High-oxidation state main-group metal complexes are potential alternatives to transition metals for electrophilic C-H functionalization reactions. However, there is little known about how selection of the p-block, main-group metal and ligand impact C-H activation and functionalization thermodynamics and reactivity. Chapter 2 reports density functional theory (DFT) calculations used to determine qualitative and quantitative features of C-H activation and metal-methyl functionalization energy landscapes for reaction between high-oxidation state d10s0 InIII, TlIII, SnIV, and PbIV carboxylate complexes with methane. While the main-group metal influences the C-H activation barrier height in a periodic manner, the carboxylate ligand has a much larger quantitative impact on C-H activation with stabilized carboxylate anions inducing the lowest barriers. For metal-methyl reductive functionalization reactions, the barrier heights, are correlated to bond heterolysis energies as model two-electron reduction energies.In Chapter 3, DFT calculations reveal that arene C-H functionalization by the p-block main-group metal complex TlIII(TFA)3 (TFA = trifluoroacetate) occurs by a C-H activation mechanism akin to transition metal-mediated C-H activation. For benzene, toluene, and xylenes a one-step C-H activation is preferred over electron transfer or proton-coupled electron transfer. The proposed C-H activation mechanism is consistent with calculation and comparison to experiment, of arene thallation rates, regioselectivity, and H/D kinetic isotope effects. For trimethyl and tetramethyl substituted arenes, electron transfer becomes the preferred pathway and thermodynamic and kinetic calculations correctly predict the experimentally reported electron transfer crossover region.In Chapter 4, DFT calculations are used to understand the C-H oxidation reactions of methane and isobutane with SbVF5. SbVF5 is generally assumed to oxidize methane through a methanium-methyl cation mechanism. DFT calculations were used to examine methane oxidation by SbVF5 in the presence of CO leading to the acylium cation, [CH3CO]+. While there is a low barrier for methane protonation by [SbVF6]-[H]+ to give the [SbVF5]-[CH5]+ ion pair, H2 dissociation is a relatively higher energy process, even with CO assistance, and so this protonation pathway is reversible. The C-H activation/[]-bond metathesis mechanism with formation of an SbV-Me intermediate is the lowest energy pathway examined. This pathway leads to [CH3CO]+ by functionalization of the SbV-Me intermediate by CO, and is consistent with no observation of H2. In contrast to methane, due to the much lower carbocation hydride affinity, isobutane significantly favors hydride transfer to give tert-butyl carbocation with concomitant SbV to SbIII reduction. In this mechanism, the resulting highly acidic SbV-H intermediate provides a route to H2 through protonation of isobutane.

<p>Measurements of thallium and indium doped Silicon-On-Insulator rib waveguidesshow optical absorption at a wavelength of 1550nm, dependent on the charge stateof the associated deep-level. Therefore, it is possible to use this effect to modulatewaveguide transmission by means of local depletion and/or injection of free-carriersto change deep-level occupancy. A one-dimensional model based on the generationand recombination process described by the modified Shockley-Read-Hall (SRH)mechanism was developed using MATLABc programming language in order to computethe optical absorption of a 1550nm wavelength as a function of the density ofneutrally-charged thallium or indium centers. This numerical model is in reasonableagreement with the experimental data for samples co-doped with low and mediumphosphorus concentrations. The values of optical absorption cross-section calculatedfor thallium are 2.9×10−17 ± 0.25cm2 and 3.2×10−17 ± 0.12cm2 for ion implantationdoses of 7.4×10−13cm−2 and 1.2×10−14cm−2, respectively. Also described is the thedesign, fabrication and characterization of an optical modulator using a four-terminalp+pnn+ diode on an indium-doped Silicon-On-Insulator rib waveguide. Modulationby controlling the charge state of deep impurity levels in silicon was thus demonstrated.Modulation bandwidth in the 2-10MHz regime was measured and the depthof modulation is approximately 0.48dB/V in forward bias and 0.25dB/V in reversebias. This is the first report of the implementation of an optical silicon-waveguidemodulator based on a periodically interleaved pn-junction configuration. In addition,the influence of indium, as a dopant in silicon (utilizing the Impurity PhotovoltaicEffect), as a means to increase the efficiency of a thin film silicon solar cell wasinvestigated using the same samples. Under certain doping conditions and geometricalconfigurations, a cell efficiency greater than 24% was measured —a somewhatremarkable result for these silicon thin films of 2.5μm</p> / Doctor of Philosophy (PhD)

