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Electron transport in vacuum deposited a-Se films has been investigated by Interrupted-Field Time-of-Flight (IFTOF) transient photoconductivity experiments to examine the effect of sample temperature (T) and applied electric field (F) on X-ray induced changes in the electron lifetime. Upon exposure to x-rays, the electron lifetime decreases. The decrease in normalized lifetime is almost linearly proportional to the absorbed dose, and is more significant at higher temperatures. Upon the cessation of x-ray irradiation, the lifetime recovers towards its equilibrium value through a structural relaxation process, and is characterized by a structural relaxation time. The structural relaxation time decreases with temperature in an Arrhenius fashion, and exhibits an activation energy that is roughly 1.4 eV. The structural relaxation time at room temperature (21 C) is 2 – 4 hrs whereas at 35 C, 6 – 10 mins. These measurements are important in characterizing the charge collection efficiency of a-Se based x-ray detectors, and its dependence on x-ray exposure and temperature. The results indicate that the rate of change of electron lifetime per unit exposure is less than 2%/Gy.

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No description available.

No description available.

Despite previous extensive study of the widely-employed ruthenium-catalysed olefin metathesis reaction, the finer mechanistic details have not been elucidated. An area that is noticeably lacking is spectroscopic exploration of the relevant complexes. In this work, organometallic ruthenium complexes of importance to olefin metathesis have been investigated using Ru K-edge X-ray absorption spectroscopy. The lowest energy feature in the Ru K-edge spectrum has been unambiguously assigned as due to Ru 4d←1s transitions. These electric-dipole-forbidden transitions are extremely sensitive to geometry. For centrosymmetric complexes, the pre-edge feature has very low intensity because it is limited by the weak electric quadrupole mechanism. By contrast, non-centrosymmetric complexes exhibit a substantial increase in pre-edge intensity because Ru 5p-4d mixing introduces electric-dipole-allowed character to the Ru 4d←1s transitions. The energy of the edge feature in the Ru K-edge spectrum corresponds to ionisation of 1s electrons and is a good indicator of the charge on the metal centre. Unexpectedly, we found that the first-generation (L = PCy₃) Grubbs precatalyst (1) has a higher 1s ionisation energy than the second-generation (L = H₂IMes) complex (2). This effect provides a compelling rationale for the unexplained differences in phosphine dissociation kinetics for complexes 1 and 2: the phosphine dissociation rate of 2 is slower than 1 because the metal centre is more electron-deficient in 2. Density functional theory calculations confirm the charge differences and offer some insight into the nature of bonding in these complexes, particularly with regard to the N-heterocyclic carbene and trialkylphosphine ligands. On the basis of these results, we propose that, for this system, the NHC ligand is a weaker σ-charge donor than the phosphine ligand, and that the NHC accepts significant π-electron density from the metal; both interactions function to reduce the electron density on the ruthenium centre. An ultimate goal is to investigate reactive species in the olefin metathesis mechanism; accordingly, we have made considerable progress toward collecting XAS data for a metallacyclobutane species, and we are pursuing methods to trap the four-coordinate intermediate in the metathesis cycle.

Dual-energy (DE) x-ray imaging of the chest decomposes two radiographs acquired at low- and high x-ray energies into 'soft-tissue' and 'bone' images, reducing the influence of background anatomical noise and providing increased conspicuity of subtle underlying structures compared to conventional radiography. This thesis derives a quantitative theoretical model of imaging performance in DE x-ray imaging and employs the resulting framework to system optimization in thoracic imaging. Fourier domain metrics of signal and noise performance - including the noise-power spectrum (NPS), modulation transfer function (MTF), detective quantum efficiency (DQE), and noise-equivalent quanta (NEQ) - were computed using cascaded systems analysis extended to DE imaging and combined with a quantitative model of imaging task to yield estimates of detectability across a broad range of DE image acquisition and decomposition techniques. Specifically, the detectability index provided an objective function for optimizing the selection of kVp pair, added filtration, allocation of dose between low- and high- energy views, and choice of decomposition algorithm and parameters therein. Theoretical calculations were validated in comparison to measurements of NPS, MTF, DQE, and NEQ performed on an experimental DE imaging system and through human observer studies for a variety of imaging tasks. Overall, the detectability index was found to provide a reliable predictor of human observer performance. Results identified optimal DE image acquisition and decomposition techniques that boost detectability beyond that achieved by conventional radiography or other DE imaging approaches, in many cases boosting conspicuity of subtle lesions from barely visible to highly conspicuous at fixed dose to the patient. The results are particularly encouraging, as such performance was achieved with the DE imaging dose equivalent to that of a single chest radiograph. The theoretical framework provided a valuable guide to optimization of a clinical prototype for high-performance DE chest imaging and may be extended to other DE imaging approaches, such as DE mammography and DE computed tomography.

