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No description available.

Ce manuscrit présente différentes études expérimentales des collisions en incidence rasante (< 3 degrés) sur LiF(001) d'ions simplement chargés tels que le néon et le fluor de basses énergies (< 3 keV). Le faisceau incident est pulsé. Le produit de la diffusion après une analyse en charge entre des plaques électrostatiques est détecté sur un détecteur sensible en position. Les particules secondaires (électrons ou ions) sont recueillies sur un détecteur composé de 16 unités de détection (2 galettes microcanaux) couvrant 2p stéradian au dessus de la surface. La technique de mesure de perte d'énergie (spectroscopie de translation) associée à la détection des particules diffusées en coïncidence avec les électrons émis de la surface lors de la collision d'ions néons simplement chargés, a permis de mettre en évidence des états excités de la surface. Ces états excités, localisés sur les ions fluors négatifs de la surface, sont soit centrés autour d'une seule lacune (les excitons), soit autour de 2 lacunes, ce dernier, complexe à 3 corps est connu dans la littérature sous le nom de trion. On trouvera dans ce manuscrit la première caractérisation de ces états par impact d'ions. Dans le cas du néon la capture correspond à une neutralisation Auger Les collisions d'atomes de fluors ont confirmé l'existence d'un seuil en vitesse, lors de la formation des ions négatifs. La formation de ces ions à partir d'ions positifs sous ce seuil, donne une preuve expérimentale d'une double capture simultanée. La valeur de la perte d'énergie s'explique correctement si l'on tient compte de l'interaction entre les deux lacunes voisines. La corrélation statistique se double donc d'une corrélation spatiale où les captures d'électrons s'effectuent sur deux sites halogènes voisins. Dans ce cas l'expérience ne permet pas de différencier un processus di-électronique d'un processus mono-électronique du second ordre alors que la théorie semble indiquer qu'il s'agit de processus du second ordre.

Novel integrated ozone contactor design and optimization tools which consist of an instrument that measures ozone decay kinetics, a program that performs predictive simulation, and an experimental method to examine mixing characteristics within the ozone contactor, were developed in this study. A multi-channel stopped-flow reactor (MC-SFR) is an instrument that performs automatic, real-time, and continuous analysis of ozone decay kinetics in natural waters. Ozone Contactor Model (OCM) is the software to simulate the performance of full-scale ozone bubble-diffuser contactors in support of current and future regulations regarding pathogen and bromate control in drinking water. The MC-SFR and OCM developed in this study were further applied to simulate Cryptosporidium parvum oocyst log inactivation and bromate formation in Linnwood Water Plant Ozone Facility (LWPOF) at Milwaukee Water Works, Milwaukee, WI and model predictions were verified with experimental results. Three dimensional laser induced fluorescence(3DLIF) allowed real time characterization of mixing conditions in a physical model ozone contactors by capturing fluorescence image emitted from a laser dye (i.e. Rhodamine 6G) using a high speed CCD camera. 3DLIF system was applied to analyze the hydrodynamics of two representative types of ozone contactor: direct discharge side-stream venturi injector (SVI) and multi-chambered fine bubble diffuser (FBD). Experimental results verified the presence of circulative swirling related for low dispersion for SVI reactor and the existence of non-ideal flow including short circuiting and internal recirculation in FBD reactor. Finally, integrated tools were applied to the design of a new ozone contactor under planning stage to assess current design and to recommend the improvement.

A new Laser Induced Fluorescence Capillary Zone Electrophoresis (LIF-CZE) bioassay to detect and study the catalytic activity of the sulfur assimilating enzyme commonly found in E. coli species; alkanesulfonate monooxygenase (EC 1.14.14.5) is described for the first time. This technique enables the possibility for direct injection onto a capillary for detection without the need for pre-concentration of sample and with minimal sample preparative steps prior to analysis. In this bioassay, a group of Fischer based cyanine dyes and two Oxazine (Nile red) derivatives were designed for further optimization as key Vis-NIR fluorescent substrate. In developing this technique, the test dyes were first assessed for their photophysical properties, based on four criteria; (1) photostable (2) solvatochromism (3) binding affinity towards both the monooxygenase active site and serum albumin and (4) chemical stability in strong electric field strength. Applying key dye characterization procedures including; molar absorptivity determination, quantum yield determination, photostability, solvatochromism and protein interaction studies it was determined that the Fischer indolium cyanine dyes were most suitable for the method development. The data revealed that under the test conditions, reduced flavin, the oxidative monooxygenase catalytically specifically converts the alkylsulfonate substituted cyanine dyes to the corresponding aldehyde. This new bioassay has proven to be quick, portable, sensitive, reliable and the exhibit the possibility of ‘on-the-spot’ detection; advantages not readily realized with other commonly applied techniques such as PCR, SPR, ELISA and GC used to study bacterial sulfur assimilation processes. In addition, recent literature results proposed by other research groups developing similar techniques showed strong reliance on GC analyses. Those assays involve the use of low molecular weight straight chain non-emissive alkanesulfonate substrates. Once enzyme catalysis occurs the aldehyde is formed becomes rather volatile and requires complex and tedious headspace sampling for GC analyses. This feature limits the in vitro applicability and eliminated the possibility in vivo development. Our goal is to further develop, optimize and present this CZE based bioassay as a suitable alternative to the current trends in the field while creating a more robust and sensitive in vitro monooxygenase detection method with the possibilities of in vivo application.

