Originally thought of as a constant and unchanging place, the Universe is full of dramas of stars emerging, dying, eating each other, colliding, etc. One of the first transient phenomena noticed were called novae (the name means "new" in Latin). Years later, supernovae were discovered. Despite their names, both novae and supernovae are events in relatively old stars, with supernovae marking the point of stellar death. Known for thousands of years, supernovae and novae remain among the most studied events in our Universe. Supernovae strongly influence the circumstellar medium, enriching it with heavy elements and shocking it, facilitating star formation. Cosmic rays are believed to be accelerated in shocks from supernovae, with small contribution possibly coming from novae. Even though the basic physics of novae is understood, many questions remain unanswered. These include the geometry of the ejecta, why some novae are luminous radio or gamma-ray sources and others are not, what is the ultimate fate of recurrent novae, etc. Supernova explosions are the primary sources of elements heavier than hydrogen and helium. The elements up to nuclear masses A around 100 can form through successive nuclear fusion in the cores of stars starting with hydrogen. Beyond iron, the fusion becomes endothermic instead of exothermic. In addition, for these nuclear masses the temperatures required to overcome the Coulomb barriers are so high that the nuclei are dissociated into alpha particles and free nucleons. Hence all elements heavier than A around 100 should have formed by some other means. These heavier nuclear species are formed by neutron capture on seed nuclei close to or heavier than iron-group nuclei. Depending on the ratio between neutron-capture timescale and beta-decay timescale, neutron-capture processes are called rapid or slow (r- and s-processes, respectively). The s-process, which occurs near the valley of stable isotopes, terminates at Bi (Z=83), because after Bi there is a gap of four elements with no stable isotopes (Po, At, Rn, Ac) until we come to stable Th. The significant abundance of Th and U in our Universe therefore implies the presence of a robust source of r-process. The astrophysical site of r-process is still under debate. Here we present a study of a candidate site for r-process, neutrino-heated winds from newly-formed strongly magnetized, rapidly rotating neutron stars ("proto-magnetars"). Even though we find such winds are incapable of synthesizing the heaviest r-process elements like U and Th, they produce substantial amounts of weak r-process (38<Z<47) elements. This may lead to a unique imprint of rotation and magnetic fields compared to such yields from otherwise analogous slowly rotating non-magnetized proto-neutron stars. Novae explosions are not as powerful as those of supernovae, but they occur much more frequently. The standard model of novae assumes a one-stage ejection of mass from the white dwarf following thermonuclear runaway. The discovery by the Fermi space telescope of gamma-rays from classical novae made the existence of shocks in novae outflows evident. The presence of shocks in novae was considered well before the discovery of gamma-ray emission; however, little previous theoretical work acknowledged the overwhelming effect of shocks on observed emission and ejecta geometry. Here we present the calculations of synchrotron radio emission from the shocks as they propagate down the density gradient and peak at the timescale of a few months. The model satisfactory fits observations and has several implications for the physics of novae.

X-ray micro-tomography has become an increasingly important technique for characterizing the 3D microstructure of materials. This became possible mainly because spatial resolution of the imaging detectors has improved, and synchrotron radiation is more accessible for micro-tomography imaging. In the presented project a novel experimental system has been designed and built at Biomedical Imaging and Therapy (BMIT)’s 05B1-1 beamline at Canadian Light Source (CLS). This system allows imaging structural transformation during in-situ loading experiments under tensile stress. The system was tested and several examples illustrating the application of this experimental system are presented. The system has been used to image the structure of porous aluminum and the size and distribution of pores was analyzed. The system was also used to image the structure of Al/Al2O3/TiC hybrid composites manufactured by accumulated roll bonding (ARB) process and this allowed analyzing the size distribution of reinforcing particles and voids. It was further demonstrated that in-situ imaging of deformation can be used to image consecutive stages of structural transformation (change in volume, change of position of reinforcing particles, creation of voids etc.) in aluminum alloy and aluminum composites during application of tensile stress and to illustrate the nucleation of failure. This system of dynamic imaging at BMIT-BM at CLS can help in better description of structural transformation associated with the application of stress and will contribute to better understanding of the failure mechanisms of different types of materials during straining.

