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1	The Role of Penetrant Structure on the Transport and Mechanical Properties of a Thermoset Adhesive Kwan, Kermit S. Jr. 24 August 1998 (has links) In this work the relationships between penetrant structure, its transport properties, and its effects on the mechanical properties of a polymer matrix were investigated. Although there is a vast amount of data on the diffusion of low molecular weight molecules into polymeric materials and on the mechanical properties of various polymer-penetrant systems, no attempts have been made to inter-relate the two properties with respect to the chemical structure of the diffusant. Therefore, two series of penetrants - n-alkanes and esters - were examined in this context, with the goal of correlating molecular size, shape, and chemical nature of the penetrant to its final transport and matrix mechanical properties. These correlations have been demonstrated to allow quantitative prediction of one property, given a reasonable set of data on the other parameters. A series of n-alkanes (C6-C17) and esters (C5-C17) have been used to separate the effects of penetrant size and shape, from those due to polymer-penetrant interactions, in the diffusion through a polyamide polymeric adhesive. These effects have been taken into account in order to yield a qualitative relationship that allows for prediction of diffusivity based upon penetrant structural information. Transport properties have been analyzed using mass uptake experiments as well as an in-situ FTIR-ATR technique to provide detailed kinetic as well as thermodynamic information on this process. The phenomenon of diffusion and its effects on the resulting dynamic mechanical response of a matrix polymeric adhesive have been studied in great detail using the method of reduced variables. The concept of a diffusion-time shift factor (log aDt) has been introduced to create doubly-reduced master curves, taking into account the effects of temperature and the variations in the polymer mechanical response due to the existence of a low molecular weight penetrant. / Ph. D. diffusion polymer polyamide alkanes esters dynamic mechanical properties time-temperature superposition diffusion-time shift factor relaxation time distribution
2	Diffusion tensor imaging at long diffusion time Rane, Swati 30 June 2009 (has links) Diffusion Tensor Imaging (DTI) is a well-established magnetic resonance technique that can non-invasively interpret tissue geometry and track neural pathways by sampling the diffusion of water molecules in the brain tissue. However, it is currently limited to tracking large nerve fiber bundles and fails to faithfully resolve thinner fibers. Conventional DTI studies use a diffusion time, t[subscript diff] of 30 ms - 55 ms for diffusion measurements. This work proposes the use of DTI at long t[subscript diff] to enhance the sensitivity of the method towards regions of low diffusion anisotropy and improve tracking of smaller fibers. The Stimulated Echo Acquisition Mode (STEAM) sequence was modified to allow DTI measurements at long t[subscript diff] (approximately 200 ms), while avoiding T2 signal loss. For comparison, DTI data was acquired using STEAM at the shorter value of t[subscript diff] and with the standard Double Spin Echo sequence with matched signal-to-noise ratio. This approach was tested on phantoms and fixed monkey brains and then translated to in vivo studies in rhesus macaques. Qualitative and quantitative comparison of the techniques was based on fractional anisotropy, diffusivity, three-phase plots and directional entropy. Tensor-field maps and probabilistic connectivity fronts were evaluated for all three acquisitions. Comparison of the tracked nerve pathways showed that fibers obtained at long t[subscript diff] were much longer. Further, the optic tract was tracked in ex vivo fixed rhesus brains for cross validation. The optic tract, traced at long t[subscript diff], conformed to the well documented anatomical description, thus confirming the accuracy of tract tracing at long t[subscript diff]. The benefits of DTI at long t[subscript diff] indeed help to realize the potential of tensor based tractography towards studying neural development and diagnosing neuro-pathologies, albeit the improvement is more significant ex vivo than in vivo. In vivo Ex vivo Fixed Rhesus Fiber tracking FA DTI Diffusion time Fractional anisotropy ADC Diagnostic imaging Imaging systems in medicine Magnetic resonance imaging Diffusion tensor imaging Diffusion magnetic resonance imaging
3	Modélisation avancée du signal dMRI pour la caractérisation de la microstructure tissulaire / Advanced dMRI signal modeling for tissue microstructure characterization Fick, Rutger 10 March 2017 (has links) Cette thèse est dédiée à améliorer la compréhension neuro-scientifique à l'aide d'imagerie par résonance magnétique de diffusion (IRMd). Nous nous concentrons sur la modélisation du signal de diffusion et l'estimation par IRMd des biomarqueurs liés à la microstructure, appelé «Microstructure Imaging». Cette thèse est organisée en trois parties. Dans partie I nous commençons par la base de l'IRMd et un aperçu de l'anisotropie en diffusion. Puis nous examinons la plupart des modèles de microstructure utilisant PGSE, en mettant l'accent sur leurs hypothèses et limites, suivi par une validation par l'histologie de la moelle épinière de leur estimation. La partie II présente nos contributions à l'imagerie en 3D et à l’estimation de microstructure. Nous proposons une régularisation laplacienne de la base fonctionnelle MAP, ce qui nous permet d'estimer de façon robuste les indices d'espace q liés au tissu. Nous appliquons cette approche aux données du Human Connectome Project, où nous l'utilisons comme prétraitement pour d'autres modèles de