Thèse (Ph. D.)--Université Laval, 2009. / Titre de l'écran-titre (visionné le 13 janvier 2010). Bibliogr.

Results of an experimental test program are presented to determine the bursting strength of polyethylene terephthalate film and fabric cylinders containing axial silts of various lengths. The results demonstrate that the fabric material is superior to the film material as regards residual strength in the presence of a slit. It is shown that the strength-weight ratio of the fabric cylinders is approximately twice that of the film cylinders, largely due to the strength advantage of fiber over film. The results are compared with the predicted bursting strength obtained from two different semiempirical analyses, one based on notch strength analysis and the other employing fracture mechanics concepts. The comparison demonstrates that large errors can result from the application of the notch-strength analysis yields a scatter band which is consistent with the data scatter and follows the trend of the data. / Master of Science

Determination of the three-dimensional structure of enzymes at atomic resolution is a key prerequisite for elucidation of molecular mechanisms of catalysis and catalysis mechanism prediction. X-ray protein crystallography is the most widely used method today for determining protein structures. In this thesis we describe the expression, purification, crystallization and structure solution of two new enzymes: PyrH and PrnB. PyrH is a member of the new emerging family of FADH dependent tryptophan halogenases. It catalyzes the regioselective halogenation of tryptophan at the C-5 position of the indole ring. Elucidation of its structure (Chapter 2) and comparison with PrnA, aregioselective 7th tryptophan halogenase whose structure has already been solved confirmed the proposed mechanism of action for this class of enzymes. PrnB is the only enzyme known to perform exquisite and peculiar ring rearrangement chemistry: it converts 7-Cl-tryptophan and tryptophan into respectively monodechloroaminopyrrolnitrin and aminophenylpyrrole. We developed a method for expression and purification of milligrams of pure and homogeneous recombinant PrnB (Chapter 3). We identified suitable crystallization conditions and determined PrnB structure (Chapter 4). Analysis of the PrnB structure helped us to propose a reaction mechanism for this unique enzyme.

Presented in this study is a wide-ranging investigation into the use of properties of balance in an operational numerical weather prediction context. Initially, a joint numerical and observational study is undertaken. We used the Unified Model (UM), the suite of atmospheric and oceanic prediction software used at the UK Met Office (UKMO), to locate symmetric instabilities (SIs), an indicator of imbalanced motion. These are areas of negative Ertel potential vorticity (in the Northern hemisphere) calculated on surfaces of constant potential temperature. Once located, the SIs were compared with satellite and aircraft observational data. As a full three-dimensional calculation of Ertel PV proved outwith the scope of this study we calculated the two-dimensional, vertical component of the absolute vorticity, to assess the inertial stability criterion. We found that at the synoptic scale in the atmosphere, if there existed a symmetric instability, it was dominated by an inertial instability. With the appropriate observational data, evidence of inertial instability from the vertical component of the absolute vorticity, predicted by the UM was found at 12km horizontal grid resolution. Varying the horizontal grid resolution allowed the estimation of a grid length scale, above which, the inertial instability was not captured by the observational data, of approximately 20km. Independently, aircraft data was used to estimate that horizontal grid resolutions above 20-25km should not model any features of imbalance providing a real world estimate of the lower bound of the grid resolution that should be employed by a balanced atmospheric prediction model. A further investigation of the UM concluded that the data assimilation scheme and time of initialisation had no effect on the generation of SIs. An investigation was then made into the robustness of balanced models in the shallow water context, employing the contour-advective semi-Lagrangian (CASL) algorithm, Dritschel & Ambaum (1997), a novel numerical algorithm that exploits the underlying balance observed within a geophysical flow at leading order. Initially two algorithms were considered, which differed by the prognostic variables employed. Each algorithm had their three-time-level semi-implicit time integration scheme de-centred to mirror the time integration scheme of the UM. We found that the version with potential vorticity (PV), divergence and acceleration divergence, CA[subscript(δ,γ)], as prognostic variables preserved the Bolin-Charney balance to a much greater degree than the model with PV, divergence and depth anomaly CA[subscript(tilde{h},δ)], as prognostic variables. This demonstrated that CA[subscript(δ,γ)] was better equipped to benefit from de-centring, an essential property of any operational numerical weather prediction (NWP) model. We then investigate the robustness of CA[subscript(δ,γ)] by simulating flows with Rossby and Froude number O(1), to find the operational limits of the algorithm. We also investigated increasing the efficiency of CA[subscript(δ,γ)] by increasing the time-step Δt employed while decreasing specific convergence criteria of the algorithm while preserving accuracy. We find that significant efficiency gains are possible for predominantly mid-latitude flows, a necessary step for the use of CA[subscript(δ,γ)] in an operational NWP context. The study is concluded by employing CASL in the non-hydrostatic context under the Boussinesq approximation, which allows weak stratification to be considered, a step closer to physical reality than the shallow water case. CASL is compared to the primitive equation pseudospectral (PEPS) and vorticity-based pseudospectral (VPS) algorithms, both as the names suggest, spectral-based algorithms, which again differ by the prognostic variables employed. This comparison is drawn to highlight the computational advantages that CASL has over common numerical methods used in many operational forecast centres. We find that CASL requires significantly less artificial numerical diffusion than its pseudospectral counterparts in simulations of Rossby number ~O(1). Consequently, CASL obtains a much less diffuse, more accurate solution, at a lower resolution and therefore lower computational cost. At low Rossby number, where the flow is strongly influence by the Earth's rotation, it is found that CASL is the most cost-effective method. In addition, CASL also preserves a much greater proportion of balance, diagnosed with nonlinear quasigeostrophic balance (NQG), another significant advantage over its pseudospectral counterparts.

