No description available.

Dissertation made openly available per email from author, 6/8/2016.

Chronic arsenic poisoning due to arsenic contamination of groundwater is a serious public health problem in Bangladesh and neighboring countries. Severe health effects associated with chronic exposure to arsenic include melanosis and several kinds of cancer. It is now generally agreed that the arsenic contamination of groundwater in Bangladesh is of geological origin. Arsenic naturally present in aquifers may be mobilized into drinking water by microbial action.<p> The formation of a novel arsenic-selenium compound: seleno-bis (S-glutathionyl) arsinium ion, [(GS)2AsSe]-, and its subsequent excretion in rabbit bile has been demonstrated previously. This molecular basis for the in vivo antagonism between arsenic and selenium was discovered using X-ray absorption spectroscopy. There is growing evidence that, in Bangladeshi people who are suffering long term chronic lowlevel arsenic poisoning, this antagonism is causing a selenium deficiency. Administering selenium supplements might provide a simple but highly effective treatment of the Bangladeshi arsenic poisoning.<p> In order to examine the disposition of [(GS)2AsSe]-, a set of rabbits were intravenously injected with selenite, arsenite or both. Whole blood, red blood cell and plasma samples were collected at different time intervals within 2hrs after injection and cecotrope samples 24hr after injection. Samples were examined using X-ray absorption spectroscopy and both arsenic and selenium K-near edge spectra were recorded.<p> iii Speciation of arsenic and selenium will be discussed in this thesis. Results indicate that [(GS)2AsSe]- is formed in blood very rapidly after injection of both arsenite and selenite, and then is removed from blood stream within 2hrs post injection. Results also show that [(GS)2AsSe]- is assembled in red blood cells, with no [(GS)2AsSe]- detected in plasma samples. [(GS)2AsSe]- is also found in cecotrope samples after injection of both arsenite and selenite.<p> The results of this study in rabbits will contribute to the understanding of chronic arsenic poisoning in humans.

The desire for low cost electronics has led to a huge increase in research focused on organic materials. These materials are appealing due to their unique electrical and material-processing properties and are rapidly being adopted in old and new electronic applications. To create practical devices requires a further understanding of the charge transport properties of the unique anisotropic molecular crystal structures. This work looks at how doping with the transition-metal element manganese can alter the electronic structure of the organic material pentacene. It has been found that using manganese as a dopant provides novel physical characteristics previously not encountered in organic field effect transistors based on pentacene. These organic thin films were characterized using X-ray absorption spectroscopy and the results compared to computational density functional theory analysis.

The desire for low cost electronics has led to a huge increase in research focused on organic materials. These materials are appealing due to their unique electrical and material-processing properties and are rapidly being adopted in old and new electronic applications. To create practical devices requires a further understanding of the charge transport properties of the unique anisotropic molecular crystal structures. This work looks at how doping with the transition-metal element manganese can alter the electronic structure of the organic material pentacene. It has been found that using manganese as a dopant provides novel physical characteristics previously not encountered in organic field effect transistors based on pentacene. These organic thin films were characterized using X-ray absorption spectroscopy and the results compared to computational density functional theory analysis.

Chronic arsenic poisoning due to arsenic contamination of groundwater is a serious public health problem in Bangladesh and neighboring countries. Severe health effects associated with chronic exposure to arsenic include melanosis and several kinds of cancer. It is now generally agreed that the arsenic contamination of groundwater in Bangladesh is of geological origin. Arsenic naturally present in aquifers may be mobilized into drinking water by microbial action.<p> The formation of a novel arsenic-selenium compound: seleno-bis (S-glutathionyl) arsinium ion, [(GS)2AsSe]-, and its subsequent excretion in rabbit bile has been demonstrated previously. This molecular basis for the in vivo antagonism between arsenic and selenium was discovered using X-ray absorption spectroscopy. There is growing evidence that, in Bangladeshi people who are suffering long term chronic lowlevel arsenic poisoning, this antagonism is causing a selenium deficiency. Administering selenium supplements might provide a simple but highly effective treatment of the Bangladeshi arsenic poisoning.<p> In order to examine the disposition of [(GS)2AsSe]-, a set of rabbits were intravenously injected with selenite, arsenite or both. Whole blood, red blood cell and plasma samples were collected at different time intervals within 2hrs after injection and cecotrope samples 24hr after injection. Samples were examined using X-ray absorption spectroscopy and both arsenic and selenium K-near edge spectra were recorded.<p> iii Speciation of arsenic and selenium will be discussed in this thesis. Results indicate that [(GS)2AsSe]- is formed in blood very rapidly after injection of both arsenite and selenite, and then is removed from blood stream within 2hrs post injection. Results also show that [(GS)2AsSe]- is assembled in red blood cells, with no [(GS)2AsSe]- detected in plasma samples. [(GS)2AsSe]- is also found in cecotrope samples after injection of both arsenite and selenite.<p> The results of this study in rabbits will contribute to the understanding of chronic arsenic poisoning in humans.