The research presented here is an effort to characterize changes in marine oxygen availability across a portion of the later Cambrian noted for unique evolutionary dynamics and which includes a significant global oceanographic event known as the SPICE event (Steptoean Positive Carbon Isotope Excursion). Previous studies have revealed the SPICE caused large changes to the global cycles of carbon, sulfur, uranium, molybdenum and the overall trace metal content of seawater. Furthermore, the initiation of these changes appears to have been temporally coupled with marine extinctions across several paleocontinents raising the possibility of a common causal linkage between all these features. In particular, expanding marine anoxia has been invoked as the most parsimonious explanation for these co-occurring features. The research presented here tests this hypothesis directly across a range of spatial scales using the iron speciation paleoredox proxy to characterize redox conditions within individual basins and to facilitate comparison of conditions between basins. In addition to these analyses, we apply a new proxy, thallium stable isotopes to this interval to assess potential global changes in deoxygenation across the event. These iron speciation analyses showed shallow environments deoxygenated coincident with the initiation of the SPICE and extinction horizons, and these conditions were dominantly ferruginous. Importantly, this work also shows deeper-water environments were deoxygenated prior to and remained so across the event and these environments were also largely. Last we looked at changes in thallium isotopes during this same interval to see if this deoxygenation would be recorded as a positive shift across the interval if expanded anoxia were to impact the areal extent of manganese-oxide sedimentation and burial. We found it did record these changes, but with a different expression than during other more recent events explored using the isotope system. We attribute these differences to the unique chemical structure of the oceans during the Cambrian, which as documented herein were widely oxygen-deficient in their deeper depths. Given this recognition we suggest that thallium isotope studies in deep time should account for this redox structure of ancient oceans likely common under the less-oxygenated atmospheres of the ancient Earth. / Doctor of Philosophy / The research presented here is a story about oxygen in the oceans during an ancient portion of Earth history within the Cambrian Period (around 500 million years ago), soon after animal life first appears in the geologic record. The emerging biosphere of this time seems to have been particularly prone to extinctions, leading to the idea that environmental conditions, such as oxygen availability at the seafloor created difficult circumstances for animals in these ancient seas. This work seeks to quantify the levels of marine oxygenation at this time, however this remains a fundamental challenge because they cannot be directly measured from the rocks we study. Therefore, we rely on how the presence or absence of oxygen changed the chemistry of these rocks at the time they were sediments deposited on the seafloor. Here we use the behavior of two different elements, iron (Fe) and thallium (Tl), to understand changes in oxygen in the oceans around a large, globally-recorded extinction event called the SPICE event. Studying how much iron is concentrated in certain minerals in the rocks formed during this event allowed us to track how changes in oxygen may relate to these notable extinctions. We found that shallow coastal areas changed from oxygenated to deoxygenated at the same time of the extinctions, suggesting a direct role for this environmental shift in the biological crisis. Furthermore, we compared other locations from around the world using more new iron measurements in conjunction with previously published ones compiled by a collaborative geochemistry database project. This work revealed the deeper oceans were deoxygenated prior to and across the SPICE event and that the decline in oxygen in shallower environments was where most environmental change occurred during this time. Last we looked at changes in thallium isotopes during this same interval to see if this deoxygenation changed its global cycle. We found it did record global changes, but they were expressed differently than during other more recent events that have been studied. We attribute these differences to the unique chemical structure of the oceans during the Cambrian, which were widely oxygen-deficient in their deeper depths.

