U, FE, AND LI ISOTOPE RATIOS IN THE MINERALIZED AND BARREN AREAS OF THE KOMBOLGIE BASIN

The Paleo- to Meso-Proterozoic Jabiluka unconformity related uranium mine is located within the Alligator River Uranium Field, found in the Northern Territories, Australia. The uranium ore is hosted in the late middle Paleoproterozoic Cahill Formation, which is unconformably overlain by a group of unmetamorphosed conglomerates known as the Kombolgie subgroup. The Kombolgie subgroup provided the source for oxidized basinal brines, carrying U as the mobile form U(VI), which interacted with reducing lithologies in the Cahill formation, thus reducing U(VI) to the solid U(IV), and leading to the precipitation of uraninite (UO2). In order to characterize fluid interaction with the ore body and compare that to areas without mineralization, several isotopic tracers were studied on a series of clay samples from drill core at Jabiluka as well as in barren areas throughout the ARUF. Among the potential tracers, three were selected: U (redox sensitive and recent fluid mobilization), Fe (redox sensitive), and Li (fractionated by hydrothermal fluids and adsorption reactions). δ238U values were found to be closely linked to the mineralogy, with samples with higher K/Al ratios (indicating high illite and low chlorite concentrations) having higher δ238U values. This demonstrates that 235U preferentially absorbs onto the surface of chlorite during hydrothermal circulation. In addition, δ234U values lie far from secular equilibrium (δ234U of 30‰), indicating there was addition or removal of 234U from the surface of the samples from recent (<2.5Ma) interactions of mobile fluids. δ57Fe values were found to be related to lithology and spatially to known uranium deposits. Decreasing δ57Fe values were found with increasing depth to the unconformity in a drill hole directly above the ore zone, but not in drill holes in the barren area. Similarly to δ238U, δ7Li is found to correlate with mineralogy, with higher δ7Li values associated with samples with more chlorite. In addition, higher δ7Li values are found at greater depth throughout the basin, indicating that the direction of the mineralizing fluid circulation was upwards from the Cahill formation to the Kombolgie subgroup.

Optical properties of chiral thin films and microparticles

In this work I study the optical properties of helical particles and chiral sculptured thin films, using computational modeling (discrete dipole approximation, Berreman calculus), and experimental techniques (glancing angle deposition, ellipsometry, scatterometry, and non-linear optical measurements). The first part of this work focuses on linear optics, namely light scattering from helical microparticles. I study the influence of structural parameters and orientation on the optical properties of particles: circular dichroism (CD) and optical rotation (OR), and show that as a consequence of random orientation, CD and OR can have the opposite sign, compared to that of the oriented particle, potentially resulting in ambiguity of measurement interpretation. Additionally, particles in random orientation scatter light with circular and elliptical polarization states, which implies that in order to study multiple scattering from randomly oriented chiral particles, the polarization state of light cannot be disregarded. To perform experiments and attempt to produce particles, a newly constructed multi stage thin film coating chamber is calibrated. It enables the simultaneous fabrication of multiple sculptured thin film coatings, each with different structure. With it I successfully produce helical thin film coatings with Ti and TiO_{2}. The second part of this work focuses on non-linear optics, with special emphasis on second-harmonic generation. The scientific literature shows extensive experimental and theoretical work on second harmonic generation from chiral thin films. Such films are expected to always show this non-linear effect, due to their lack of inversion symmetry. However no experimental studies report non-linear response of chiral sculptured thin films. In this work I grow films suitable for a second harmonic generation experiment, and report the first measurements of non-linear response.

Reversibly Photo-Crosslinkable Polycarbonate-Based Polymersomes for Drug Encapsulation and Delivery

This thesis describes the preparation of polymersomes from poly(ethylene glycol)-block-polycarbonate (PEG-PC) copolymers functionalized with pendant coumarin groups. Coumarin groups undergo photo-reversible dimerization when irradiated with specific ultraviolet wavelengths, so they can be used to prepare polymers with photo-responsive properties. In this case, the pendant coumarin groups enable stabilization of the polymersome membrane through photo-crosslinking of the hydrophobic block. Initially, several novel cinnamoyl and coumarin functionalized cyclic carbonate monomers were synthesized using ester, ether, or amide linkages. While the homopolymerization of these functionalized monomers proved challenging due to their high melting points, both cinnamoyl and coumarin functionalized monomers were successfully copolymerized with trimethylene carbonate (TMC) at 100 ℃ using a catalyst-free melt polymerization process where the TMC doubled as a solvent for the higher melting point monomer. Using this system, polycarbonate copolymers with up to 33% incorporation of the functionalized monomers were prepared. In addition, an investigation of some anomalous polymerization results identified previously unreported triethylamine-based catalysts for the melt polymerization of carbonate monomers. These studies also demonstrated that the catalyst-free polymerization of TMC occurs faster and at lower temperatures than previously reported. Subsequently, the photo-crosslinking of cinnamoyl and coumarin functionalized polycarbonates was compared and coumarin was identified as the more effective crosslinking agent when using 300-400 nm UV. An investigation of the photo-reversibility of the coumarin dimerization revealed no discernible change in the properties of crosslinked networks, but rapid photo-reversion in dilute solutions. The photo-crosslinking and photo-reversion kinetics of the coumarin functionalized polycarbonates were determined to be second-order in both cases. Finally, the self-assembly of PEG-PC diblock copolymers functionalized with coumarin was examined and both reverse solvent evaporation and solvent displacement were found to induce self-assembly, with hydrophilic mass fractions (f-factors) of 12-28% resulting in the formation of solid microparticles and nanoparticles and f-factors of 33-43% resulting in the formation of polymersomes. The stabilization of these polymersome membranes through photo-initiator-free photo-crosslinking was demonstrated with the crosslinking allowing polymersomes to withstand centrifugation at 12,000 x g. In addition, the encapsulation of calcein, as a model small molecule drug, in the stabilized polymersomes was successfully demonstrated using confocal microscopy.