Dual-energy (DE) x-ray imaging of the chest decomposes two radiographs acquired at low- and high x-ray energies into 'soft-tissue' and 'bone' images, reducing the influence of background anatomical noise and providing increased conspicuity of subtle underlying structures compared to conventional radiography. This thesis derives a quantitative theoretical model of imaging performance in DE x-ray imaging and employs the resulting framework to system optimization in thoracic imaging. Fourier domain metrics of signal and noise performance - including the noise-power spectrum (NPS), modulation transfer function (MTF), detective quantum efficiency (DQE), and noise-equivalent quanta (NEQ) - were computed using cascaded systems analysis extended to DE imaging and combined with a quantitative model of imaging task to yield estimates of detectability across a broad range of DE image acquisition and decomposition techniques. Specifically, the detectability index provided an objective function for optimizing the selection of kVp pair, added filtration, allocation of dose between low- and high- energy views, and choice of decomposition algorithm and parameters therein. Theoretical calculations were validated in comparison to measurements of NPS, MTF, DQE, and NEQ performed on an experimental DE imaging system and through human observer studies for a variety of imaging tasks. Overall, the detectability index was found to provide a reliable predictor of human observer performance. Results identified optimal DE image acquisition and decomposition techniques that boost detectability beyond that achieved by conventional radiography or other DE imaging approaches, in many cases boosting conspicuity of subtle lesions from barely visible to highly conspicuous at fixed dose to the patient. The results are particularly encouraging, as such performance was achieved with the DE imaging dose equivalent to that of a single chest radiograph. The theoretical framework provided a valuable guide to optimization of a clinical prototype for high-performance DE chest imaging and may be extended to other DE imaging approaches, such as DE mammography and DE computed tomography.

This thesis addresses the electronic structure of molecules and solids using resonant X-ray emission and photoemission spectroscopy. The use of monochromatic synchrotron radiation and the improved performance of the instrumentation have opened up the possibility of detailed analyses of the response of the electronic systems under interaction with X-rays. The experimental studies are accompanied by numerical ab initio calculations in the formalism of resonant inelastic scattering. The energy selectivity has made it possible for the first time to study how the chemical bonds in a molecule break up during resonant inelastic X-ray scattering. In the conjugated polymer systems, the element selectivity of the X-ray emission process made it possible to probe the different atomic elements separately. The X-ray emission technique proved to be useful for extracting isomeric information, and for measuring the change in the valence levels at different degrees of doping. In this thesis, spectral satellite features in transition metals were thoroughly investigated for various excitation energies around a core-level threshold. By measuring the relative spectral intensity of the satellites it was possible to extract information on the partial core-level widths. Using the nickel metal system as an example, it was shown that it is possible to probe the different core-excited states close toshake-up thresholds by measuring the relative spectral intensity variation of the Auger emission.Resonant photoemission measurements showed unambiguous evidence of interference effects. Theseeffects were also thoroughly probed using angle-dependent measurements. The combination of X-rayemission and absorption were useful for studying buried layers and interfaces due to the appreciable penetration depth of soft X-rays. X-ray scattering was further found to be useful for studying low-energy excited states of rare earth metallic compounds and transition metal oxides.

Bacterial membranes are dynamic structures, and contain lipid components that are individually simple, but complex as a whole system. The presence of charged functional groups makes them capable of interaction with ubiquitous environmental metals. Physiological responses of bacteria to metals, in preservation of membrane functions and integrity, are unclear. In this study, membrane lipid profiles were characterized for Shewanella putrefaciens CN32. Both fatty acid chemistry and hydrophilic headgroup chemistry were assayed, after growing the cells in a chemically defined medium spiked with Mn, V, or U. Cultures were grown in both aerobic and anaerobic conditions, to examine the effects of O2 and CO2 gases, as well as the combined effects of these gases with metals. The results were compared to scanning transmission X-ray microscopy (STXM) elemental maps and near-edge X-ray absorption fine structure (NEXAFS) spectra of isolated and purified S. putrefaciens CN32 envelopes at V, Mn, Ca, C, N, and O edges. It was found that there were strong correlations between membrane fluidity and fatty acid composition of strain CN32 membranes. The acyl chain chemistry was minimally affected by metal presence in the growth medium, however these subtle changes correlated with significant alterations in the fluid states of the membranes. Uranium seemed to fall outside this relationship, strongly stabilizing cell membranes. Metals in all treatments adsorbed to cell membranes, determined using either NEXAFS or electron microscopy, with the exception of V in aerobic conditions. Permeability effects of metal exposure to Ca(II), Cu(II), Mn(II), U(VI), V(IV), and Zn(II) were also assessed. Bacterial strains for these studies included S. putrefaciens CN32, Escherichia coli AB264 (wildtype K-12), Pseudomonas aeruginosa PAO1 wildtype, and Bacillus subtilis 168, in order to compare published data from the membrane chemistry of those organisms to S. putrefaciens CN32 membranes. Each metal had the same overall impact on each bacterial strain, regardless of variations in cell membrane and surface sugar chemistry, however the strengths of these effects were different for each organism. All metals with the exception of U permeabilized cell walls, while U rendered the membrane much less permeable. These impacts on permeability were concentration dependent from 0.001 mM to 1 mM concentrations. The research demonstrated that growth environment has a significant impact on the physicochemical state of bacterial membranes. Metals in those environments have varying complexation chemistry according to pH and redox conditions, and impact membrane attributes and dynamics depending on cell wall chemical composition. / This research was funded by the National Science and Engineering Research Council of Canada, as well as the Advanced Food and Materials Network.