Reductive electron transfer has been successfully utilized to facilitate the first enantioselective desymmetrisation of malonate derivatives. Selective monoreduction of cyclic 1,3-diesters through the combined use of SmI2-Et3N and chiral non-racemic diols has granted rapid access to enantioenriched β-hydroxy acids containing challenging quaternary centres – an abundant motif in many drug molecules. Unique radical anions generated from the single electron reduction of cyclic 1,3-diesters have been exploited in cyclisation cascades. Capture of acyl-type radical anions by both alkene and alkyne acceptors have permitted the construction of complex bicyclic architectures in a single synthetic operation. The reductive cyclisation cascade of lactones has also been demonstrated, using SmI2-H2O to achieve a challenging domino 5-exo-trig/6-exo-trig cyclisation event. This process generates highly decorated carbo[5.4.0]bicyclic scaffolds with complete diastereocontrol.

Marine ascidian metabolite perophoramidine has since its isolation in 2002 attracted the interest of several research groups. The complex polycyclic structure with vicinal quaternary carbon stereocenters and two amidine functionalities constitutes a formidable synthetic challenge. In this project a new synthetic approach to dehalogenated perophoramidine has been investigated. The vicinal quaternary carbon stereocenters were introduced via a samarium mediated reductive dialkylation, in which the stereochemistry was determined by the metal chelate that formed, as outlined below. Several of the steps suggested in the synthetic approach have been successfully evaluated. Future work is needed to assess the remaining steps of the suggested route to dehalogenated perophoramidine.

<p> The magnetic susceptibility of samarium orthophosphate (SmPO4) has been measured over the temperature range from 0.4 to 270°K. A theoretical expression for the susceptibility has been developed assuming a crystal field of cubic symmetry and fitted to the experimental data. </p> / Thesis / Master of Science (MSc)

Entropy, first introduced in thermodynamics, is used in a wide range of fields. Chapter 1 discusses some important theoretical and practical aspects of entropy: what is entropy, is it subjective or objective, and how to properly apply it to living organisms. Chapter 2 presents applications of entropy to evolution. Chapter 3 shows how cellulosic biofuel production can be improved. Chapter 4 shows how lattice vacancies influence the thermodynamic properties of materials. To determine the nature of thermodynamic entropy, Chapters 1 and 2 describe the roots, the conceptual history of entropy, as well as its path of development and application. From the viewpoint of physics, thermal entropy is a measure of useless energy stored in a system resulting from thermal motion of particles. Thermal entropy is a non-negative objective property. The negentropy concept, while mathematically correct, is physically misleading. This dissertation hypothesizes that concepts from thermodynamics and statistical mechanics can be used to define statistical measurements, similar to thermodynamic entropy, to summarize the convergence of processes driven by random inputs subject to deterministic constraints. A primary example discussed here is evolution in biological systems. As discussed in this dissertation, the first and second laws of thermodynamics do not translate directly into parallel laws for the biome. But, the fundamental principles on which thermodynamic entropy is based are also true for information. Based on these principles, it is shown that adaptation and evolution are stochastically deterministic. Chapter 3 discusses the hydrolysis of cellulose to glucose, which is a key reaction in renewable energy from biomass and in mineralization of soil organic matter to CO2. Conditional thermodynamic parameters, ΔhydG', ΔhydH', and ΔhydS', and equilibrium glucose concentrations are reported for the reaction C6H10O5(cellulose) + H2O(l) ⇄ C6H12O6(aq) as functions of temperature from 0 to 100°C. Activity coefficients of aqueous glucose solution were determined as a function of temperature. The results suggest that producing cellulosic biofuels at higher temperatures will result in higher conversion. Chapter 4 presents the data and a theory relating the linear term in the low temperature heat capacity to lattice vacancy concentration. The theory gives a quantitative result for disordered vacancies, but overestimates the contribution from ordered vacancies because ordering leads to a decreased influence of vacancies on heat capacity.