Les cryptophanes sont des récepteurs moléculaires qui présentent des propriétés de complexation intéressantes vis-à-vis de nombreux substrats. Ces quinze dernières années, les cryptophanes ont fait l’objet de beaucoup d’études portant sur leur utilisation pour l’obtention de biosondes pour l’IRM du xénon hyperpolarisé. De très nombreux progrès ont été réalisés, et des études in vivo semblent à présent envisageables, à condition de parvenir à synthétiser les biosondes en larges quantités. Plus récemment, un champ d’application parallèle s’est développé. Celui-ci porte sur la complexation des cations métalliques monovalents en solution aqueuse au sein de cryptophanes polyphénoliques. Ceci laisse envisager des applications pour la dépollution des eaux contaminées par des cations Cs+ ou Tl+. Cependant, ici encore, l’un des enjeux majeurs est la synthèse de larges quantités de cryptophanes présentant les caractéristiques recherchées. Les travaux réalisés au cours de cette thèse traitent de la conception et de la synthèse de nouvelles plateformes moléculaires pour l’obtention de biosondes au xénon hyperpolarisé et pour la complexation des cations métalliques monovalents Cs+ et Tl+. Les voies de synthèse mises au point permettent l’obtention de quantités appréciables d’un ensemble de nouvelles plateformes hydrosolubles pour chacune de ces applications. Les propriétés d’encapsulation de ces molécules hôtes envers leur substrat de prédilection ont été étudiées par RMN des noyaux encapsulés, par dichroïsme circulaire ou encore par titrage calorimétrique. Dans chaque cas, les nouvelles plateformes remplissent les caractéristiques recherchées et ouvrent la voie aux applications visées. / Cryptophanes are molecular receptors known for their complexation properties of various substrates. Over the last fifteen years, cryptophanes were the subject of numerous studies for they can be used to obtain biosensors for xenon MRI. This field has experienced significant growth and advances to the point were in vivo applications are now envisioned, provided that large amounts of biosensors can be synthesized. More recently, polyphenolic cryptophanes have been studied for their ability to encapsulate monovalent metallic cations like Cs+ and Tl+ in aqueous solution. This could lead to applications for depollution of contaminated water sources but would require, once again, the synthesis of large amounts of cryptophanes.The work carried out during this thesis focus on the conception and the synthesis of new molecular platforms that could either be used to obtain new hyperpolarized xenon biosensors or to encapsulate monovalent metallic cations as Cs+ and Tl+. Synthetic routes have been developed to produce good amounts of a variety of new hydrosoluble molecular platforms designed for each application. The encapsulation properties of these new host molecules were studied through NMR of the encapsulated nucleus, circular dichroism or isothermal calorimetry. In each case, the new platforms meet the expected requirements thus opening the door for the envisioned applications.