Barley grain is one of the main sources of feed for ruminants in Canada. Although barley varieties may have similar chemical composition, they exhibit different rumen degradation characteristics and nutrient availabilities. These biological differences may be related to structural chemical make-up or structural features among the varieties. The objectives of this study were to use the in situ technique and two Mid-IR Spectroscopy techniques, Diffuse Reflectance Fourier Transform IR Spectroscopy (DRIFT) and Synchrotron-based Fourier Transform IR Microspectroscopy (SFTIRM) to determine ruminal nutrient availabilities and inherent structural features in the hull, seed and endosperm of six barley varieties (AC Metcalfe, McLeod, CDC Dolly, CDC Helgason, CDC Trey, and CDC Cowboy) and to study the relationships between structural characteristics, mean and median particle size and nutrient availability. The nylon bag technique was used to incubate coarsely dry-rolled barley samples for 0, 2, 4, 8, 12, 24 and 48 h in the rumen of three mature Holstein dry dairy cows, which were ruminally cannulated. The rumen degradation kinetics of dry matter (DM), crude protein (CP) and starch were determined using first order degradation kinetics equations. Results indicated that there were significant differences in the mean and median particle size, degradation kinetics of each individual nutrient (DM, CP, and starch) among the six barley varieties. CDC Helgason showed the lowest degradation rate and extent of all nutrients (DM, CP, and starch) among the six barley varieties with larger particle size. Compared with other five varieties, CDC Helgason may be more suitable for ruminants feeding because of the lowest degradation rate and extent. The results also revealed a strong correlation between median particle size and the rate and extent of rumen degradation.<p> The results also showed that both DRIFT and SFTIR techniques associated with uni- and two multi- variate analyses were capable to efficiently discriminate and classify the inherent molecular structural features among the different varieties of barleys. Uni-variate analyses were conducted using both the DRIFT spectroscopy (hull and whole seed sample) and SFTIR microspectroscopy (endosperm tissue). The results from hull samples showed significant differences in the peak area of aromatic lignin, cellulosic compound, and total carbohydrates (CHO), and the ratio of lignin to cellulosic compound among the six barley varieties. The results from whole seed samples showed significant difference in the peak area and height of Amide I, peak area of total CHO and structural CHO (cellulosic), and the ratio of Amide I to total CHO area, and the ratio of total CHO to structural CHO. Significant differences were also found in the SFTIR results from endosperm tissue. With two multivariate spectral analysis techniques: Agglomerative hierarchical cluster (AHCA) and Principal component analyses (PCA) applied on whole seed sample, the CDC Helgason was distinguished from AC Metcalfe, CDC Dolly, McLeod and CDC Cowboy in fingerprint (1800-800 cm-1) and CHO region (1185-800 cm-1), from AC Metcalfe, McLeod and CDC Cowboy in protein region (1715-1485 cm-1). Information from this study involving probing the seed internal structure of barley may provide a further insight as to why barley varieties exhibit different rumen degradations.

The radiation-induced decomposition of glycine is studied using a combination of Near Edge X-ray Absorption Fine Structure (NEXAFS) measurements and density functional theory calculations. Principal Component Analysis was used to determine the number of distinct molecules that were needed to explain the observed changes in the measured spectra, and the emerging absorption features are assigned to various product molecules through comparison with simulated spectra of several model compounds. It is clear from the experiment that the major effect of soft X-ray irradiation is the fragmentation of the molecule, primarily at the carbonyl sites. Peptide formation is shown to occur under irradiation; a condensation reaction initiated by the removal of a carbonyl oxygen is the proposed mechanism. This study utilizes a novel approach to the study of radiation damage that can occur during measurements, and suggests that it may be possible to use simulated model spectra to correct for these effects in measured spectra.<p> A study of oligothiophene-based molecular semiconductor materials with potential applications in light-emitting and photovoltaic devices is undertaken. Angle-resolved NEXAFS measurements of the star-shaped 4(HPBT) molecules on an amorphous indium surface show a strong dichroic signal indicating a well-ordered, uniformly upright arrangement of planar molecules. The X-ray excited optical luminescence (XEOL) measurements showed several sharp features associated with vibronic splitting of the LUMO-HOMO luminescent transition. The HOMO-LUMO gap determined from the XEOL measurements is 2.28 eV; this value is in agreement with previously published optical measurements as well as with the value that is estimated from the combination of NEXAFS and X-ray emission spectroscopy (XES) measurements. Films formed from blended solutions of 4(HPBT) and the hole-transporting molecular semiconductor PCBM are shown to form a bilayer structure with the PCBM adjacent to the substrate. Annealing causes desorption of the 4(HPBT) from the surface.