Les buts de cette thèse sont (1) de déterminer si les âges modèles en Nd obtenus sur des terrains protérozoïques migmatisés correspondent réellement à l'âge d'extraction du magma de sa source mantellique (exemple du Limpopo Belt en Afrique du Sud) et (2) de comparer les âges Sm-Nd sur grenat et les âges U-Pb sur zircon déterminés sur des éclogites (exemple du Dabieshan en Chine Centrale). La Zone Centrale du Limpopo Belt est constituée principalement d'orthogneiss et de paragneiss. Elle a subi un métamorphisme granulitique suivi par des conditions métamorphiques de décompression à 2.0 Ga (trajectoire pression et température dans le sens horaire). Nous avons effectué des analyses isotopiques en Sm-Nd et U-Pb combinées aux analyses en éléments majeurs et traces sur trois examples de migmatites formées à 2.0 Ga afin d'étudier le fractionnement chimique et isotopique qui pourrait avoir lieu au cours de la migmatisation. La fusion partielle selon la réaction de déhydratation de la biotite met en exergue des comportements différents du système isotopique Sm-Nd dans les métagreywackes et dans les métapélites. Dans le premier cas, l'équilibre chimique et l'homogénéisation isotopique en Nd n'ont pas été achevés à cause de la fusion incongruente du plagioclase et de l'influence des minéraux accessoires sur la composition chimique des liquides. Il est démontré que la monazite est préférentiellement entraînée dans les leucosomes plutôt que l'apatite, provoquant ainsi la domination de la composition chimique de la monazite sur celles des liquides. De plus, la composition isotopique en Nd non-radiogénique de ce minéral accessoire domine celle du leucosome. Ainsi, les âges modèles en Nd des leucosomes sont jusqu'à 400 Ma plus vieux que ceux obtenus sur les paléosomes. Les âges modèles en Nd obtenus sur ces roches ne peuvent donc pas être uti lisés comme âge de formation de la croûte continentale en Afrique du Sud. Dans le cas des métapelites, la fusion incongruente du plagioclase a influencé la distribution des éléments majeurs, des Larges Ion Lithophi le Element ainsi que des Rare Earth Efement entre les paléosomes et les leucosomes. L'échange isotopique -en Nd entre les différents composants migmatitiques a été pratiquement atteint, au contraire des isotopes du Pb qui ne montrent qu'une homogénéisation partielle. Cependant, deux leucosomes à grenat présentent des compositions isotopiques en Sm-Nd et U-Pb supérieures aux autres composants migmatitiques. Ceci suggère qu'en règle générale les minéraux accessoires ont été chimiquement et isotopiquement équilibrés avec les leucosomes et les paléosomes. De ce fait, les âges modèles en Nd calculés sur les paléosomes et les leucosomes représentent des âges significatifs pour la formation de la croûte continentale dans la Zone Centrale du Limpopo Belt. Le dernier exemple est un orthogneiss migmatitique qui s'est formé par ségrégation métamorphique à des conditions subsolidus. La distribution des éléments majeurs et traces est directement proportionnelle à la quantité de chaque minéraux formant les composants migmatitiques. L'échange __ _ ___ _ isotopique en Pb a été achevé comme le montre l'isochrone en Pb-Pb sur les roches -:_~~ totales à 2.0 Ga. De plus, les caractéristiques géochimiques associées à une modélisation de la distribution des REE indiquent que le système est resté clos à - -----l'échelle de la roche totale durant le processus de migmatisation .. Ainsi, la composition isotopique en Nd du protolithe a pu être déterminée grâce à l'équation de conservation de masse et peut être utilisée pour défini~ l'âge de la formation de la croûte continentale. Le terrain Métamorphique de Ultra-Haute Pression (UHPM) du Dabieshan ______ est caractérisé par la présence de coésite et de quartz pseudomorphe dans les éclogites de composition basaltique mais aussi dans les roches d'origine sédimentaire. Les Isochrones en Sm-Nd sur grenat-omphacite-roche totale des éclogites à coésite du Massif de Bixiling donnent des âges variant entre 210 ± 9 Ma et 218 ± 4 Ma, très similaires aux âges U-Pb sur zircon à 218.4 ± 1.8 Ma et 218.4 ± 2.5 Ma (Ames et al., 1995). De plus, une isochrone Sm-Nd sur grenat-disthène-roche totale d'une éclogite rétromorphosée donne un âge à 231 ± 35 Ma en accord avec un âge à 233 ± 21 Ma (intercepte bas dans le diagramme concordia). Nous avons (:lffectué des datations par les méthodes Rb-Sr et Ar-Ar sur des phengites et des biotites de l'encaissant des éclogites à coésite de Bixiling. Les âges varient entre 198 ± 4 Ma et 212 ± 2 Ma recouvrant les âges précedemment obtenus par Sm-Nd sur les éclogites à coésite. Par conséquent, les âges Sm-Nd sur grenat sont en accord avec les âges U-Pb sur zircon et montrent que les gneiss quartzo-feldspathiques ont subi un événement métamorphique à -210 Ma comme les éclogites. L'homogénéisation isotopique en Nd entre les différents minéraux semblent être atteinte à l'âge du métamorphisme.

This report describes the growth and characterization of thin amorphous samarium-cobalt alloy films. The samarium-cobalt alloy was grown by DC magnetron sputtering in the presence of an external magnetic field parallel to the thin film. The external magnetic field induces a uniaxial in-plane magnetic anisotropy in the samarium-cobalt alloy. The thin films were characterized with x-ray scattering, and the magnetic anisotropy was characterized with the magneto optic Kerr effect. The measurements showed a uniaxial in-plane magnetic anisotropy in the samarium-cobalt alloy films. It is not clear how amorphous the samples really are, but there are indications of crystalline and amorphous areas in the alloys.

