, in order to observe differences in the kinetic behaviour of the polymerizations and, as a result, the efficiencies of the dithioesters in mediating the polymerizations.

Thesis (PhD (Chemistry and Polymer Science))--University of Stellenbosch, 2011. / ENGLISH ABSTRACT: Due to the commercial, nutritional and health value of vegetable oils, seeds and beans, the analysis of their components is of much interest. In this dissertation oil-containing food products, specifically vegetable oils, seeds and beans, were investigated. Selected minor components of three locally produced vegetable oils, namely apricot kernel, avocado pear and macadamia nut oils were investigated using 31P NMR spectroscopy. These minor components, including 1,2 diacylglycerols, 1,3 diacylglycerols and free fatty acids, were identified in the 31P NMR spectra of each of the three vegetable oils for the first time. Two approaches were used for the quantification of the minor components present in the spectra. A calibration curve approach used known concentrations of standard minor components to establish calibration curves while a direct correlation approach calculated the unknown concentration of minor components in the vegetable oils using a known amount of standard compound within the analysis solution. These approaches aided in determining the concentration of minor components during storage studies in which vegetable oils were stored in five different ways: exposed to light, in a cupboard, in a cupboard wrapped in tin foil, at -8 °C and at 5 °C. It was found that determining the best storage condition for each oil was difficult since individual minor components were affected differently by the various storage conditions. However, in general the best storage conditions appeared to be 5 °C and -8 °C. The oil, protein and carbohydrate contents of sesame, sunflower, poppy, and pumpkin seeds, and soy, mung, black and kidney beans were analysed by thermogravimetric analysis and 13C NMR solid state NMR spectroscopy. It was shown that the first derivative of TGA data for seeds and beans can give valuable information about the carbohydrate, moisture, protein and fat content. This has not been previously demonstrated. For the seeds, the integration of a region between 270–480 ºC was equal to the sum of the oil and protein content and compared well to quantitative results obtained by other conventional methods. For beans the integration of a region between 180-590 ºC, gave a value which represented the sum of the oil, protein and carbohydrate content. 13C solid state NMR spectroscopy, including SPE-MAS, CP-MAS and variable contact time experiments, was carried out on these seeds and beans and gave valuable information on the solid-like and liquid-like components. To our knowledge these seeds and beans have never been previously analysed using this technique. 13C SPE-MAS NMR spectroscopy indicated that the seeds contained more liquid-like components than the beans. In turn the 13C CP-MAS NMR spectra indicated that beans had higher levels of solid-like components than the seeds. These conclusions correlated well with the quantities of liquid-like components and solid-like components that were determined by conventional methods and TGA. Preliminary studies using T1pH experiments on the components present in the seeds and beans led to a few observations. Most interesting is that a model using a two- phase fit in order to determine T1pH values appears to be more accurate than a one-phase model. / AFRIKAANSE OPSOMMING: Groente olies, sade en bone is ‘n onderwerp van groot belang omrede hul kommersiële, voeding en gesondheidswaardes. In hierdie tesis is olie-bevattende voedselprodukte, spesifiek groente-olies, sade en bone geanaliseer. Geselekteerde komponente teenwoordig in klein hoeveelhede in drie lokaal geproduseerde groente-olies, naamlik appelkoos-pit, avokadopeer en makadamia-neut olies is geanaliseer met behulp van 31P KMR spektroskopie. Hierdie komponente, insluitend 1,2 diasielglyserole, 1,3 diasielglyserole en ongebonde vetsure, is vir die eerste keer geïdentifiseer in die 31P KMR spektra van die drie groente olies. Twee benaderings is gebruik vir die hoeveelheids-bepaling van die komponente in die spektra. ‘n Yking-kurwe metode het gebruik gemaak van bekende hoeveelhede konsentrasies standaard komponente vir die opstel van yking-kurwes, terwyl ‘n direkte korrelasie metode gebruik is om die onbekende konsentrasie van komponente in groente olies te bepaal met behulp van ‘n bekende hoeveelheid standaard verbinding teenwoordig in die oplossing. Hierdie metodes het gelei tot die bepaling van die konsentrasies van die komponente gedurende vyf verskillende berging toestande wat ingesluit het: Blootgestel aan lig, in ‘n donker kas, in ‘n donker kas toegevou in tin foelie, bevries by -8 °C en in ’n koelkas by 5 °C. Dit was bevind dat bepaling van die beste bergingstoestand vir elke olie moeilik is aangesien die individuele komponente verskillend geaffekteer word deur die verskeie berging toestande. Die beste bergings toestand oor die algemeen blyk egter om by 5 °C en -8 °C te wees. Sesamsaad, sonneblomsaad, papawersaad en pampoensaad sowel as sojaboontjie, mungboontjie, swartboontjie en pronkboontjie se olie, protein en koolhidraat komponente was geanaliseer met behulp van termogravimetriese analise (TGA) en 13C soliede toestand KMR spektroskopie. Dit was bevind dat die eerste afgeleide van die TGA data waardevolle inligting lewer oor die komponent inhoud van elk van die sade en bone. Hierdie is nog nie vantevore bevind nie. Vir die sade, was die integrasie van ‘n area tussen 270–480 ºC gelyk aan die som van die olie en proteïen inhoud en het goed vergelyk met die waardes verky deur algemene analitiese metodes. Vir die boontjies, was die integrasie van ‘n area tussen 180-590 ºC gelyk aan die som van die olie, protein en koolhidraat inhoud. 13C vaste staat KMR spektroskopie, insluitende SPE-MAS, CP-MAS en variëerbare kontak-tyd eksperimente, was gedoen en het waardevolle inligting gelewer omtrent die solied-agtige en mobiel-agtige komponente. Hierdie sade en bone is tot ons kennis nog nie van te vore met die tegnieke ondersoek nie. 13C SPE-MAS NMR spektroskopie het aangedui dat daar ‘n groter hoeveelheid mobiel-agtige komponente in sade as in bone teenwoordig is. 13C CP-MAS NMR spektroskopie het weer aangedui dat daar ‘n groter hoeveelheid solied-agtige komponente in bone as in sade teenwoordig is. Hierdie gevolgtrekkings het goed vergelyk met die waarnemings verkry deur konvensionele analitiese metodes en TGA. Voorlopige studies op die komponente van sade en bone deur T1pH eksperimente het tot ‘n paar gevolgtrekkings gelei waarvan die mees interessantste was dat ‘n twee-fase model vir die bepaling van T1pH waardes beter resultate lewer as ‘n een-fase model.