Thesis (MScMed)--Stellenbosch University, 2004. / Copy not signed by author. / ENGLISH ABSTRACT: This study involved 33 patients, 19 men and 14 women. The age range was wide (20-90 years) and median age was 57 years. These patients had a single pulmonary nodule (SPN) defined radiologically as a well defined, round or oval intrapulmonary lung lesion not associated with atelectasis or adenopathy on chest radiography or computed tomography. Patients were investigated with Tc-99m MIBI and TI-201 (25 patients) and with Tc-99m MIBI alone (8 patients). Single photon emission computed tomography images were reconstructed using both iterative reconstruction (Ordered Subsets - Expectation Maximisation: aSEM) and filtered backprojection (FBP), on the Hermes system. Transverse, coronal and sagittal slices were displayed on the screen using a grey scale. The aSEM and FBP images for each study were co-registered semi-automatically using the multimodality programme on the Hermes. The best slice for the lesion was chosen according to the best view used to locate the SPN on chest radiograph. Regions of interest (Ral) were drawn manually outside the outer margin of the detected lesion, first on the aSEM image. This was automatically mirrored on the co-registered FBP image. For most patients, the background was automatically mirrored horizontally on the contralateral side, again, first on the OSEM then automatically on the FBP image. Automatic vertical mirroring or manual horizontal mirroring was used when background was found to be in a visually 'hot' area like the heart or vertebrae. The average counts and standard deviation of the Ral and background were generated automatically. Semi-quantitative image analysis was done by calculating the signal-to-noise ratio (SNR) and tumour-to-background (TIB) ratio using the following formulae: SNR = Mean counts ROI(lesion) - Mean counts background Standard deviation background TIB rati.o = -M---e-a-n-'--c-o--u-n-'t-s- ROI(lesion) Mean counts background Detection was found to be the same for the two reconstruction algorithms, that is, every lesion detected by using OSEM could also be detected by using FBP. However lesion detection did differ between Tl-201 and Tc-99m-MIBI. Sensitivity and specificity were calculated for different thresholds of SNR and TIB ratios. Receiver operating characteristics (ROC) curves were drawn to represent the different sensitivities and specificities at each threshold. Tuberculosis (TB) was not included in this analysis as uptake of Tl-20l was found to be significantly high and comparable to that of malignant nodules. However the effect of OSEM and FBP on the 'positive' TB nodules was assessed separately. By calculating the area under the ROC curves, TI-201 using OSEM was shown to be more accurate at differentiating malignant nodules from benign ones than FBP. Although this difference was not statistically significant (p=0.1 0), there was a clear tendency. The two reconstruction algorithms were found to be almost equally accurate, when using Tc-99m-MIBI, the difference between them being considerably insignificant. In conclusion, it was shown that there is a tendency that OSEM outperforms FBP for studies using Tl-201 but not for Tc-99m-MIBI. / AFRIKAANSE OPSOMMING: Hierdie studie sluit 33 pasiënte in, 19 mans en 14 vroue. Die ouderdomme wissel tussen 20 en 90 jaar met 'n gemiddelde ouderdom van 57 jaar. Elkeen van die pasiënte het 'n enkel longnodule (SPN) op borskas X-straal en/of rekenaar tomografie getoon, wat radiologies gedefinieer word as 'n goed omskrewe, ronde of ovaal intrapulmonale longletsel wat nie met atelektase of adenopatie geassosieer is nie. Pasiënte is met Tc-99m MIDI en TI-201 (25 pasiënte) of slegs met Tc-99m MIBI (8 pasiënte) ondersoek. Enkelfoton emissie rekenaar tomografiese (EFERT) beelde is met beide iteratiewe rekonstruksie (Ordered Subsets - Expectation Maximisation: OSEM) en gefilterde terugprojeksie (FBP) met die Hermes sisteem gerekonstrueer. Transvers, koronale en sagittale snitte is in grysskaal op die sisteem vertoon. Die OSEM en FBP beelde vir elke studie is semi-outomaties gekoregistreer met behulp van die multimodaliteitsprogram op die Hermes. Die optimale snit vir elke letsel is gekies volgens die beste aansig op die borskas X-straalom die SPN te lokaliseer. Gebiede van belang (ROl) is met die hand buite-om die buitenste rand van die letsel getrek op die OSEM beeld en daarna outomaties in die ooreenstemmende area op die gekoregistreerde FPB beeld geplaas. Vir die meeste pasiënte is die agtergrond outomaties as horisontale spieëlbeeld op die kontralaterale kant geplaas, eers op die OSEM en dan outomaties op die FBP beeld. 