Axonal degeneration is a major pathological feature of the central nervous system (CNS) inflammatory demyelinating disease multiple sclerosis (MS). This axonal degeneration has major consequences, as functional axonal regeneration in the CNS is largely absent. Cumulative axonal degeneration is the likely cause of the majority of progressive MS-related disability, and therefore, the need for novel neuroprotective therapies for MS exists. Experimental autoimmune encephalomyelitis (EAE), an animal model of MS pathology, also produces axonal injury. In particular, the optic nerve and spinal cord are key sites of neuroinflammation in mouse EAE. By utilizing this model, the short term and long term effects of the putative neuroprotective cytokine, leukaemia inhibitory factor (LIF), were investigated in the optic nerve and spinal cord utilising a number of outcome measures of axonal dysfunction. These included MRI measures of water diffusivity along (ADC ||) and across (ADC┴) the optic nerves, serum levels of phosphorylated neurofilament heavy chain subunit (pNF-H) and histological morphometric measures. LIF treatment reduced EAE grade and pNF-H plasma levels, decreased ADC┴, but had no effect on ADC ||, axon counts or inflammatory infiltration. / In contrast, genetic deletion of LIF and its sister cytokine ciliary neurotrophic factor (CNTF), not only increased EAE grade and pNF-H levels, but also decreased optic nerve ADC|| and optic nerve and spinal cord axon densities. After reviewing current literature, we hypothesize that the target cell for endogenously upregulated LIF in EAE may be the neuron or axon, whereas the target cell for exogenously administered therapeutic LIF may be another cell type, possibly infiltrating macrophages and activated microglial cells. LIF antagonist treatment did not have any affect on EAE grade, pNF-H levels or MRI parameters. This lack of effect may be due to the inability of the LIF antagonist to enter the CNS, supporting the hypothesis that endogenous LIF has a centrally acting mechanism.

Equation d'´etat du fer comprime par choc laser Cette thèse s'inscrit dans le cadre des recherches menées sur l'équation d'´etat de matériaux fortement comprimés. En particulier cette étude se focalise sur le cas du fer comprimé par choc laser. Le but est alors de se rapprocher des conditions du noyau terrestre, constitué d'une graine solide entourée de fer liquide. La compréhension des phénomènes décrivant la thermodynamique du noyau et le processus de geodynamo requiert la connaissance du lieu de la courbe de fusion du fer à l'interface solide-liquide du noyau à 3,3 Mbar. Plusieurs expériences ont été menées dans ce but. Dans un premier temps, une mesure absolue de l'Hugoniot du fer a ete effectuée. Vient ensuite une étude des états en détente partielle du fer dans un matériau fenêtre, le fluorure de lithium (LiF). Cette configuration permet un accès direct aux propriétés optiques du fer comprimé (réceptivité et émission propre). La mesure de la vitesse d'interface, largement dépendante des propriétés optiques du LiF comprimé, sert de jauge de pression. A l'aide d'un diagnostic de réceptivité à deux longueurs d'onde, la conductivité électrique continue du fer comprimé a été estimée et se trouve être en bon accord avec les résultats annoncés par la littérature géophysique. Le diagnostic d'émission propre a quant à lui permis d'effectuer une mesure de la température du fer en détente partielle, mettant en évidence le changement d'état solide-liquide a des pressions de l'ordre du Mbar.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第15645号 / 工博第3303号 / 新制||工||1499(附属図書館) / 28182 / 京都大学大学院工学研究科社会基盤工学専攻 / (主査)教授 禰津 家久, 教授 椎葉 充晴, 教授 後藤 仁志 / 学位規則第4条第1項該当

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Preterm birth (PTB) results in over 15 million early births annually and is the leading cause of neonatal deaths. There are no clinical methods currently available to evaluate risk of PTB at early stages in pregnancy; thus, a rapid diagnostic to analyze PTB risk would be beneficial. Microfluidic immunoaffinity extraction is a promising platform for preparing complex samples, such as maternal serum with PTB risk biomarkers. 3D printed microfluidic devices have advantages over conventional microfluidic systems including simple fabrication and potential for iterative optimization to improve designs. In this work, I developed immunoaffinity monoliths in 3D printed microfluidic devices modified with antibodies to enrich PTB biomarkers from human blood serum. I retained and eluted a peptide PTB biomarker in both buffer and blood serum using an immunoaffinity column. An additional three PTB biomarkers were also successfully extracted either from buffer or blood serum on single-antibody columns. Both polyclonal and monoclonal antibodies to PTB biomarkers were characterized by dot blots, biolayer interferometry, and surface plasmon resonance to determine their specificity and dissociation constants. I created multiplexed immunoaffinity columns to simultaneously enrich three PTB biomarkers from depleted human blood serum in a single extraction. This is the first demonstration of multiplexed immunoaffinity columns for PTB biomarkers in a 3D printed microfluidic device. My work is a key step towards the future development of 3D printed microfluidic devices for rapid PTB testing.