When a liquid is cooled below its equilibrium freezing temperature, it becomes supercooled and the molecular motions slow down until the system becomes kinetically arrested, forming a glass, at the glass transition temperature. These amorphous materials have the mechanical properties of a solid while retaining the structural properties of a liquid, but do not exhibit the usual features of a thermodynamic phase transition. As such, they present a number of important challenges to our understanding of the dynamics and thermodynamics of condensed phases. For example, supercooled liquids are classified on the basis of the temperature dependence of their transport properties and structural relaxations times. Strong liquids display an Arrhenius behavior, with the logarithm of their viscosity growing linearly with inverse temperature. Fragile liquids behave in a super-Arrhenius manner, where the viscosity appears to diverge at temperatures above absolute zero, suggesting the possibility of an underlying thermodynamic origin to the glass transition. Some complex, network forming liquids, such as water and silica have also been shown to have a dynamical crossover from fragile to strong liquid behavior as the temperature is decreased. The potential energy landscape paradigm, combined with inherent structure formalism, provide a framework for connecting the way particles pack together with the thermodynamics and dynamics of the liquid and glassy phases. However, the complexity of this multi-dimensional surface makes it difficult to fully characterize and rigorous relationships between the nature of particle packing and glass forming properties have not been established. The goal of this thesis is to study some of the general features of glass transition and find the connection between the dynamics and the thermodynamics of glass forming liquids. To this end, the packing landscapes of quasi-one-dimensional hard discs and hard spheres are studied. A two dimensional system of hard discs with diameter σ, confined between two hard walls (lines) of length L, separated by a distance 1<Hd/σ< 1+√(3/4), is studied by using the Transfer Matrix (TM) method and Molecular Dynamics (MD) simulations. The complete packing landscape is characterized in terms of the density distribution of inherent structures and the number of local defect states. It is shown that this model exhibits a dynamic fragile-strong liquid crossover at the maximum in the constant pressure heat capacity (Cp) for the system, similar to that observed in anomalous network forming liquids such as water and silica. Furthermore, we find that rescaling the relaxation times of systems with different channel widths by the relaxation time at the Cp maximum causes all the data to collapse on a single master curve. The Cp maximum occurs at a critical value of the defect concentration. At high defect concentrations, where the defects interact, the fluid is fragile. When the defect concentration is low, relaxation appears to occur through the hopping of isolated defects, leading to Arrhenius dynamics. This suggests the thermodynamics associated with the Cp maximum is intimately related to the dynamic crossover. A system of three-dimensional hard spheres confined in a narrow channel was used to study the effect of a more complicated landscape on the dynamics of the system. For this system, the thermodynamic and dynamic properties of the system were studied for two different channel diameters, the 1<Hd/σ<1+√(3/4) case, which only allows first neighbors contact for the spheres and, 1+√(3/4)< Hd/σ < 1.98, which allows second neighbors contact to exist. For the first case, the TM method was implemented to obtain the thermodynamic properties and MD simulation was used to measure the dynamics. For the case that the second neighbor contact is allowed 1+√(3/4)< Hd/σ < 1.98. The thermodynamic and dynamic properties were obtained using MD simulations. In this channel diameter range, the system creates chiral helical jammed packings and defect states appear where sections of helices with different local chiralities come into contact. The equation of state (EOS) shows the presence of two heat capacity maxima. The high density Cp maximum is linked to fragile strong crossover. Finite size scaling analysis shows that the low density Cp maximum is related to an orientational order transition stabilized by the presence of the defects. This type of transition has been shown to exist in bulk two-dimensional systems but this work is the first study that provides strong evidence of the existence of this transition in a quasi-one-dimensional system in a system with short-range interactions.

No description available.

Les aciers ODS (Oxide Dispersion Strengthened) sont envisagés comme matériau de gainage du combustible pour les futurs réacteurs nucléaires au sodium de Génération IV. Ces matériaux présentent une excellente résistance au fluage à haute température et au gonflement sous irradiation, mais des interrogations subsistent quant à leur propriété de résilience. L'objectif de ce travail de thèse est alors de comprendre l'effet de différents paramètres (composition chimique, texture, vieillissement thermique...) sur le comportement à l'impact des aciers ODS et sur l'apparition de la rupture de type fragile. L'objectif à terme est d'appréhender l'apparition de ce type de rupture afin d'assurer l'intégrité des composants en acier ODS en conditions normales ou incidentelles.Dans un premier temps, cette étude a permis d'évaluer la stabilité de deux nuances d'acier ODS contenant 14%Cr et 18%Cr dans des conditions de vieillissement thermique. La nuance à 18%Cr a été écartée à cause de la formation d'une phase intermétallique fragilisante de type sigma à 600°C. Par contre, la nuance à 14%Cr est plus prometteuse puisque son comportement est resté stable entre 400°C et 600°C pour une durée de vieillissement maximale de 10000 heures, et ce même si des précipités de phases alpha', de Laves Fe2W et des carbures de chrome ont été observés. D'autre part, la texture morphologique, caractérisée par des grains allongés selon la direction de filage, est propice à la propagation de fissures intergranulaires selon cette direction. La texture cristallographique régit, quant-à elle, les micromécanismes de clivage. En effet, les entités microstructurales qui contrôlent la propagation du clivage sont des groupes de grains faiblement désorientés les uns des autres d'un point de vue cristallographique, et qui sont associés à la notion de grains effectifs. Enfin, le comportement en traction et en flexion d'une nuance d'acier ODS à 14%Cr a été modélisé, et un critère de rupture fragile basé sur une valeur de contrainte critique a été proposé. Ce modèle nous a alors permis de simuler des essais sur différentes géométries et de prédire l'apparition de la rupture fragile sur cette nuance.

