Oxidative stress is a natural consequence of photosynthetic oxygen evolution and redox enzyme processes. Trp oxidation to N-formylkynurenine (NFK) is a specific, reactive oxygen species (ROS)-mediated reaction. This thesis work describes the identification and functional characterization of NFK in oxygen evolving Photosystem II (PSII). Although proteomics studies have confirmed NFK modifications in many types of proteins, limited knowledge on the biochemical significance exists. In vitro studies in thylakoids and PSII membranes were used to establish a correlation between oxidative stress, NFK formation, and photoinhibition. The in vivo effect of preventing Trp oxidation to NFK was assessed by site-directed mutation in the cyanobacteria Synechocystis sp. PCC 6803. This work provides insight into the role of NFK in photosynthetic oxygen evolution and photoinhibition. Based on the current knowledge of NFK, ROS, and repair, a new model is described. In this modified model for photoinhibition and repair, NFK plays a role in signaling for turnover of damaged proteins. NFK may play a similar role in replacement of damaged proteins in other systems.

As one category of energetic materials, impact-initiated reactive materials are able to release a high amount of stored chemical energy under high strain rate impact loading, and are used extensively in civil and military applications. In general, polymers are introduced as binder materials to trap the reactive metal powders inside, and also act as an oxidizing agent for the metal ingredient. Since critical attention has been paid on the metal / metal reaction, only a few types of polymer / reactive metal interactions have been studied in the literature. With the higher requirement of materials resistant to different thermal and mechanical environments, the understanding and characterization of polymer / reactive metal interactions are in great demand. In this study, PTFE (Polytetrafluoroethylene) 7A / Ti (Titanium) composites were studied under high strain rates by utilizing the Taylor impact and SHPB tests. Taylor impact tests with different impact velocities, sample dimensions and sample configurations were conducted on the composite, equipped with a high-speed camera for tracking transient images during the sudden process. SHPB and Instron tests were carried out to obtain the stress vs. strain curves of the composite under a wide range of strain rates, the result of which were also utilized for fitting the constitutive relations of the composite based on the modified Johnson-Cook strength model. Thermal analyses by DTA tests under different flow rates accompanied with XRD identification were conducted to study the reaction mechanism between PTFE 7A and Ti when only heat was provided. Numerical simulations on Taylor impact tests and microstructural deformations were also performed to validate the constitutive model built for the composite system, and to investigate the possible reaction mechanism between two components. The results obtained from the high strain rate tests, thermal analyses and numerical simulations were combined to provide a systematic study on the reaction mechanism between PTFE and Ti in the composite systems, which will be instructive for future energetic studies on other polymer / reactive metal systems.

This study deals with reactively compatibilized Polyamide 6 / High Density Polyethylene blends. More precisely, it focuses on the relationship between (1) the formulation, the processing parameters in corotating twin screw extrusion and (2) the morphologies and the microstructures of blends. Multi-scale morphologies were observed by Scanning and Transmission Electron Microscopy. At the micron scale, the following morphologies were developed: nodular dispersions, stretched nodules and co-continuous morphology. As the processing conditions did not influence the types of morphology, the different morphological regions were reported in ternary diagrams. In the case of compatibilized blends, two mechanisms for morphology development have been proposed: (1) the compatibilization reaction, being very fast, leads to the formation of nano-dispersions by interfacial instabilities and (2) the standard break-up/coalescence mechanism of domains poor in copolymer could lead to the formation of morphologies up to the micron scale. Both the evolution of the largest size as a function of the composition and the distribution of sizes were modeled using percolation concepts. The stability of the morphologies was then studied either during static annealing or controlled shear or in a second step processing. The copolymer formed at the interface allows stabilizing the size of the morphologies. Finally, crystallization at lower temperature was observed by Differential Scanning Calorimetry when the polymers are confined in submicron domains.