'n Outomatiese vertikale spieëlbeeld of manuele horisontale verskuiwing van die agtergrondsarea is gedoen indien die agtergrond oorvleuel het met 'n 'warm' area soos die hart of werwels. Die gemiddelde tellings en standaardafwyking van die ROl en agtergrond is outomaties gegenereer. Semi-kwantitatiewe beeldanalise is gedoen deur berekening van die sein-tot-agtergrond verhouding (signal-to-noise ratio - SNR) en tumor-tot-agtergrond (TIB) verhouding met behulp van die volgende formules: SNR = gemiddelde tellings ROI(letsel) - gemiddelde tellings agtergrond Standaard afwyking van agtergrond TIB rati.o = -g=em--id-d-e-l-d-e--te=ll-in-g-s__R:_O-I(-le-t-s'e-l) gemiddelde tellings agtergrond Opsporing is soortgelyk bevind vir die twee rekonstruksie algoritmes, dit wil sê elke letselopgespoor met behulp van OSEM kon ook met FBP opgespoor word. Letselwaameming het egter verskil tussen TI-201 en Tc-99m-MIBI. Sensitiwiteit en spesifisiteit is vir verskillende drempels van SNR en TIB verhoudings bereken. 'Receiver operating characteristics' (ROC) kurwes is getrek om die verskillende sensitiwiteite en spesifisiteite by elke drempel te verteenwoordig. Tuberkulose (TB) is nie in hierdie analise ingesluit nie aangesien opname van Tl-201 beduidend hoog en vergelykbaar met die van maligne nodules was. Die effek van OSEM en FBP op die 'positiewe' TB nodules is egter apart beoordeel. Deur berekening van die area onder die ROC kurwes, is getoon dat OSEM van Tl-201 tomografiese data meer akkuraat as FBP was om maligne van benigne nodules te onderskei. Alhoewel hierdie verskil nie statisties betekenisvol was nie (p=0.10), is daar wel 'n duidelike neiging gevind. Die twee rekonstruksie algoritmes was byna ewe akkuraat wanneer Tc-99m-MIBI gebruik is, met duidelik geen betekenisvolle verskil tussen die algoritmes nie. Gevo lgtrekking In hierdie studie is dit getoon dat daar 'n neiging is dat OSEM beter vaar as FBP vir studies met tallium-201 maar nie vir Tc-99m-MIBI nie.

Neste trabalho é apresentado o estudo de alguns dos principais parâmetros envolvidos na fabricação de filmes finos de brometo de tálio (TlBr) por meio da técnica de spray pyrolysis. Investigamos a possibilidade desta técnica vir a se tornar um método alternativo para fabricação de filmes finos de TlBr com qualidade adequada para a confecção de dispositivos detectores de radiação de altas energias, como raios-X e raios-&#947;. O tempo de fabricação e a qualidade dos filmes eram limitados pelo problema da formação de gotas d’água na parte superior da câmara de deposição, o que resultava na incidência destas gotas sobre os filmes, posteriormente. O problema foi resolvido por meio de um sistema de aquecimento extrínseco ao equipamento. A investigação dos parâmetros citados se deu pela variação dos fluxos de nitrogênio e da solução de TlBr, pelas variações da posição dos substratos no porta substrato, da temperatura e do grau de saturação das soluções. As propriedades cristalinas e estruturais dos filmes foram verificadas pela técnica de difração de raios-X e por microscopia eletrônica de varredura, respectivamente. Os resultados mostram que o pico de intensidade dos planos cristalinos preferenciais dos filmes tendem a se tornar mais intensos para soluções saturadas, fabricados com baixo fluxo de nitrogênio e a temperaturas próximas de 100oC. No entanto, dependendo da posição dos filmes sobre o porta-substrato, a intensidade dos picos, assim como a rugosidade superficial, variam significativamente. Com efeito, conseguimos estender o processo de deposição para qualquer tempo desejado, o que implica, a princípio, em filmes mais espessos e de melhor qualidade. / This work presents the results about the investigation of the importance of some of the main parameters related to the fabrication of thin films of thallium bromide (TlBr) using the spray pyrolysis technique. We evaluated the possibilities for the future use of this technique in the development of high quality TlBr thin films to be used as high-energy radiation (such as X- and gamma rays) detectors. The total deposition time as well as the quality of the films were limited due to the formation of water droplets at the inner part of the top surface of the deposition chamber. These droplets would eventually fall over the substrates damaging the sample. This problem was solved by the use of an external heating system. The investigated deposition parameters were: nitrogen and solution flows, substrate position on top of the substrate holder, deposition temperature and composition of the solution. The crystalline and structural properties of the thin films were investigated by X-ray diffraction and Scanning Electron Microscopy. According to the results obtained from the diffraction experiments, the crystalline peaks increase with the saturation of the solution, low nitrogen flow and deposition temperatures close to 100oC. Nevertheless, the substrate position can also influence the crystallinity and amount of deposited material. In summary, we optimized the deposition parameters for the development of thick and high quality films that could be used for the development of sensors in the future.

