The objective of this project is to apply the Optical Stimulated Luminescence (OSL) technique to date the palaeo sediment from Mu Us Desert, part of the Inner Mongolia in northern China and reconstruct the palaeo environment. Five OSL samples were collected from Dagouwan, Salawusu River Valley at Inner Mongolia by Dr S. H. Li and his team in 2009. Extraction of 150μm to 180μm silt-size feldspar from collected dune sand, lacustrine facies and fluvial facies samples and running of luminescence dating therefore to obtain the age from 50ka to 90ka. Climate proxies - magnetic susceptibility, grain size, fossil vertebrates and fossil pollens have been analyzed and it is concluded that significant climate change occurred within this period, which change from domination of warm, humid and rainy summer monsoons (before 70ka) to cold, wind, windy strengthened dry winter wind and back to warm and humid again after 55ka. / published_or_final_version / Applied Geosciences / Master / Master of Science

abstract / Earth Sciences / Doctoral / Doctor of Philosophy

A library of variously-substituted dipyrrins and their first-row transition metal (Mn, Fe, Cu, Zn) complexes have been synthesized, and the effects of peripheral substituents on the spectroscopic, electrochemical, and structural properties of both the free-base dipyrrins and their metal complexes has been explored. The optical and electrochemical properties of the free dipyrrins follow systematic trends; with the introduction of electron-withdrawing substituents in the 2-, 3-, 5-, 7-, and 8-positions of the dipyrrin, bathochromic shifts in the absorption spectra are observed, oxidation becomes more difficult, and reduction becomes more facile. Similar effects are seen for iron(II) dipyrrinato complexes, where peripheral substitution of the dipyrrinato ligand induces red-shifts in the absorption spectra and increases the oxidation potential of the bound iron. Steric interactions between the peripheral halogens and the 5-substituent of the dipyrrinato ligand can induce distortion of the ligand from planarity, resulting in widely varying 57Fe Mössbauer quadrupole splitting (|ΔEQ|) parameters. / Chemistry and Chemical Biology

published_or_final_version / Physics / Master / Master of Philosophy

A detailed study is made on the luminescence of Pb('2+) ions in alkali halide single crystals. The emission spectra of KX:Pb('2+) (X = Cl, Br, I) excited in the A-absortpion band at various temperatures are reported. In addition, the excitation spectra of the A-band emission measured at 4.2 and 78 K are also given. The temperature dependence and the effect of an external magnetic field on the decay time of the A-band emission from KX:Pb('2+) is also investigated. / The results are interpreted in terms of a model that includes the Jahn-Teller effect, the spin-orbit interaction and an additional perturbation caused by the charge compensating cation vacancy (CV, v(,c)('-)). In this model, the Jahn-Teller effect is much smaller than the spin-orbit interaction and the CV is smaller still. The experimental results for KX:Pb('2+) are well in accord with this model. / The angular dependence of the polarization of the A-band emission from KX:Pb('2+) confirms that the Pb('2+) - v(,c)('-) pair is located on the C(,4) crystallographic axis. The temperature dependence of the polarization is treated within the framework of the above model in terms of the nonradiative processes between the relaxed excited states.

The impact of a tri-substituted boron moiety on the chelate sensitization of Tb(III) and Eu(III) lanthanide luminescence and their resulting photophysical properties was investigated. Two triarylboron-functionalized carboxylate ligands 1 and 2 and their respective Tb(III) and Eu(III) complexes, 1Tb, 2Tb, 1Eu and 2Eu were synthesized and fully characterized. The photophysical properties of these compounds were studied and it was established that these three-coordinate boron ligands are highly effective in selective activation of Tb(III) and Eu(III) luminescence yielding high efficiency green and red luminescence, respectively. Potential applications of these triarylboron-functionalized chelate Tb(III) and Eu(III) complexes as luminescent sensors for dipicolinic acid (DPA), a biomarker for anthrax spores, as well as small anions such as F- and CN- in organic solution were examined by titration experiments using UV-Vis absorption and fluorescence emission measurements. Further studies were carried out into the application of the lanthanide complexes as solid substrate luminescent sensors for the same analytes. Furthermore a novel zinc-binding compound, composed of both an 8-hydroxyquinoline fluorophore and a dipyridyl metal binding site, was designed for application as a luminescent sensor for Zn(II), due to the recent link between the metal ion and certain high-profile neurological conditions such as Alzheimer’s and epilepsy. The target ligand compound 1-OH was successfully synthesized and characterized using UV-Vis, Fluorescence and NMR spectroscopy. Further studies of the ligand are recorded by studying the effects of the addition of both four-coordinate boron and tris(8-hydroxyquinolinato)aluminum active sites to the 1-OH molecule frame. The four compounds’ abilities in luminescent Zn(II) detection in organic media were examined by titration experiments with Zn(II) using UV-Vis absorption and fluorescence emission measurements. / Thesis (Master, Chemistry) -- Queen's University, 2012-09-11 16:36:17.004