microstructure. Enfin, nous comparons les biomarqueurs dans une étude ex-vivo de rats Alzheimer à différents âges. La partie III présente nos contributions au représentation de l’espace qt - variant sur l'espace q 3D et le temps de diffusion. Nous présentons une approche initiale qui se concentre sur l'estimation du diamètre de l'axone depuis l'espace qt. Nous terminons avec notre approche finale, où nous proposons une nouvelle base fonctionnelle régularisée pour représenter de façon robuste le signal qt, appelé qt-IRMd. Ce qui permet l'estimation des indices d’espace q dépendants du temps, quantifiant la dépendance temporelle du signal IRMd. / This thesis is dedicated to furthering neuroscientific understanding of the human brain using diffusion-sensitized Magnetic Resonance Imaging (dMRI). Within dMRI, we focus on the estimation and interpretation of microstructure-related markers, often referred to as ``Microstructure Imaging''. This thesis is organized in three parts. Part I focuses on understanding the state-of-the-art in Microstructure Imaging. We start with the basic of diffusion MRI and a brief overview of diffusion anisotropy. We then review and compare most state-of-the-art microstructure models in PGSE-based Microstructure Imaging, emphasizing model assumptions and limitations, as well as validating them using spinal cord data with registered ground truth histology. In Part II we present our contributions to 3D q-space imaging and microstructure recovery. We propose closed-form Laplacian regularization for the recent MAP functional basis, allowing robust estimation of tissue-related q-space indices. We also apply this approach to Human Connectome Project data, where we use it as a preprocessing for other microstructure models. Finally, we compare tissue biomarkers in a ex-vivo study of Alzheimer rats at different ages. In Part III, we present our contributions to representing the qt-space - varying over 3D q-space and diffusion time. We present an initial approach that focuses on 3D axon diameter estimation from the qt-space. We end with our final approach, where we propose a novel, regularized functional basis to represent the qt-signal, which we call qt-dMRI. Our approach allows for the estimation of time-dependent q-space indices, which quantify the time-dependence of the diffusion signal. IRM de diffusion Imagerie microstructure Imagerie q-espace Dépendance au temps de diffusion Régularisation de Laplace Signal sparsity Validation histologique Diffusion MRI Microstructure Imaging Q-space imaging Diffusion time dependence Regularized reconstruction Laplace regularization Sparsity signal Histology validation
4	Darstellung und Verwendung von Nucleolipiden zur Lipophilisierung von Nucleinsäuren sowie deren Wechselwirkung und Duplex-Bildung an horizontalen Lipid-Bilayers und Phasengrenzen zur Entwicklung einer neuartigen RNA/DNA-Analytik / Synthesis and Application of Nucleolipids for the Lipophilization of Nucleic Acids and Their Interaction and Duplex Formation at Horizontal Lipid-Bilayers and Phase Boundaries for the Development of a Novel RNA/DNA Analytics Werz, Emma 17 February 2016 (has links) Ziel der vorgestellten Arbeit war die Synthese von Nucleolipiden zur Lipophilisierung von Oligonucleotiden sowie deren Untersuchung im Hinblick auf ihre Wechselwirkung und Duplex-Bildung an horizontalen Lipidmembranen und verschiedenen Phasengrenzen zur Entwicklung eines neuartigen Bio-Chips für die RNA/DNA-Analyse. Mit der Synthese N(3)-prenylierter und 2’,3’-O-ketalisierter Pyrimidinbasen Uridin und Methyluridin wurden Nucleolipid-Bausteine dargestellt, die auch als terminale Kopfgruppen eines Oligonucleotid-Dodecamers den lipophilen Charakter dieser Oligonucleotid-Sequenz erhöhten. Für den Einsatz solcher LONs (Lipo-Oligonucleotide) in einer vereinfachten RNA/DNA-Analytik wurde eine Vielzahl von Lipo-Oligonucleotiden mit diversen Nucleolipid-Kopfgruppen synthetisiert und auf ihr Einlagerungsverhalten in künstliche Lipid-Bilayer untersucht. Fluoreszenz-spektroskopische Untersuchungen zeigten, dass alle Lipo-Oligonucleotide in der Lage sind, sich in künstliche Lipid-Bilayer einzulagern. Abhängig von der Struktur, der Länge und der Anzahl der C-Atom-Ketten dieser lipophilen Anker-Bausteine wurden die Geschwindigkeit und die Festigkeit der Verankerung im Lipid-Bilayer beeinflusst. Des Weiteren wurde die Hybridisierung von LONs mit komplementären Oligomeren an Lipidmembranen untersucht. Es konnte gezeigt werden, dass die im Bilayer verankerten Lipo-Oligonucleotide mit komplementären Oligomeren DNA-Duplexe bilden. Die hybridisierte DNA wurde nicht nur über einen kovalent gebundenen Cy5-Fluorophor am Gegenstrang nachgewiesen, sondern auch über den DNA-Interkalator SYBR Green I (SG). Am Beispiel von zwei Lipo-Oligonucleotiden (LON 20 und 23), die sich schnell und fest in der Bilayermembran verankern, konnte eine spontane Akkumulation dieser LONs an CHCl3/H2O sowie H2O/n-Decan Grenzflächen direkt nach der Probenzugabe beobachtet werden. Diese und andere Ergebnisse stützen den Einsatz von Lipo-Oligonucleotiden als Ziel-Oligomere in einem neuartigen RNA/DNA-Nachweisverfahren an Phasengrenzen. Lipid-Bilayer FCS Lipo-Oligonucleotide Fluoreszenz lipophilisierte DNA Akkumulation Phasengrenzen Diffusionskoeffizient Nucleolipide SYBR Green I Lipophilie DNA-Duplex Diffusionszeit DNA-Interkalator Cy5 DNA-Duplex-Bildung DNA duplex formation Alkylierung 2`,3`-O-Ketale Farnesyl LONs lipid-bilayer FCS lipo-oligonucleotides fluorescence lipophilized DNA accumulation phase boundaries diffusion coefficient nucleolipids SYBR Green I lipophilicity DNA duplex diffusion time DNA intercalator Cy5 alkylation 2`,3`-O-ketals farnesyl LONs 35.78 - Lipide 42.12 - Biophysik 35.65 - Nukleinsäuren 35.66 - Terpene, Steroide, Alkaloide ddc:540 ddc:570

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