abstract: Photocatalytic water splitting over suspended nanoparticles represents a potential solution for achieving CO2-neutral energy generation and storage. To design efficient photocatalysts, a fundamental understanding of the material’s structure, electronic properties, defects, and how these are controlled via synthesis is essential. Both bulk and nanoscale materials characterization, in addition to various performance metrics, can be combined to elucidate functionality at multiple length scales. In this work, two promising visible light harvesting systems are studied in detail: Pt-functionalized graphitic carbon nitrides (g-CNxHys) and TiO2-supported CeO2-x composites. Electron energy-loss spectroscopy (EELS) is used to sense variations in the local concentration of amine moieties (defects believed to facilitate interfacial charge transfer) at the surface of a g-CNxHy flake. Using an aloof-beam configuration, spatial resolution is maximized while minimizing damage thus providing nanoscale vibrational fingerprints similar to infrared absorption spectra. Structural disorder in g-CNxHys is further studied using transmission electron microscopy at low electron fluence rates. In-plane structural fluctuations revealed variations in the local azimuthal orientation of the heptazine building blocks, allowing planar domain sizes to be related to the average polymer chain length. Furthermore, competing factors regulating photocatalytic performance in a series of Pt/g-CNxHys is elucidated. Increased polymer condensation in the g-CNxHy support enhances the rate of charge transfer to reactants owing to higher electronic mobility. However, active site densities are over 3x lower on the most condensed g-CNxHy which ultimately limits its H2 evolution rate (HER). Based on these findings, strategies to improve the cocatalyst configuration on intrinsically active supports are given. In TiO2/CeO2-x photocatalysts, the effect of the support particle size on the bulk/nanoscale properties and photocatalytic performance is investigated. Small anatase supports facilitate highly dispersed CeO2-x species, leading to increased visible light absorption and HERs resulting from a higher density of mixed metal oxide (MMO) interfaces with Ce3+ species. Using monochromated EELS, bandgap states associated with MMO interfaces are detected, revealing electronic transitions from 0.5 eV up to the bulk bandgap onset of anatase. Overall, the electron microscopy/spectroscopy techniques developed and applied herein sheds light onto the relevant defects and limiting processes operating within these photocatalyst systems thus suggesting rational design strategies. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2019

abstract: Extended crystal defects often play a critical role in determining semiconductor device performance. This dissertation describes the application of transmission electron microscopy (TEM) and aberration-corrected scanning TEM (AC-STEM) to study defect clusters and the atomic-scale structure of defects in compound semiconductors. An extensive effort was made to identify specific locations of crystal defects in epitaxial CdTe that might contribute to degraded light-conversion efficiency. Electroluminescence (EL) mapping and the creation of surface etch pits through chemical treatment were combined in attempts to identify specific structural defects for subsequent TEM examination. Observations of these specimens revealed only surface etch pits, without any visible indication of extended defects near their base. While chemical etch pits could be helpful for precisely locating extended defects that intersect with the treated surface, this study concluded that surface roughness surrounding etch pits would likely mitigate against their usefulness. Defect locations in GaAs solar-cell devices were identified using combinations of EL, photoluminescence, and Raman scattering, and then studied more closely using TEM. Observations showed that device degradation was invariably associated with a cluster of extended defects, rather than a single defect, as previously assumed. AC-STEM observations revealed that individual defects within each cluster consisted primarily of intrinsic stacking faults terminated by 30° and 90° partial dislocations, although other defect structures were also identified. Lomer dislocations were identified near locations where two lines of strain contrast intersected in a large cluster, and a comparatively shallow cluster, largely constrained to the GaAs emitter layer, contained 60° perfect dislocations associated with localized strain contrast. In another study, misfit dislocations at II-VI/III-V heterovalent interfaces were investigated and characterized using AC-STEM. Misfit strain at ZnTe/GaAs interfaces, which have relatively high lattice mismatch (7.38%), was relieved primarily through Lomer dislocations, while ZnTe/InP interfaces, with only 3.85% lattice mismatch, were relaxed by a mixture of 60° perfect dislocations, 30° partial dislocations, and Lomer dislocations. These results were consistent with the previous findings that misfit strain was relaxed primarily through 60° perfect dislocations that had either dissociated into partial dislocations or interacted to form Lomer dislocations as the amount of misfit strain increased. / Dissertation/Thesis / Doctoral Dissertation Physics 2020