Monothiolate protected gold nanoclusters with near IR luminescence underwent a five-to-ten fold enhancement of quantum efficiency by heating in the presence of excess thiols. Two monothiolate nanoclusters, mercaptosuccinic acid and tiopronin, were shown to benefit from this procedure. Emission maximum around 700-900 nm is favorable for bioimaging applications due to reduction of background signal from autofluorescence. Dithiolate lipoic acid protected gold nanoclusters with higher near IR quantum efficiency present an interesting candidate for biological imaging due to the difference in hydrophobicity, resistance to quenching by divalent cations and cell growth media, and retained quantum efficiency when coupled to agents such as polyethylene glycol. Intracellular and nuclear internalization of mercaptosuccinic gold nanoclusters demonstrate a potential vector for delivery of nuclear targeting agents. The small size, chemical stability, high luminescence, and potential for targeting various intracellular domains make gold nanoclusters worthwhile for further studies as potential bioimaging probes.

This thesis presents an investigation of the phenomenon of efficient, room temperature luminescence from dislocation-engineered (DE) silicon. Previous work had demonstrated that the introduction of near-surface dislocation loops to a silicon substrate by boron ion implantation and high temperature annealing produced efficient electroluminescence at room temperature. However, the mechanism by which high efficiency luminescence is produced was not understood. A wide matrix of specimens containing dislocations was fabricated by a variety of methods, including ion implantation, and their luminescence efficiencies were correlated to their physical properties. Transmission electron microscopy was used to characterise the defect structures created by ion implantation. In the majority of specimens a band of dislocation loops in close proximity to the surface was observed. The dislocation loops were shown to be consistent with a mixture of Frank and perfect dislocation loops, the relative proportions of which were dependent upon processing conditions. The thermal evolution of the dislocation loop size distribution was investigated. For the first time, a size distribution displaying a double peak was observed. The size distribution was shown to be consistent with the Gaussian distribution of two defect populations of different mean diameter. The thermal evolution of the size distribution was investigated in silicon implanted samples. A flux of self-interstitials from Frank dislocation loops to perfect dislocation loops was deduced. The evolution of the dislocation loop sizes was found to be consistent with Ostwald ripening. Cathodoluminescence (CL) was used to investigate the luminescent properties of silicon at room temperature for the first time. A new CL system was installed for this work, initially the CL system was characterised and a routine to ensure a high degree of reproducibility was formed. The luminescence mechanism of DE-silicon was shown to be the same as in unprocessed silicon wafers; TO phonon-assisted recombination. The mechanism of enhanced luminescence from DE-silicon was unambiguously shown to be due to the gettering of electrically active impurities from the specimen bulk. A reduction in the bulk transition metal impurity concentration of up to 35 times was inferred. In samples which were implanted with boron the degree of gettering was found to show a logarithmic dependence on the dislocation density. Using a crosssectional mapping technique, implanted samples were shown to contain a lower concentration of transition metal impurities throughout the entire wafer in comparison to as-received, unprocessed specimens. Furthermore, the impurity concentration was found to be lowest in close proximity to the band of dislocation loops. The dislocation loops were found to act as non-radiative recombination centres and their strength was strongly influenced by the local carrier concentration. The high doping levels of samples implanted with boron were found to minimise the non-radiative recombination action of the dislocations. Low temperature annealing was used to improve the luminescence efficiency of DE-silicon further.

Quorum sensing is a cell density-dependent bacterial gene regulatory mechanism used for the expression of colonization-related genes. The symbiotic relationship between the luminescent bacterium Vibrio fischeri and the Hawaiian bobtail squid Euprymna scolopes serves as a model system to study the molecular processes underlying bacterial colonization. This system is especially well-suited for the investigation of the impact of quorum sensing on colonization because (i) it is an easily accessible, natural, two-species colonization model, and (ii) quorum sensing regulates luminescence expression in V. fischeri, which allows the non-invasive detection of quorum-sensing activity both in culture and in symbiosis. While the impact of one of V. fischeri's quorum-sensing systems, lux, on luminescence expression and symbiotic competence has been extensively studied, little was known about other putative systems. The results of this study demonstrate that the V. fischeri ain system is essential for both maximal luminescence expression and symbiotic competence. The ain system predominantly induces luminescence expression at intermediate cell densities, which occur in culture, while the lux system is responsible for luminescence expression at the high cell densities found in symbiosis, suggesting the sequential induction of luminescence gene expression by these two systems. Furthermore, the ain quorum sensing system is important for the processes underlying colonization initiation, while the impact of the lux system is apparent only in later stages of the symbiosis, indicating distinct functions of these two systems during the colonization process. A global transcriptome. analysis of quorum-sensing mutants revealed that ain quorum sensing represses motility gene expression, providing a likely explanation for the initiation defect. Although it has been known that many bacterial species possess multiple quorum-sensing systems, this is the first study demonstrating that two quorum-sensing systems are employed to specifically regulate functions important at distinct cell densities occurring during the colonization process.

Thesis (Ph. D.)--University of Hong Kong, 2008. / Also available in print.