The radiation-induced decomposition of glycine is studied using a combination of Near Edge X-ray Absorption Fine Structure (NEXAFS) measurements and density functional theory calculations. Principal Component Analysis was used to determine the number of distinct molecules that were needed to explain the observed changes in the measured spectra, and the emerging absorption features are assigned to various product molecules through comparison with simulated spectra of several model compounds. It is clear from the experiment that the major effect of soft X-ray irradiation is the fragmentation of the molecule, primarily at the carbonyl sites. Peptide formation is shown to occur under irradiation; a condensation reaction initiated by the removal of a carbonyl oxygen is the proposed mechanism. This study utilizes a novel approach to the study of radiation damage that can occur during measurements, and suggests that it may be possible to use simulated model spectra to correct for these effects in measured spectra.<p> A study of oligothiophene-based molecular semiconductor materials with potential applications in light-emitting and photovoltaic devices is undertaken. Angle-resolved NEXAFS measurements of the star-shaped 4(HPBT) molecules on an amorphous indium surface show a strong dichroic signal indicating a well-ordered, uniformly upright arrangement of planar molecules. The X-ray excited optical luminescence (XEOL) measurements showed several sharp features associated with vibronic splitting of the LUMO-HOMO luminescent transition. The HOMO-LUMO gap determined from the XEOL measurements is 2.28 eV; this value is in agreement with previously published optical measurements as well as with the value that is estimated from the combination of NEXAFS and X-ray emission spectroscopy (XES) measurements. Films formed from blended solutions of 4(HPBT) and the hole-transporting molecular semiconductor PCBM are shown to form a bilayer structure with the PCBM adjacent to the substrate. Annealing causes desorption of the 4(HPBT) from the surface.

Barley grain is one of the main sources of feed for ruminants in Canada. Although barley varieties may have similar chemical composition, they exhibit different rumen degradation characteristics and nutrient availabilities. These biological differences may be related to structural chemical make-up or structural features among the varieties. The objectives of this study were to use the in situ technique and two Mid-IR Spectroscopy techniques, Diffuse Reflectance Fourier Transform IR Spectroscopy (DRIFT) and Synchrotron-based Fourier Transform IR Microspectroscopy (SFTIRM) to determine ruminal nutrient availabilities and inherent structural features in the hull, seed and endosperm of six barley varieties (AC Metcalfe, McLeod, CDC Dolly, CDC Helgason, CDC Trey, and CDC Cowboy) and to study the relationships between structural characteristics, mean and median particle size and nutrient availability. The nylon bag technique was used to incubate coarsely dry-rolled barley samples for 0, 2, 4, 8, 12, 24 and 48 h in the rumen of three mature Holstein dry dairy cows, which were ruminally cannulated. The rumen degradation kinetics of dry matter (DM), crude protein (CP) and starch were determined using first order degradation kinetics equations. Results indicated that there were significant differences in the mean and median particle size, degradation kinetics of each individual nutrient (DM, CP, and starch) among the six barley varieties. CDC Helgason showed the lowest degradation rate and extent of all nutrients (DM, CP, and starch) among the six barley varieties with larger particle size. Compared with other five varieties, CDC Helgason may be more suitable for ruminants feeding because of the lowest degradation rate and extent. The results also revealed a strong correlation between median particle size and the rate and extent of rumen degradation.<p> The results also showed that both DRIFT and SFTIR techniques associated with uni- and two multi- variate analyses were capable to efficiently discriminate and classify the inherent molecular structural features among the different varieties of barleys. Uni-variate analyses were conducted using both the DRIFT spectroscopy (hull and whole seed sample) and SFTIR microspectroscopy (endosperm tissue). The results from hull samples showed significant differences in the peak area of aromatic lignin, cellulosic compound, and total carbohydrates (CHO), and the ratio of lignin to cellulosic compound among the six barley varieties. The results from whole seed samples showed significant difference in the peak area and height of Amide I, peak area of total CHO and structural CHO (cellulosic), and the ratio of Amide I to total CHO area, and the ratio of total CHO to structural CHO. Significant differences were also found in the SFTIR results from endosperm tissue. With two multivariate spectral analysis techniques: Agglomerative hierarchical cluster (AHCA) and Principal component analyses (PCA) applied on whole seed sample, the CDC Helgason was distinguished from AC Metcalfe, CDC Dolly, McLeod and CDC Cowboy in fingerprint (1800-800 cm-1) and CHO region (1185-800 cm-1), from AC Metcalfe, McLeod and CDC Cowboy in protein region (1715-1485 cm-1). Information from this study involving probing the seed internal structure of barley may provide a further insight as to why barley varieties exhibit different rumen degradations.