Dichapetalum cymosum (poison leaf) is a very common problem plant in southern Africa. Fluoroacetic acid, believed to be the poisonous entity in the plant, is produced by the plant, but the micro-organisms associated with this plant may also play a role in the production thereof. A previous study on Burolderia cepacia, an endophyte of D. cymosum showed active metabolism of fluoroacetate by this endophyte. The isolated endophytes from D. cymosum were studied to determine whether they synthesise any fluorinated compounds. It seemed from preliminary results that symbionts might play a role in the synthesis of the poisonous entities in D. cymosum, but further investigation is required. The detection of glandular lesions on the abaxial side of the leaf led to closer examination and the cross sections revealed unusually deformed epidermis cells with adjacent cells containing vacuoles filled with phenolic-like crystals. Transmission electron microscopy (TEM) of the spongy parenchyma cells directly above the glandular lesions indicated the presence of clusters of small, virus-like particles (VLPs) in the chloroplasts. Observations by TEM showed that these VLPs have analogous structures to phytoferritin. Tapura fischeri (leafberry tree) is a tree member of the same family, and it was found to also contain a fluorinated compound. Endophytes were also found in the plant and similar glandular lesions with analogous VLPs were observed at these sites. This might indicate that endophytes have a share in the biosynthesis of the fluorinated compounds found in Dichapetalaceae. Numerous factors ought to be considered in order to fully understand the chemical ecology of the intricate system regarding the endophytes and the possible toxicity of the family Dichapetalaceae. / Dissertation (MSc)--University of Pretoria, 2012. / Plant Science / unrestricted

Les puits quantiques InGaN/GaN montrent la plus grande efficacité connue dans le bleu-UV et le défi actuel dans ce type de matériau est de pousser leur émission vers les grandes longueurs d’ondes. Ceci serait possible en augmentant la composition en indium, mais il faut alors gérer les contraintes résultantes. Ce travail a mis en œuvre la microscopie électronique en transmission et la diffraction des rayons X pour déterminer la composition chimique à l’intérieur des couches InGaN, le taux de relaxation et le type de défauts présents. Les résultats montrent qu’il n’y a pas de fluctuations de composition en indium dans les couches d’InGaN étudiées avec des taux d’indium de l’ordre de 20%. Ainsi, la différence d’émission des échantillons pourrait s’expliquer par la variation d’épaisseur des puits quantiques InGaN et laprésence de défauts. En effet, plusieurs types de défauts ont été observés et caractérisés tels que les pinholes ou des domaines de défauts plans selon leur origine. Dans les multicouches InGaN/GaN avec couches AlGaN compensatrices de contrainte,la diffraction des rayons X a montré que lorsque l’épaisseur des couches d’AlGaN augmente en gardant constante l’épaisseur entre les couches actives d’InGaN (avec une valeur d’environ 16-17 nm), les puits quantiques sont totalement contraints dans le plan de croissance et en dehors. Par microscopie électronique, nous montrons queleur relaxation se fait par formation aussi bien de défauts en domaines plans que de dislocation de type a. Ces dislocations se propagent des pits quantiques vers la surface, et la densité des défauts augmente avec l’épaisseur des couches d’AlGaN. / InGaN/GaN quantum wells show the highest known emission efficiency in UV-blue and the current challenge is to push to longer wavelengths. This would be possible by increasing the indium composition but the challenge becomes how to handle the resulting strains. This work has combined transmission electron microscopy and Xray diffraction in order to determine the relaxation rates, the local chemical composition and defects formation in these systems. The results show that there are no composition fluctuations in these InGaN layers where the indium content was around 20%. Therefore, the differences in emission may be explained by the changes in quantum wells thicknesses and/or the presence of defects. Indeed, several types of defects have been observed and characterized, such as pinholes or planar defect domains. For InGaN/GaN quantum wells with strain compensating AlGaN layers, Xray diffraction showed that, when the AlGaN layer thickness increases, keeping constant the spacing between InGaN layers (around 16-17 nm), the quantum wellsare totally strained in and out the growth plan. Using transmission electron microscopy, it is shown that the relaxation occurs through the formation of domains as well as a type dislocations. The dislocations propagate from the quantum well tothe surface and the density of the defects increases with the thickness of the AlGaN layers.