Organometallic pyridazines and compounds derived from them have been of interest in polymer research due to their atypical environmental stability (as compared to other non-aromatic organic semiconductors) as well as their conductivity. The off-metal synthesis and characterization of several pyridazyl thallium, manganese, and rhenium complexes, beginning with fulvenes 1,2- C5H3(COHR)(COR), are reported here. The diacyl fulvenes were treated with hydrazine hydrate to ring close to pyridazines. Next, the pyridazines were converted to their respective thallium salts through treatment with thallium (I) ethoxide. Lastly, the salts were transmetallated into the respective rhenium or manganese complexes through treatment with the respective metal bound to five carbonyl groups and one bromide (MnCO5Br, ReCO5Br). Our research focused on the synthesis of a variety of 5,6-fused ring pyridazines that will act as a model for homeland security research in polymer studies and medicinal research. Synthesis and characterization of several aryl-substituted 5,6-fused ring pyridazines have been completed. The fulvenes, pyridazines, and thallium salts are important compounds for research due to their reactivity and stability in moisture and air. The complexes synthesized were confirmed using mass spectrometry, infrared spectroscopy, nuclear magnetic resonance spectroscopy, and elemental analysis. Single crystal X-ray diffraction confirmed the structure of x compound 1A. As evidenced by related previous papers published by the research group, the synthesized complexes displayed stability to air, moisture, and temperature.18, 19, 23, 25

L'utilisation croissante de l'aluminium dans les applications les plus diverses a suscité un développement important des recherches consacrées à ses composés fluorés qui jouent un rôle essentiel dans l'élaboration du métal. Il n'en est pas de même pour ses homologues de la colonne III B : lorsque nous avons commencé ce travail la chimie des composés fluorés du gallium, de l'indium et du thallium n'avait pratiquement pas été explorée. Cette lacune s'expliquait par la relative rareté des ces éléments, mais également par les difficultés inhérentes à la chimie du fluor...

In preparation for the large backgrounds expected to be present in the Belle II detector from the SuperKEKB e+e- collider, the radiation hardness of several large (5 x 5 x 30 cm3) thallium doped cesium iodide (CsI(Tl)) scintillation crystals are studied. The crystal samples studied consist of 2 spare crystals from the Belle experiment using PIN diode readout and 7 spare crystals from the BaBar experiment using photomultiplier tube readout. The radiation hardness of the scintillation properties of the CsI(Tl) crystals was studied at accumulated 1 MeV photon doses of 2, 10 and 35 Gy. At each dose, the longitudinal uniformity of the crystals light yield, scintillation decay times, time resolution and energy resolution was measured. As the Belle II collaboration is considering an upgrade to pure CsI crystals if CsI(Tl) does not satisfy radiation hardness requirements, the scintillation properties of a pure CsI scintillation crystal were also measured and compared to the CsI(Tl) crystal measurements. In addition to experimental work, Monte Carlo simulations using GEANT4 were written to compare ideal pure CsI and CsI(Tl) crystals and to study the effects of radiation damage on the performance of the Belle II electromagnetic calorimeter. / Graduate

Made available in DSpace on 2014-10-09T12:34:47Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:03:29Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP