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In order to achieve efficient therapeutic effect, it is important to understand the structure of biomaterials that are used in the therapeutic delivery system. This dissertation is dedicated towards understanding the hydrolysis pattern of plasmid DNA (pDNA) delivery vehicles comprised of poly(glycoamidoamine)s (PGAAs) under physiological conditions and effects of subtle changes in the chemical structure of the PGAAs on its biological performance. The unusual hydrolysis of the tartarate and galactarate based PGAAs was investigated by studying the hydrolysis of small model molecules which mimic the repeat unit of the respective polymers. In the case of galactarate and tartarate based molecules with terminal amines showed faster hydrolysis of the amide bonds. In addition for the tartarate based compounds, it was also found that it is necessary to have terminal amine functionality for the intramolecular hydrolysis to occur. The model compounds consists of two amide bonds and were designed symmetric, however amide bond on only one side of the tartarate moiety show underwent hydrolysis. Further studies show that one side of the amine assists the hydrolysis of the amide bond on the other side of the tartarate moiety. The degradation of poly(L-tartaramidopentaethylenetetramine) (<strong>T4</strong>) was also used to study the sustained release of pDNA from the layer-by-layer constructs of <strong>T4</strong>/pDNA. The thickness of the constructs was characterized by ellipsometry while the UV-visible spectroscopy was used to characterize the loading capacity of the constructs for pDNA. The indirect sustained release of pDNA under the physiological conditions with respect to time was characterized by the cellular uptake studies in HeLa cells. The increase in the uptake of the Cy5 labeled pDNA was seen at extended period of eleven days. The integrity of the sustained released pDNA for the transgene expression was characterized with an assay to see the expression of the green fluorescent protein (GFP) from the <strong>T4</strong>/GFP-pDNA layer-by-layer constructs. PGAAs show a very efficient delivery of the pDNA in a non-toxic manner. The chemical structure of the polymer can dictate the binding with pDNA and also the release of the pDNA form the polymer-pDNA complexes. In order to better understand the fundamentals of the nucleic acid delivery and to better design the nucleic acid delivery vehicles, subtle changes in the chemical structure of the PGAAs were designed and studied for the biological activity. The effect of charge type was investigated by designing and synthesizing guanidine based polymer series analogues to galactarate and tartarate based PGAAs (<strong>G1</strong> and <strong>T1</strong>) which incorporate secondary amines as the charge type on the polymer backbone. The guanidine based polymer series, poly(glycoamidoguanidine)s (PGAGs), show very non toxic behavior in HeLa cells at all the different polymer to pDNA ratio (<i>N/P</i> ratio) studied. Interestingly PGAGs are the only non-toxic guanidine containing polymers which are reported in the literature to the date. The cellular uptake of pDNA assisted from the PGAGs is a little higher than PGAAs compared although both the series of polymers show similar transgene expression. The transgene expression in case of PGAGs also imply the release of the polymer-pDNA complexes from the endosome. In another study of structure-bioactivity relationship based on the degree of polymerization (DP) of poly(galactaramidopentaethylenetetramine) (<strong>G4</strong>), it was found that the increase in the DP of <strong>G4</strong> increases the toxicity of the polymers in the HeLa cells. / Ph. D.

The use of plastic materials in the design of vehicle components is primarily driven by the need for vehicle weight and cost reduction. Additionally, these materials give design engineers freedom in creating appealing exterior designs. However, creating self-carrying exterior structures with polymers must fulfill long-term strength, creep and fatigue life requirements. Thus, the polymer polyDicyclopentadiene (pDCPD) has been chosen for this purpose. Its aging mechanics need to be understood by the design engineers to make the right decisions. This thesis has carried out mechanical tests such as uniaxial tensile testing, fatigue, and creep testing. Digital image correlation (DIC) system has been used to capture strain data from tensile tests. In the final analysis, DIC measurements proved more accurate than extensometer data retrieved from the testing machine. The rise in temperature has been captured using thermal imaging. Several degradation processes have been explored including physical aging, thermo-oxidation, photo-oxidation, chemical- and bio- degradations. Test results showed significant changes in mechanical properties after 17 years of aging. Additionally, severe thermal degradation has been observed in one of the tested panels of pDCPD. Temperature can rise to significant levels during cyclic loading at high stresses, which could have an impact on physical aging effects. Viscoelastic behavior has been explored and changes in dynamic and creep properties have been observed. The investigation also reviled that different defects caused by flawed manufacturing also can affect the material severely as one case has proved in this research.