Surfactants self-assemble into aggregates above a certain concentration. In this work mixtures of the cationic surfactant cetyltrimetylammonium bromide (CTAB) and the anionic surfactant sodium octyl sulfate (SOS) were investigated systematically. The measurements were accomplished by combining the two complimentary techniques static light scattering (SLS) and cryo-transmission electron microscopy (CRYO-TEM). It was found that CTAB-rich samples contain large threadlike micelles rather close to mole fractions where vesicles start to form. The mole fraction x of the surfactant in excess in the aggregates was calculated and it was found that it differs a lot from the mole fraction in the bulk, and the transition from micelles to vesicles occurs when x is about 0.7. In the SOS-rich samples small globular micelles were observed that transform into vesicles upon dilution. Some of the samples rich in SOS were found to contain open vesicles with CRYO-TEM and the reasons for this behavior have been discussed. One question that needs to be further investigated is whether or not these structures are the result of some kind of distortion of the equilibrium process during sample preparation in connection with CRYO-TEM measurements. In most cases the two methods showed consistent results and trends, but for some samples differences could be observed.

Intracellular calcium is a major determinant of a wide variety of cell functions and thus of organ function. In order to get a clear picture of the intracellular calcium status it is preferable to assess the content of the various intracellular calcium pools as well as the characteristics of the transmembrane calcium movements, Le., the magnitude of the transmembrane Ca2+ flux upon stimulation and the rate of the subsequent return to baseline levels. The first aim of this study was to establish and evaluate the methods in the laboratory. The methods investigated include atomic absorption spectrometry, graphite furnace atomic absorption spectrometry and inductively coupled plasma mass spectrometry for the determination of the total cell calcium content, fluorescence spectrophotometry for the determinations of intracellular free Ca2+ and transmembrane Ca2+ movements and transmission electron microscopy for the localisation of intracellular calcium. The methods eventually identified as feasible included fluorescence spectrophotometry for the determination of intracellular free Ca2+ and transmembrane Ca2+ movements and transmission electron microscopy for the localisation of intracellular calcium. The newly developed fluorescent calcium indicator, fura-PE3, was presently shown to be the most reliable fluorescent indicator for the intracellular free Ca2+ determinations. The best method for the calcium localisation by transmission electron microscopy was an adaptation of the antimonate precipitation technique. The following objectives were set in order to contribute to the knowledge in chronic renal failure; examination of the intracellular free Ca2+ content in the neutrophils of end stage renal failure patients on maintenance haemodialysis treatment, as the result of renal failure, dialysis treatment and medication combined; examination of the characteristics of the transmembrane Ca2+ movements; investigation of the intracellular calcium distribution in the neutrophils; exploration of a possible link between the alterations in intracellular calcium status and factors known to influence the calcium status, including the lipid composition of the membrane, the oxidative status as reflected by anti-oxidant vitamin levels, as well as the levels of parathyroid hormone, and ionised serum calcium. This study involved 14 chronic renal failure patients on maintenance haemodialysis. An increase in intracellular free Ca2+, the magnitude of the transmembrane Ca2+ flux upon fMLP stimulation and an increase in the rate of the subsequent decrease in intracellular free calcium were found. In separating the patients into those receiving rHuEPO and those not receiving rHuEPO, it was seen that the significance in the increase in intracellular free Ca2+ could be ascribed to the values obtained in those patients receiving rHuEPO - despite the fact that they were the only patients receiving calcium channel blockers. No overt indications of oxidative stress could be detected by anti-oxidant vitamin levels. Nevertheless, a decrease in the content of specific membrane fatty acids occurred, supporting the previous suggestions of the presence of a mild chronic inflammatory condition in the chronic renal failure patient on maintenance haemodialysis treatment. These results suggest that factors other than those associated with uraemia, such as rHuEPO administration, might result in an increase in intracellular free Ca2+ in cells of CRF/MHT patients. The magnitude of the rHuEPD-induced increase in intracellular free Ca2+ and the effects of the various calcium channel blockers need urgent further investigation as ineffective counteraction of the rHuEPO effect, as indicated by the relative ineffectivity of Norvasc, may have serious side-effects. / Dissertation (MSc)--University of Pretoria, 2000. / Physiology / unrestricted

The urinary bladder is a unique organ in that its normal function is storage and release of urine, and vasculature in its wall exhibits specialized features designed to accommodate changes in pressure with emptying and filling. Although we have previously described the fine details of the microvasculature of the urinary bladder of the rabbit and dog, information on the fine details of the microvasculature of the mouse bladder were deemed to be of value because of the increasing use of this species in developing genetic models for studying human disorders. The present study shows that many of the special features of the microvasculature of the mouse urinary bladder are similar to those described in the rabbit and dog, including vessel coiling, abundant collateral circulation, arterial sphincters, and a dense mucosal capillary plexus.