This Thesis reports the synthesis, purification and characterisation of gold nanoparticles (NPs) functionalised with a monolayer of hydrazone ligands in order to perform post-synthetic manipulations of the NP-bound monolayer exploiting dynamic covalent chemistry. NP post-synthetic manipulation based on reversible non-covalent interactions between oligonucleotides represents a promising approach to achieve functionalisation and self-assembly for potential applications in biology and medicine. However, the stability of these nanosystems is ensured only in a narrow window of environmental conditions. On the other hand, irreversible covalent strategies potentially allow the full range of synthetic chemistry to be exploited but they provide poor control over the manipulation of the NP-bound monolayer and can only produce kinetically controlled amorphous NP aggregates. Dynamic covalent chemistry represents an interesting and an attractive alternative approach because it would combine the reversibility of non-covalent interactions with the stability of covalent bonds. By this way, ligand-functionalised NPs could be manipulated in order to introduce a large variety of molecular functionalities on the NP surface not only to subtly tune the NP physicochemical properties but also to access an entire range of novel nanomaterials.

We analyze the pass-through of cost changes to retail tariffs in the German electricity market over the 2007-2014 period. We find an average pass-through rate of around 60%. This significantly varies with demand factors: while the pass-through rate to baseline tariffs, where firms have greater market power because customers are less willing to switch, is only 50%, it increases to 70% in the competitive segment of the market. Although the pass- through rate of independent firms is significantly higher than that of other firms in the competitive market segment, the extent of supply-side heterogeneity is limited. Thus, the firms' ability to exercise market power and reduce pass-through appears to be constrained by competition and largely determined by demand side factors. Finally, we find that the pass-through rate in the competitive market segment has been approaching unity over the past years, indicating a rise in competitive pressure.