Dans cette thèse, une solution de caoutchouc de styrène-butadiène (SBR) réticulé avec du peroxyde organique, a été transformé en un gel autodégradable par l’ajout d’hydropéroxyde comme agent de dégradation. La formulation a été caractérisée en rhéologie dynamique. Les spectres de temps de relaxation ont été calculés à partir des modules dynamiques de cisaillement, par une nouvelle méthode développée dans ces travaux présentée avec une revue complète de méthodes pour le calcul des spectres de relaxation à partir de données de rhéométrie de cisaillement. Des expériences in-situ et ex-situ ont été réalisées afin d’évaluer l’évolution de les réactions de réticulation et dégradation. Les changements de la structure du réseau polymérique sont mises en évidence dans les spectres de temps de relaxation. La cinétique de la dégradation de la solution de SBR a été étudiée dans des conditions anaérobies et caractérisée par diffusion de la lumière multi-angles couplée à la chromatographie d’exclusion stérique (SEC-MALS). En utilisant des équations de bilan de populations, nous avons pu calculer les constantes cinétiques de dégradation thermique et thermo-oxydative. Différentes formulations de ces gels auto-dégradables à base d’huile ont été évaluées en tant que potentiels agents de dérivation pour des opérations de traitement de puits. Le comportement rhéologique de ces gels a été mesuré en fonction du temps, pour vérifier la réticulation du polymère, la force de gel, et la dégradation ; ces variables peuvent être ajustées aux nécessités de l’opération de traitement en jouant sur la formulation. Des tests d’écoulement dans carotte simples ont été réalisés pour évaluer la résistance à la pression en fonction de la force du gel et de sa dégradation. Des tests d’écoulement dans carottes parallèles ont également été menés, afin d’évaluer l’efficacité de la dérivation et la restauration de mobilité. / In this work, a solution of peroxide crosslinked styrene-butadiene rubber (SBR) has been transformed to a self-degradable gel system by adding hydroperoxide as a degradation agent to the formulation. Dynamic rheometry was employed to calculate the relaxation time with a new method presented along with a full review of methods for calculation of the relaxation time spectrum from oscillatory rheometry. In-situ and ex-situ experiments were performed to evaluate the evolution of crosslinking and degradation reactions. Structural changes in the polymer network were visible within the relaxation time spectra. The degradation kinetics of styrene butadiene rubber (SBR) in solution was studied in anaerobic conditions and the characterization was performed by multiangle light scattering coupled to size exclusion chromatography (SEC-MALS). Using population balance equations, it was possible to calculate the kinetic constants for thermal and thermooxidative degradation. Different formulations of these oil-based self-degradable gels have been evaluated as possible diverting agents during oil wells operations. The time dependent rheological behavior of the gels was measured to verify polymer crosslinking, maximum gel strength and gel degradation, all of which can be adjusted by varying formulation depending on operation needs. Single core tests were performed to evaluate pressure resistance as a function of gel strength and gel degradation. Parallel cores tests were also carried out to validate diversion efficiency and mobility restoration.

Les fibres d'acide polylactique (PLA), issues de ressources agricoles renouvelables, ont suscité à leur apparition un grand intérêt car il s'agit de fibres ayant les avantages des fibres synthétiques. Or très vite des inconvénients sont apparus en particulier lors de leur teinture : elles se saturent très facilement conduisant a des nuances pastel et les solidités aux lavages des teintures sont médiocres. Nous avons vérifié que la cristallinité des fibres de PLA est du même ordre de grandeur que celle du polyester classique (55- au pire 60%). Par contre les traitements aqueux type teinture font croître cette cristallinité, peut-être par hydrolyse des zones amorphes. Mais la teinture est très rapide, ce qui signifierait que les zones amorphes sont à peine orientées ce qui est confirmé par RX (un fond continu vraiment plat) et de ce fait elles ne retiennent pas le colorant. Les isothermes d'adsorption montrent également qu'il n'y a pas d'adsorption mais « solution » puisqu'elles sont de type Nernst et que la fixation de colorant décroît avec la croissance de la température. En plus, à chaque traitement aqueux de la fibre est hydrolysée ce qui entraîne une perte de colorant et une réduction lente des propriétés mécaniques de la fibre. Ce dernier phénomène étant relativement long d'où nous avons formulé une hypothèse que l'hydrolyse des bouts de chaine serait plus rapide que celle des milieux de chaine. / The fibers of poly (lactic acid) (PLA), derived from annually renewable agricultural resources, had a great potential when they were first introduced into the market as they have the advantages of synthetic fibers, as well as they are biodegradable. Some current challenges and limitations associated with these new fibers have constrained their popularity, especially when they were dyed. They easily become saturated leading to pastel shades and their washfastness is poor. We verified that the crystallinity of PLA fibers is comparable to that of conventional polyester (55 - 60% at worst). However, this crystallinity has increased during the wet treatment, especially dyeing, which may be due to the hydrolysis of amorphous regions. Rapid stricke of the dye means that the amorphous regions are barely oriented (hence X-ray background intensity is really flat) and they do not retain the dye molecules.The adsorption isotherms also show that there is no adsorption but it is a "solution" as they are of the Nernst type and the dye fixation decreases with increasing temperature. But each wet treatment leads to a fiber hydrolysis which causes a loss of dye and a slow loss of mechanical properties of the fiber. The latter phenomenon is relatively long leading to a hypothesis that the hydrolysis by side-group elimination would be faster than the degradation of weak points in the macromolecular polymer chains.

Non-conventional techniques for polymerization and depolymerization were investigated. The rates of polymerization were enhanced higher in ultrasonic, supercritical fluids and microwaves. However in these system under certain conditions, simultaneous degradation also occurred. Depolymerization was studied by various methods like thermal degradation in supercritical fluids and in presence of oxidizers, Lewis acid and other organic acids. Degradation by ultrasound and thermal degradation of polymer mixtures were also investigated. The scission of the polymer backbone is random for thermal degradation while the scission occurs at the midpoint for ultrasonic degradation. The degradation rates in all the investigated techniques were higher than the degradation rates observed for pyrolysis. Degradation was possible at low temperature (< 50°C) for oxidative and ultrasound degradation while the degradation rates were two orders of magnitude higher in supercritical conditions. The molecular weight distribution was obtained by GPC analysis and the continuous distribution models were used to obtain the rate coefficients. The activation energies were calculated from the temperature dependence of the rate coefficients.

Characterization of cellulose by its molecular weight distribution is afforded after polymeranalogeous dissolution. Additionally, a molecular dispersion of the polymer is a prerequisite. Common processes are dissolution of cellulose in dimethylacetamide-lithiumchloride, nitration and carbanilation. Degradation of the polysaccharide chains can occur in each of the mentioned processes. It is shown that degradation in pyridine occurs via beta-elimination at carbonyl groups along the cellulose chains. Carbanilierung in DMSO is much more pronounced. It comprises oxidation along the Pfitzner-Moffatt-mechanism and subsequent beta-elimination at the thus formed carbonyl-groups. This was elucidated with model systems and by investigation of the carbanilation in different media. Carbonyl groups of cellulose are masked through reaction with phenylisocyanate. This was shown with model. Therefore, the determination of carbonyl groups in cellulose-tricarbanilates is not possible. The separation of low-molecular weight byproducts was optimised. The influence of pretreatment and preactivation of cellulose-samples on the completeness of the conversion was studied. A standard protocol for the carbanilation of cellulose is provided. / Cellulose wird u.a. durch ihre Molmassenverteilung charakterisiert, deren Ermittlung ein polymeranaloges Verfahren zur molekulardispersen Auflösung des Polymers erfordert. Hierfür sind die Direktlösung, die Nitrierung und die Carbanilierung in Gebrauch. Bei allen Prozessen kann es zum Abbau der Polysaccharidketten kommen, wobei diesen Prozessen wenig Beachtung geschenkt wurde. In der Arbeit wird gezeigt, daß der Abbau bei der Carbanilierung in Pyridin durch Beta-Eliminierung an vorhandenen Carbonylgruppen erfolgt. Die Carbanilierung in DMSO fällt stets stärker aus als bei Einsatz von Pyridin und umfasst die Prozesse Oxidation nach dem Pfitzner-Moffatt-Mechanismus und anschließende Beta-Eliminierung an den neu gebildeten Carbonylgruppen. Dies wird durch Untersuchungen an Modellsystemen und am Polymer herausgearbeitet. Carbonylgruppen an Cellulose werden durch die Umsetzung mit Phenylisocyanat maskiert, was an Modellverbindungen gezeigt wurde (Bildung von Endioldicarbanilaten und carbanilierten Halbacetalen). Ihre Bestimmung in Cellulosecarbanilaten ist daher nicht möglich. Die Abtrennung von niedermolekularen Nebenprodukten der Umsetzung wurde optimiert. Der Einfluss der Vorbehandlung und Voraktivierung von Celluloseproben auf die Vollständigkeit der Umsetzung wurde eingehend untersucht. Es wird ein Standardverfahren zur Carbanilierung von Cellulose angegeben.

This PhD project has expanded the knowledge in the area of profluorescent nitroxides with regard to the synthesis and characterisations of novel profluorescent nitroxide probes as well as physical characterisation of the probe molecules in various polymer/physical environments. The synthesis of the first example of an azaphenalene-based fused aromatic nitroxide TMAO, [1,1,3,3-tetramethyl-2,3-dihydro-2-azaphenalen-2-yloxyl, was described. This novel nitroxide possesses some of the structural rigidity of the isoindoline class of nitroxides, as well as some properties akin to TEMPO nitroxides. Additionally, the integral aromatic ring imparts fluorescence that is switched on by radical scavenging reactions of the nitroxide, which makes it a sensitive probe for polymer degradation. In addition to the parent TMAO, 5 other azaphenalene derivatives were successfully synthesised. This new class of nitroxide was expected to have interesting redox properties when the structure was investigated by high-level ab initio molecular orbitals theory. This was expected to have implications with biological relevance as the calculated redox potentials for the azaphenalene ring class would make them potent antioxidant compounds. The redox potentials of 25 cyclic nitroxides from four different structural classes (pyrroline, piperidine, isoindoline and azaphenalene) were determined by cyclic voltammetry in acetonitrile. It was shown that potentials related to the one electron processes of the nitroxide were influenced by the type of ring system, ring substituents or groups surrounding the moiety. Favourable comparisons were found between theoretical and experimental potentials for pyrroline, piperidine and isoindoline ring classes. Substitution of these ring classes, were correctly calculated to have a small yet predictable effect on the potentials. The redox potentials of the azaphenalene ring class were underestimated by the calculations in all cases by at least a factor of two. This is believed to be due to another process influencing the redox potentials of the azaphenalene ring class which is not taken into account by the theoretical model. It was also possible to demonstrate the use of both azaphenalene and isoindoline nitroxides as additives for monitoring radical mediated damage that occurs in polypropylene as well as in more commercially relevant polyester resins. Polymer sample doped with nitroxide were exposed to both thermo-and photo-oxidative conditions with all nitroxides showing a protective effect. It was found that isoindoline nitroxides were able to indicate radical formation in polypropylene aged at elevated temperatures via fluorescence build-up. The azaphenalene nitroxide TMAO showed no such build-up of fluorescence. This was believed to be due to the more labile bond between the nitroxide and macromolecule and the protection may occur through a classical Denisov cycle, as is expected for commercially available HAS units. Finally, A new profluorescent dinitroxide, BTMIOA (9,10-bis(1,1,3,3- tetramethylisoindolin-2-yloxyl-5-yl)anthracene), was synthesised and shown to be a powerful probe for detecting changes during the initial stages of thermo-oxidative degradation of polypropylene. This probe, which contains a 9,10-diphenylanthracene core linked to two nitroxides, possesses strongly suppressed fluorescence due to quenching by the two nitroxide groups. This molecule also showed the greatest protective effect on thermo-oxidativly aged polypropylene. Most importantly, BTMIOA was found to be a valuable tool for imaging and mapping free-radical generation in polypropylene using fluorescence microscopy.

Roofing foils are known for several years as building material for roof hydro insulation but their life service is not yet fully known. This thesis is focused on problematics of life service of roofing foils. In theoretical part there is discribed structure of foils and impacts which assist degradation processes. Practical part modifies the methodology artificial aging which is simulated in QUV tester and Q-SUN XE3 tester lumber-rooms. The thesis is trying reach with the results to natural aging as close as possible. The testing captures attributes which are more prone to degradation.