The urinary bladder is a unique organ in that its normal function is storage and release of urine, and vasculature in its wall exhibits specialized features designed to accommodate changes in pressure with emptying and filling. Although we have previously described the fine details of the microvasculature of the urinary bladder of the rabbit and dog, information on the fine details of the microvasculature of the mouse bladder were deemed to be of value because of the increasing use of this species in developing genetic models for studying human disorders. The present study shows that many of the special features of the microvasculature of the mouse urinary bladder are similar to those described in the rabbit and dog, including vessel coiling, abundant collateral circulation, arterial sphincters, and a dense mucosal capillary plexus.

The cast products Mg–Sn based alloys are promising candidates for automobile industries, since they provide a cheap yet thermally stable alternative to existing alloys. One drawback of the Mg–Sn based alloys is their insufficient hardness. The hardenability can be improved by engineering the microstructure through additions of Zn to the base alloy and selective aging conditions. Therefore, detailed knowledge about the microstructural characteristics and the role of Zn to promote precipitation hardening is essential for age hardenable Mg-based alloys. In this work, microstructural investigation of the Mg–1.4Sn–1.3Zn–0.1Mn (at.%) precipitation system was performed using TEM. The chemical composition of the precipitates was analyzed using EDS. APT was employed to obtain precise chemical information on the distribution of Zn in the microstructure. It was found from microstructural studies that different precipitates with varying sizes and phases were present; lath-shaped precipitates of the Mg2Sn phase have an incoherent interface with the matrix, unlike the lath-shaped MgZn2 precipitates. Furthermore, nano-sized precipitates dispersed in the microstructure with short-lath morphology can either be enriched with Sn or Zn. On the other hand, APT analysis revealed the strong repulsion between Sn and Zn atoms in a portion of the analysis volume. However, larger reconstruction volume required to identify the role of Zn is still limited to the optimization of specimen preparation.

abstract: Non-stoichiometric oxides play a critical role in many catalytic, energy, and sensing technologies, providing the ability to reversibly exchange oxygen with the ambient environment through the creation and annihilation of surface oxygen vacancies. Oxygen exchange at the surfaces of these materials is strongly influenced by atomic structure, which varies significantly across nanoparticle surfaces. The studies presented herein elucidate the relationship between surface structure behaviors and oxygen exchange reactions on ceria (CeO2) catalyst materials. In situ aberration-corrected transmission electron microscopy (AC-TEM) techniques were developed and employed to correlate dynamic atomic-level structural heterogeneities to local oxygen vacancy activity. A model Ni/CeO2 catalyst was used to probe the role of a ceria support during hydrocarbon reforming reactions, and it was revealed that carbon formation was inhibited on Ni metal nanoparticles due to the removal of lattice oxygen from the ceria support and subsequent oxidation of adsorbed decomposed hydrocarbon products. Atomic resolution observations of surface oxygen vacancy creation and annihilation were performed on CeO2 nanoparticle surfaces using a novel time-resolved in situ AC-TEM approach. Cation displacements were found to be related to oxygen vacancy creation and annihilation, and the most reactive surface oxygen sites were identified by monitoring the frequency of cation displacements. In addition, the dynamic evolution of CeO2 surface structures was characterized with high temporal resolution AC-TEM imaging, which resulted in atomic column positions and occupancies to be determined with a combination of spatial precision and temporal resolution that had not previously been achieved. As a result, local lattice expansions and contractions were observed on ceria surfaces, which were likely related to cyclic oxygen vacancy activity. Finally, local strain fields on CeO2 surfaces were quantified, and it was determined that local strain enhanced the ability of a surface site to create oxygen vacancies. Through the characterization of dynamic surface structures with advanced AC-TEM techniques, an improvement in the fundamental understanding of how ceria surfaces influence and control oxygen exchange reactions was obtained. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2019