Previous studies have attempted to probe the structure of ultra-thin Nickel silicide films as they evolve in the manufacturing process with limited success. These studies have used ultra-thin Nickel silicide films that were quenched during the manufacturer's annealing process at select temperatures. This study aims to determine the structure of quenched ultra-thin Ni-Si films using Grazing Incidence X-Ray Absorption Near Edge Spectroscopy (GI-XANES) and ab-initio calculations (FDMNES). Successful calculations were prepared for the δ and θ Ni2Si phases, as well as the Ni3Si2, NiSi and NiSi2 phases. The GI-XANES experimental data was taken at the Canadian Light Source, at the Hard X-Ray Microanalysis Beamline (HXMA). XANES and FDMNES are used to identify two phases of the ultra-thin films: the as-deposited phase as a low-ordered Ni3Si2 phase, and the epitaxial NiSi2 phase was found in samples annealed past 400˚C.

No description available.

In this thesis, two aspects of research in soft X-ray absorption spectroscopy chemistry are explored. The first objective was to measure the natural circular dichroism of small chiral organic molecules at soft X-ray wavelengths. The second objective was to characterize the electronic structure and spectra of a series of organometallic polymers. <p>The goal of the first part of this thesis was to enhance the sensitivity of Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy to the intrinsic handedness of chiral organic molecules. The phenomenon of X-ray natural circular dichroism (XNCD) has been well described by theoreticians; however, there have been few successful measurements reported, mainly due to the weakness of the effect and the difficulty of preparing suitable samples. The fourth chapter of this thesis outlines the requirements for XNCD experiments and the efforts made to prepare appropriate samples. <p>The goal of the second part was to use NEXAFS spectroscopy as an analytical technique for the elemental and chemical characterization of innovative materials based on organoiron compounds. The interpretation of transition metal compounds by NEXAFS spectroscopy is difficult due to complex interactions between the metal and its surroundings. Two approaches are commonly used; an atomic multiplet model and a covalent bonding model, which lead to conflicting spectral assignments. Earlier NEXAFS studies of metallocene complexes were found to be lacking as these two models were not adequately rationalized. Owing in part to greatly improved instrumental sensitivity and to efficient theoretical calculations, the interpretation of NEXAFS spectra for a series of metallocene and metal arene complexes was refined. Enhanced understanding of the spectroscopy of these compounds eventually contributed to the characterization of a series of organometallic polymeric materials.<p>Underlining these studies is the remarkable complementarity of NEXAFS spectroscopy and chemistry. A comprehensive understanding of the chemistry of the samples examined in the measurement of XNCD is shown to be crucial for a successful advancement of this spectroscopy. In return, optimization of soft X-ray spectroscopy of metallocenes is demonstrated to remarkably benefit the understanding of the organometallic polymers.

Living organisms constantly respond to changing environmental conditions, and some changes can be far from optimal for many organisms. Insects represent the majority of species in many ecosystems and play an important role in bioaccumulation and biotransformation of environmental contaminants such as selenium and arsenic. Some insectivorous predators feeding on these insects are highly sensitive to such elements resulting in reduced growth, reproductive failures and low population numbers. The mechanisms of selenium and arsenic uptake through the food chain are poorly understood. The determination of chemical speciation is a prerequisite for a mechanistic understanding of a contaminants bioavailability and toxicity to an organism. Synchrotron-based X-ray absorption spectroscopy was used to identify the chemical form of selenium and arsenic in insects in both the field and laboratory conditions. Insects living in streams near Hinton, Alberta affected by coal mine activities were examined for selenium speciation. Results showed higher percentages of inorganic selenium in primary consumers, detritivores and filter feeders than in predatory insects. Selenides and diselenides constitute a major fraction of selenium in these insects. In another field setting, speciation of selenium was studied in insects attacking selenium hyperaccumulating plant <i>Astragalus bisulcatus</i>. The effect of selenate and arsenate alone and the combined effects of selenate and arsenate on insects and parasitoids were monitored using a laboratory-reared moth (<i>Mamestra configurata</i>). Hosts receiving selenium biotransformed selenate to organic selenides and diselenides, which were transferred to the parasitoids in the third trophic level. Arsenic fed larvae biotransformed dietary arsenate to yield predominantly trivalent arsenic coordinated with three aliphatic sulfurs. Larvae receiving arsenate used a novel six-coordinated arsenic form as an excretory molecule in fecal matter and cast skin. X-ray absorption spectroscopy imaging with micro X-ray fluorescence imaging on selenate and arsenate fed larvae revealed highly localized selenium and arsenic species, zinc and copper within the gut. The results provide insights into how the insects cope with their toxic cargo, including how selenium and arsenic are biotransformed into other chemical forms and how they can be eliminated from the insects. The implication of selenium and arsenic species in the diet of predators and detritivores is discussed.