Shock compaction experiments were performed on soft magnetic phases Fe₄N and Fe₁₆N₂, and hard magnetic phases Nd₂Fe₁₄B and Sm₂Fe₁₇N₃ in order to determine their thermo-mechanical stability during shock loading and explore the possibility of fabricating a textured nanocomposite magnet. Gas gun experiments performed on powders pressed in a three capsule fixture showed phase transformations occurring in Fe₄N, Fe₁₆N₂, and Nd₂Fe₁₄B, while Sm₂Fe₁₇N₃ was observed to be relatively stable. Shock compaction of FCC Fe₄N resulted in a partial transformation to HCP Fe₃N, consistent with previous reports of the transition occurring at a static pressure of ~3 GPa. Shock compaction of Fe₁₆N₂ produced decomposition products alpha-Fe, Fe₄N, and FeN due to a combination of thermal effects associated with dynamic void collapse and plastic deformation. Decomposition of Nd-Fe-B, producing alpha-Fe and amorphous Nd-Fe-B, was observed in several shock consolidated samples and is attributed to deformation associated with shock compaction, similar to decomposition reported in ball milled Nd-Fe-B. No decomposition was observed in shock compacted samples of Sm-Fe-N, which is consistent with literature reports showing decomposition occurring only in samples compacted at a pressure above ~15 GPa. Nd-Fe-B and Sm-Fe-N were shown to accommodate deformation primarily by grain size reduction, especially in large grained materials. Hard/Soft composite magnetic materials were formed by mixing single crystal particles of Nd-Fe-B with iron nanoparticles, and the alignment-by-magnetic-field technique was able to introduce significant texture into green compacts of this mixture. While problems with decomposition of the Nd₂Fe₁₄B phase prevented fabricating bulk magnets from the aligned green compacts, retention of the nanoscale morphology of the alpha-Fe particles and the high alignment of the green compacts shows promise for future development of textured nanocomposite magnets through shock compaction.

Microbeam radiation therapy (MRT) is an experimental form of radiation treatment which causes less damage to normal tissue in comparison with customary broad-beam radiation treatment. In this method the synchrotron generated X-ray beam is passed through a multislit collimator and applied to the tumor in the form of an array of planar microbeams. MRT dosimetry is an extremely challenging task and no current detector can provide the required wide dynamic rang and high spatial resolution. In this thesis, fluorophosphate (FP) and fluoroaluminate (FA) glass plates doped with trivalent samarium (Sm3+) are characterized towards developing a potential X-ray detector suitable for MRT dosimetry. The detection is based on the difference in the photoluminescence signatures of Sm3+ ions and Sm2+ ions; the latter are formed under X-ray irradiation. This valency conversion is accompanied by the formation of defects including hole centers (HCs) and electron centers (ECs) in the glass structure which absorb light in the UV and visible regions (induced absorbance). Both FP and FA glasses show promising dynamic range for MRT and may be used as a linear sensor up to ~150 Gy and as a nonlinear sensor up to ∼2400 Gy, where saturation is reached. X-ray induced defects saturate at the same dose. The optimum doping concentration is in the 0.001˗ 0.2 at.% range. Doping with higher concentrations will decrease the conversion efficiency. The glass plates also show a very promising spatial resolution (as high as a few microns) for recording the dose profile of microbeams which is readout using a confocal fluorescence microscopy technique. These plates are restorable as well and the response is reproducible. The effects of previous X-ray exposure including samarium valency conversion as well as induced absorbance may be erased by annealing at temperatures exceeding the glass transition temperature Tg while annealing at TA < Tg enhances the response. This enhancement is explained by a thermally stimulated relaxation of host glass ionic matrix surrounding X-ray induced Sm2+ ions. Optical erasure is another practical means to erase the recorded data. Nearly complete Sm2+ to Sm3+ reconversion (erasure) is achieved by intense optical illumination at 405 nm. While, existing X-ray induced bands would be only partially erased. Electron spin resonance (ESR) and optical absorbance spectroscopy are used to investigate the nature of X-ray induced defects and their correlation with Sm valency conversion. A model based on competition between defect center formation and the Sm3+ ⇆ Sm2+ conversion successfully explains the different processes occurring in the glass matrix under X-ray irradiation.

Rare-earth ions holmium (Ho+3), Thulium (Tm+3), and Samarium (Sm+3) were investigated for infrared emission and their possible biomedical applications by a photoluminescence (PL) system. Holmium’s (Ho+3) emission peaks were the result of transitions 5 S2 → 5 I7, and 5 S2 → 5 I5 respectively. Samarium’s (Sm+3) emission peaks were 936 nm and 1863 nm. Thulium’s (Tm+3) emission peaks were the a result of transitions 3 H4 → 3 H6, 3 H5 → 3 H6 , and 3 F4 → 3 H6 respectively. Erbium Oxide nanoparticles (Er2O3) mixed with water by a photoluminescence (PL) system. Erbium Oxide’ (Er2O3) nanoparticle’s emission peaks were the a result of transitions 4 I15/2 → 4 S3/2 , 4 I15/2 → 4 I13/2 respectively. The process was also repeated in vacuum and it was found that the green emission enhances tremendously when the nanoparticles are excited in vacuum. This enhanced luminescence from the Erbium Oxide nanoparticles shows their potential importance in the optical devices and Biomedical applications. / Department of Physics and Astronomy

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