Fragile-X syndrome (FXS) is the most common form of inherited intellectual impairment. Caused by the transcriptional repression of the Fmr1 gene on the X chromosome, FXS results in the loss of the Fragile-X Mental Retardation Protein (FMRP). Human female patients with FXS are heterozygous for the Fmr1 mutation whereas males are hemizygous. FXS has been studied far less in females than in males due to a generally less severe clinical phenotype. Previous research has implicated the metabotropic glutamate receptor (mGluR) in synaptic plasticity alterations in the cornu ammonis area 1 (CA1) region of the juvenile male Fmr1 knock-out (KO) hippocampus. In contrast, our investigations into the young adult dentate gyrus (DG) subfield of the hippocampus have revealed N-methyl-D-aspartate receptor (NMDAR)-associated impairments in synaptic plasticity. The current study sought to extend these investigations to the young adult female Fmr1 heterozygous (Het) and Fmr1 KO mouse as well as investigate NMDAR- and mGluR-mediated long-term depression (LTD) in the DG and CA1 of the young adult male Fmr1 KO mouse. Input-output curves and paired pulse measures of short-term plasticity were also evaluated in all genotypes. Field electrophysiology revealed a significant impairment in long-term potentiation (LTP) and LTD in male Fmr1 KO and female Fmr1 Het mice that was associated with NMDAR alteration. A more robust synaptic protocol was not able to rescue LTP in the male Fmr1 KO DG. Paired-pulse low-frequency stimulation and (RS)-3,5-dihydroxyphenylglycine (DHPG)-induced mGluR-LTD was intact in all genotypes and brain regions examined. Although further investigation will be required to expand our understanding of FXS and to fully elucidate the mechanisms behind intact synaptic plasticity in the female Fmr1 KO mouse, our results suggest that NMDARs may be poised as important contributors to hippocampal pathophysiology in FXS. / Graduate

The purpose of this study was to examine the expression of GABAergic proteins in Fmr1 knockout mice during brain maturation and to assess behavioural changes potentially linked to perturbations in the GABAergic system. Quantitative western blotting of the forebrain revealed that compared to wild-type mice, the GABAA receptor α1, β2, and δ subunits, and the GABA catabolic enzymes GABA transaminase and SSADH were down-regulated during postnatal development, while GAD65 was up-regulated in the adult knockout mouse forebrain. In tests of locomotor activity, the suppressive effect on motor activity of the GABAA β2/3 subunit-selective drug loreclezole was impaired in the mutant mice. In addition, sleep time induced by the GABAA β2/3-selective anaesthetic drug etomidate was decreased in the knockout mice. Our results indicate that disruptions in the GABAergic system in the developing brain may result in behavioural consequences in adults with fragile X syndrome.

The purpose of this study was to examine the expression of GABAergic proteins in Fmr1 knockout mice during brain maturation and to assess behavioural changes potentially linked to perturbations in the GABAergic system. Quantitative western blotting of the forebrain revealed that compared to wild-type mice, the GABAA receptor α1, β2, and δ subunits, and the GABA catabolic enzymes GABA transaminase and SSADH were down-regulated during postnatal development, while GAD65 was up-regulated in the adult knockout mouse forebrain. In tests of locomotor activity, the suppressive effect on motor activity of the GABAA β2/3 subunit-selective drug loreclezole was impaired in the mutant mice. In addition, sleep time induced by the GABAA β2/3-selective anaesthetic drug etomidate was decreased in the knockout mice. Our results indicate that disruptions in the GABAergic system in the developing brain may result in behavioural consequences in adults with fragile X syndrome.

Copies of author's previously published works inserted. / Bibliography: leaves 321-370. / xv, 370, [21] leaves : ill. (chiefly col.) ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / The aim of the project presented in this thesis is to isolate microsatellite markers and to construct a high resolution genetic map of the human X chromosome using these and pre-existing microsatellite markers. AC dinucleotide repeat markers are isolated from a bacteriophage library for application to the genetic localisations of X-linked disease genes, particularly those responsible for non-specific mental retardation (MRX). The genetic map is used to refine the location of the disease gene segregating in five families affected with X-linked mental retardation. / Thesis (Ph.D.)--University of Adelaide, Dept. of Genetics, 1997

Typescript (Photocopy) / Includes published papers co-authored by the author at the end of volume 2 / Bibliography: leaves 195-237 of vol. 1 / 2 v. : ill ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--Dept. of Paediatrics, Faculty of Medicine, University of Adelaide, 1991

Thesis (Ph. D.)--University of Adelaide, Dept. of Paediatrics, 1994. / Errata slip inserted at back. Includes bibliographical references (leaves 159-192).

Thesis (Ph. D.)--University of Washington, 1998. / Vita. Includes bibliographical references (leaves [103]-137).