The research reported in this thesis tested the hypothesis that low-income families purchase private brands of selected food products because they represent acceptable quality at lower prices. The six food products selected were coffee, flour, peanut butter, bread, pork and beans, and margarine. The data collected in field interviews and subsequent statistical analyses consistently refuted the hypothesis. This finding is true for the low-income consumer segment and its sub-categories, white and Negro. The low-income consumers do not purchase private brands heavily, but test data indicate that this market segment buys more private brands than does the C > $7000 consumer group. There is evidence of substantial differences in the buying habits of low-income Negro and white consumers. While neither market segment purchases more private brands than national labels, the N < $3000 consumer tends to buy more private brands than does the W < $3000 consumer. Contrary to the hypothesis the indication is that the C > $7000 consumer knows price better than does the low-income consumer. Also, greater importance is attached to price by the C > $7000 group than by the low-income segment. This is not true of the Negro consumer. As stated above, the N < $3000 consumer buys more private brands than does the W < $3000 consumer. This tendency exists for price knowledge and the importance attached to price. The Negro consumer tends to know prices better, and he attaches more importance to price than does any of the other income segments tested. Regarding private-brand awareness, none of the market segments tested was well informed about private-brand market offerings. However, low-income consumers were able to name more private brands than were the C > $7000 consumers. Negro consumers were able to name more private labels than the W < $3000 group. The field data and test results all indicate that the Negro consumer tends to spend his money on the selected products more knowledgeably than the lower income white consumer. The Negro is better informed as to price and the private-brand offering. / M.S.

L’infiltration d’éosinophiles dans la muqueuse bronchique est une caractéristique majeure de l’asthme. Les protéases sont essentielles pour réguler la migration cellulaire du sang vers la muqueuse bronchique. Les travaux présentés dans cette thèse décrivent quelques mécanismes de la modulation de l’activité protéolytique des éosinophiles. Parmi les nombreuses protéases exprimées par l’éosinophile, la métalloprotéinase de la matrice (MMP)-9 et la plasmine générée via la protéine activatrice de type urokinase (uPA) sont cruciales dans la migration de ces cellules dans les tissus. Cette thèse décrit le mécanisme d’action de deux types de médiateurs lipidiques, les cystéinyl-leucotriènes (cysLTs) et l’acide 5-oxo-6,8,11,14-éicosatétraénoïque (5-oxo-ETE), dans le recrutement des éosinophiles. En présence de 5-oxo-ETE, l’éosinophile migre en sécrétant la MMP-9, la plasmine et exprime plus fortement le récepteur de l’uPA (uPAR). Nous avons démontré que les cysLTs sont impliqués dans la migration sans toutefois influencer la protéolyse. Par contre, le montelukast, un antagoniste du récepteur cysLT de type 1 (CysLT1), diminue l’expression d’uPAR, la sécrétion de MMP-9 et la génération de plasmine. Ces résultats suggèrent que le montelukast ne serait pas un antagoniste neutre du CysLT1, mais un agoniste inverse, quoique cette hypothèse doive être confirmée. Ensuite, pour mieux comprendre comment le 5-oxo-ETE induit la sécrétion de protéases, la signalisation sous-jacente a été étudiée. Les travaux démontrent que la protéine kinase C (PKC)-δ, la PKC-ζ, l’extracellular signal-regulated kinase (ERK)-1/ 2 et la p38 mitogen-activated protein kinase (MAPK) jouent un rôle majeur dans la migration induite par le 5-oxo-ETE. Notamment, l’activation d’ERK-1/2 semble dépendre de la présence de plasminogène dans le milieu. La plasmine générée à partir du plasminogène peut activer ERK-1 /2 et ainsi stimuler la sécrétion de MMP-9. Ces résultats démontrent la complexité de la régulation des protéases chez l’éosinophile et documente le rôle primordial des PKC et des MAPK dans cette modulation. / Infiltration of eosinophils into the bronchial mucosa is a key feature in asthma pathology. With the influence of mediators, eosinophils have the capacity to interact with structural cells, modulate their functions, promote airway remodelling, and activate and recruit other inflammatory cells. Proteases are essential to promote cell migration from blood into tissue and interactions with tissue structural cells and extracellular matrix components. This work presents some of the mechanisms modulating eosinophil protease activity, more specifically the production of MMP-9 and plasmin. Herein, we evaluated the mechanism of action of two lipid mediators, the cysteinyl-leukotrienes (cysLTs) and the 5-oxo-ETE, in eosinophil recruitment. 5-Oxo-ETE elicits eosinophil migration by activating MMP-9 secretion, plasmin generation and by increasing uPAR expression. The cysLTs are also implicated in eosinophil migration but not in protease activation. On the other hand, montelukast, a cysLT type 1 receptor antagonist, decreases uPAR expression, MMP-9 secretion and plasmin generation. These results suggest that montelukast is not a neutral antagonist, but an inverse agonist in eosinophils, although this hypothesis needs to be validated. Thereafter, we were interested in signalling induced by 5-oxo-ETE. Our results demonstrated that protein kinase C (PKC)-δ, PKC-ζ, extracellular signal-regulated kinase (ERK)-1/2 and p38 mitogen-activated protein kinase (MAPK) play a major role in eosinophil migration. The implication of ERK-1/2 seems to depend on plasminogen presence in the medium. Plasmin generated from plasminogen activates ERK-1/2 and stimulates MMP-9 secretion. These results demonstrate the complex regulation of eosinophil proteases and the essential implication of PKC and MAPK in this process.