La modélisation quantitative du transfert de l'eau et des solutés dans la zone non saturée des sols nécessite la mesure in situ des paramètres hydro-dispersifs. L'infiltrométrie sous pression controlée couplée à l'utilisation de traceurs de l'écoulement de l'eau est pour cela un outil efficace et simple à mettre en oeuvre sur le terrain. La modélisation des transferts et l'analyse des résultats des calculs conduit à une methode simplifiée de caracterisation hydro-dispersive par infiltrométrie. La conductivité hydraulique K et la sorptivité S sont estimées à partir de l'analyse aux temps courts ou aux temps longs de l'infiltration cumulée. La méthode mono-tracage est utilisée pour le calcul de la fraction d'eau mobile F. Une nouvelle méthode d'estimation du coefficient de dispersion D est proposée. Elle est telle que D reste l'unique paramètre à ajuster sur les données issues de l'échantillonnage du sol à la fin de l'infiltration. L'incertitude d'estimation est de plus définie pour chacun des paramètres. Le domaine de validité des méthodes est precisé à partir de données genérées numeriquement. Pour le calcul de K, S et F, il est défini à partir des temps caracteristiques de l'écoulement de l'eau, de la lame de solution infiltrée et de la dispersivité du milieu. La validité du mode de détermination de D dépend du nombre adimensionnel pext. Trois sols sont caracterisés in situ. La porosité bimodale des deux premiers induit une forte augmentation des paramètres hydrodynamiques à l'approche de la saturation, et de F avec la taille moyenne de pores hydrauliquement fonctionnels. Le troisième est soumis à l'encroutement de surface. Les résultats de la caractérisation hydro-dispersive renforcés par l'observation du réseau poral sur lames minces montre que le rôle des croutes de surface sur l'infiltrabilité est minimisé par rapport à celui du sol sous-jacent. De plus, le sol sous-jacent semble protegé de la coalescence par les croutes de surface.

Secessionist movements have been found historically on both sides of the political spectrum, and sometimes have tried to remain apolitical completely, but because of the rise of partisan politics, secessionism has inevitably become politicized. Variations in Western European secessionism can be noticed, and as such, explanations put forward may be deemed insufficient, or incomplete. In my thesis I tested the hypothesis that secessionism varied on the political spectrum because it has been consolidated against ideological Others (in Scotland against Thatcher’s Conservatives between 1974 and 1990). I tested this methodologically through process tracing and theoretically by looking at the consolidation of the Scottish National Party through reactive nationalism. Specifically I analyzed the nationalist discourse used to justify ideological positioning in the 1970s and 1980s in propaganda materials and archival documents, and if and how this ideological choice was reflected or interpreted in newspapers (for opinions on how this consolidation was perceived by the electorate).

In traditional Wireless Sensor network's (WSN's), the sink is the only unconditionally trusted authority. If the sink is not connected to the nodes for a period of time then the network is considered as unattended. In Unattended Wireless Sensor Network (UWSN), a trusted mobile sink visits each node periodically to collect data. This network differs from the traditional multi hop wireless sensor networks where the nodes close to the sink deplete their power earlier than the other nodes. An UWSN can prolong the life time of the network by saving the battery of the nodes and also it can be deployed in environments where it is not practical for the sink to be online all the time. Saving data in the memory of the nodes for a long time causes security problems due to the lack of tamper-resistant hardware. Data collected by the nodes has to be secured until the next visit of the sink. Securing the data from an adversary in UWSN is a challenging task. We present two non-cryptographic algorithms (DS-PADV and DS-RADV) to ensure data survivability in mobile UWSN. The DS-PADV protects against proactive adversary which compromises nodes before identifying its target. DS-RADV makes the network secure against reactive adversary which compromises nodes after identifying the target. We also propose a data authentication scheme against a mobile adversary trying to modify the data. The proposed data authentication scheme uses inexpensive cryptographic primitives and few message exchanges. The proposed solutions are analyzed both mathematically and using simulations proving that the proposed solutions are better than the previous ones in terms of security and communication overhead.

The thesis provides a political analysis of a position paper on government programming recently adopted by the Ukrainian Canadian Congress (UCC) a national ethno-cultural organisation that ostensibly represents over one million Canadians of Ukrainian heritage and a historically important player in the development of multiculturalism in Canada. The impetus for such an analysis is to explore whether there are alternative policy directions available to the UCC that could satisfy its mandate developing and enhancing the Ukrainian-Canadian community while taking into account the reality that Ukrainian-Canadians culturally resemble more and more the broader Canadian society. <p>In a wide-ranging analysis that criticizes both, official Canadian multiculturalism for falling short in meeting its commitment to cultural pluralism and the UCC for upholding a position that relies on a static or retrograde version of culture, the thesis makes the case for a multiculturalism that can recognize cultural differences while allowing for change. <p>The thesis is significant because it asks relevant questions concerning how multiculturalism in Canada takes into account an increasingly heterogeneous citizenship characterized by cultural change. In this regard, the thesis is of particular importance to Canadians who claim a multiplicity of cultures rather than a single ethnicity and yet still express a desire to be included in the discourse on Canadian national identity.