Reproduction de : Thèse de doctorat : Physique des matériaux : Lyon 1 : 2005. Reproduction de : Thèse de doctorat : Physique des matériaux : Université de Turin : 2005. / Thèse soutenue en co-tutelle. Thèse en anglais. Titre provenant de l'écran titre. 129 réf. bibliogr.

The level of information provided by electrochemical measurements can be substantial as evident by the use of electrochemistry in varied disciplines spanning from materials research to cellular biochemistry. However, electrochemistry on its own does not provide direct information concerning redox induced changes in molecular structure. This information can only be elucidated by coupling spectroscopic and/or separation techniques with traditional electrochemical methodologies. In principle, infrared (IR) spectroelectrochemistry (SEC) is ideal for such studies but in practice coupling IR spectroscopy and electrochemistry are often experimentally incompatible. Since the inception of in-situ IR SEC techniques in the 1980’s, two competing methodologies (using either external- or internal- IR reflection geometries), were developed to deal with the two major challenges associated with IR SEC (strong infrared absorption of the electrolytes and weak analytical signals). The primary focus of this thesis is the successful advancement of IR SEC techniques through the implementation of synchrotron infrared radiation with ultramicroelectrodes (UMEs; electrode diameters < 25 µm) to study spectroelectrochemical processes on the microsecond time scale. Several examples using Surface Enhanced Infrared Absorption Spectroscopy (SEIRAS) are presented including the adsorption of dimethylaminopyridine (DMAP) on gold substrates and the proton-coupled electron-transfer (PCET) kinetics of electrochemically-active 1,4-benzoquinone terminated self-assembled monolayers (SAMs). These studies highlight the benefits of coupling electrochemistry and infrared spectroscopy. For instance, in-situ spectroscopic evidence shows that small amounts of DMAP’s conjugate acid (DMAPH+) adsorb on gold electrodes in acidic electrolytes and at negative potentials. This result was not forthcoming from previous electrochemical measurements and was only realized through in-situ SEIRAS. Finally, the largest contribution in advancing in-situ IR SEC methodologies was through the development of utilizing synchrotron infrared radiation on UMEs to study fast electrochemical processes. This work was technically very challenging and emphasized the interfacing of an electrochemical cell containing an UME with fast infrared data acquisition techniques (i.e. rapid scan and step-scan interferometry). The use of a prototypical electrochemical system, i.e. the mass-transport controlled reduction of ferricyanide, indicate that at short times the spectroscopic signal closely matches the electrochemical signal but at long time scales it deviates due to edge effects associated with the diffusion environment of the UME.

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