Today's information and communication industry is confronted with a serious bottleneck due to the prohibitive energy consumption and limited transmission bandwidth of electrical interconnects. Silicon photonics offers an alternative by transferring data optically and thereby eliminating the restriction of electrical interconnects over distance and bandwidth. Due to the inherent advantage of using the same material as that used for the electronic circuitry, silicon photonics also promises high volume and low cost production plus the possibility of integration with electronics. In this thesis, I introduce an all-silicon optical interconnect architecture that promises very high integration density along with very low energy consumption. The basic building block of this architecture is a vertically coupled photonic crystal cavity-waveguide system. This vertically coupled system acts as a highly wavelength selective filter. By suitably designing the waveguide and the cavity, at resonance wavelength of the cavity, large drop in transmission can be achieved. By locally modulating the material index of the cavity electrically, the resonance wavelength of the cavity can be tuned to achieve modulation in the transmission of the waveguide. The detection scheme also utilizes the same vertically coupled system. By creating crystal defects in silicon in the cavity region, wavelength selective photodetection can be achieved. This unique vertical coupling scheme also allows us to cascade multiple modulators and detectors coupled to a single waveguide, thus offering huge channel scalability and design and fabrication simplicity. During this project, I have implemented this vertical coupling scheme to demonstrate modulation with extremely low operating energy (0.6 fJ/bit). Furthermore, I have demonstrated cascadeability and multichannel operation by using a comb laser as the source that simultaneously drives five channels. For photodetection, I have realized one of the smallest wavelength selective detector with responsivity of 0.108 A/W at 10 V reverse bias with a dark current of 9.4 nA. By cascading such detectors I have also demonstrated a two-channel demultiplexer.

This thesis asks how voice enables youth to claim agency within divided societies, and what are the implications of this in terms of conflict and peacebuilding? It is an analysis of the significance of young people's voices to international relations. The research is framed in terms of human rights and human security, children's rights, and recognition theories. Its aim is to draw conclusions both about the nature of voice and agency, or power, and about how the framing of the present research in this area impacts the ability of the discourse to take into account the significance of listening to those who are marginalized. From these starting points the thesis will explore questions such as the following: In what ways do children have a voice? If young people had more of a voice, would it make a difference? Does having a voice lead to power? If so, does this create a culture of respect for this voice, and in turn an increase in the speaker's ability to claim agency? Does increasing participation have an impact upon people's likeliness to resort to violence? These aspects are important because they contribute to knowledge and frameworks for peacebuilding in post-conflict areas and the link between voice and violence may provide a key to reducing youth violence in post-conflict areas, but most significantly, hearing young voice could contribute to a sustainable peace, envisioned by and cultivated by the very generation that must own that peace if it is to become lasting.