In order to investigate the structural features responsible for the cytotoxicity of the naturally occurring lignan nordihydroguaiaretic acid, the synthesis of four structural analogues of NDGA is proposed for the purpose of studying their oxidative metabolism. One analogue in particular (1), a mono-catechol analogue, is successfully synthesized employing a double Stobbe condensation approach. Following synthesis of this compound a series of oxidation experiments is performed consisting of: incubation in rat liver microsomes with and without the trapping agent glutathione (GSH), oxidation with mushroom tyrosinase, oxidation with silver oxide, and oxidation with horseradish peroxidase. Results are analyzed via HPLC and UPLC-MS. It is found that 1 does not autoxidize at pH 7.4 as NDGA does. Two products are produced during incubation of 1 in rat liver microsomes with UPLC-ESI(-)-MS results giving m/z of 879.2 and 574.18. This is consistent with 1 plus 2 GSH and 1 plus 1 GSH respectively; confirming 1 will oxidize to an electrophilic moiety. Oxidation with mushroom tyrosinase is found to produce high levels of product two with m/z 574.2. Oxidation with horseradish peroxidase is found to produce high levels of the m/z 879.2 product. Silver Oxide produced multiple products rather than the expected one major product, but most are found to be inconsistent with the products seen during rat liver microsomal incubation, and are not pursued.

Nevirapine (NVP) can cause serious skin rashes and hepatotoxicity. It also causes an immune-mediated skin rash in rats but not hepatotoxicity. There is strong evidence that the rash is due to 12-hydroxynevirapine (12-OH-NVP), which is further metabolized to a reactive benzylic sulfate in the skin. This could both act as a hapten and induce a danger signal. In contrast, most of the covalent binding in the liver appears to involve oxidation of the methyl group leading to a reactive quinone methide. In this study we examined the effects of NVP and 12-OH-NVP on gene expression in the liver and skin. Both NVP and 12-OH-NVP induced changes in the liver, but the list of genes was different, presumably reflecting different bioactivation pathways. In contrast, many more genes were up-regulated in the skin by 12-OH-NVP than by NVP, which is consistent with the hypothesis that the 12-hydroxylation pathway is involved in causing the rash. Some genes up-regulated by 12-OH-NVP were Trim63, S100a7a, and IL22ra2, etc. Up-regulation of genes such as S100a7a, which is considered a danger signal, supports the danger hypothesis. Up-regulation of genes such as the ubiquitin ligase and Trim63 are consistent with protein-adduct formation. Up-regulation of IL-22ra2 gene suggests an immune response. These results provide important clues to how NVP causes induction of an immune response, in some cases leading to an idiosyncratic drug reaction.

Listeria monocytogenes is an intracellular bacterium that utilizes two phospholipases C (PLCs) and a pore-forming cytolysin (listeriolysin O, LLO) to escape the phagosome. However, prior to escape, the bacterium must overcome a number of phagosomal defenses, including autophagy and NOX2 NADPH oxidase production of reactive oxygen species (ROS). Autophagy, the cellular process of self-digestion, is a key component of innate immunity. Previously, it has been shown that L. monocytogenes is targeted by autophagy (LC3+) at 1 h post infection (p.i.) but the mechanism remains elusive. Here, I show that at 1 h p.i., diacylglycerol (DAG) and ROS production are required for autophagy targeting to the bacteria, which are predominantly in phagosomes. It has been shown that autophagy targeting of cytosolic L. monocytogenes is mediated via protein ubiquitination. However, protein ubiquitination is not associated with LC3+ bacteria at 1 h p.i.. Thus, my data suggest that distinct signals mediate autophagy targeting of L. monocytogenes depending on the location within host cells. Given that ROS mediate autophagy targeting to L. monocytogenes and that previous studies have demonstrated that ROS production limits bacterial escape, I investigated how L. monocytogenes overcomes ROS production prior to phagosomal escape. I found that LLO inhibits ROS production by preventing NOX2 NADPH oxidase localization to L. monocytogenes-containing phagosomes. LLO-deficient bacteria can be complemented by perfringolysin O, a related cytolysin, suggesting that other pathogens may also use pore-forming cytolysins to inhibit ROS production. While PLCs can activate ROS production, this effect is alleviated by LLO pore-formation. Therefore, the combined activities of PLCs and LLO allow L. monocytogenes to efficiently escape the phagosome while avoiding microbicidal ROS. Together, this thesis provides a clearer understanding of the balance between host defense versus bacterial evasion. Greater insight into host-bacterial interaction may lead to better therapeutics that can “tip the balance” in the host’s favour.