Dans cette thèse, nous étudions un système à temps discret de dimension N, dont les paramètres varient périodiquement. Le système de dimension N est construit à partir de n sous-systèmes de dimension un couplés symétriquement. Dans un premier temps, nous donnons les propriétés générales du système de dimension N. Dans un second temps, nous étudions le cas particulier où le sous-système de dimension un est défini à l’aide d’une transformation logistique. Nous nous intéressons plus particulièrement à la structure des bifurcations lorsque N=1 ou 2. Des zones échangeurs centrées sur des points cuspidaux sont obtenues dans le cas de courbes de bifurcation de type fold (noeud-col).Ensuite, nous nous intéressons au comportement de circuits de type Chua couplés lorsqu’un paramètre varie lui aussi périodiquement, la période étant celle d’une des variables d’état interne au système. A partir de l’étude des bifurcations du système, la non existence de cycles d’ordre impair et la coexistence de plusieurs attracteurs est mise en évidence. D’autre part, on peut mettre en évidence la coexistence de différents attracteurs pour lesquels les états de synchronisation sont distincts. Le cas continu est comparé avec le cas discret. Des phénomènes tout à fait similaires sont obtenus. Il est important de noter que l’étude d’un système à temps discret est plus facile et plus rapide que celle d’un système à temps continu. L’étude du premier système permet donc d’avoir des informations sur ce qui peut se produire dans le cas continu. Pour terminer, nous analysons le comportement d’un autre système couplé à temps continu, basé lui aussi sur le circuit de Chua, mais pour lequel la commutation qui contrôle la variation du paramètre s’effectue différemment du premier système. Ce type de commutation génère une augmentation du nombre d’attracteurs / In this thesis, we propose a N-dimensional coupled discrete-time system whose parameters are forced into periodic varying, the N-dimensional system being constructed of n same one-dimensional subsystems with mutually influencing coupling and also coupled continuous-time system including periodically parameter varying which correspond to the periodic varying in the discrete-time system.Firstly, we introduce the N-dimensional coupled parametrically forced discrete-time system and its general properties. Then, when logistic maps is used as the one-dimensional subsystem constructing the system, bifurcations in the one or two-dimensional parametrically forced logistic map are investigated. Crossroad area centered at fold cusp points regarding several order cycles are confirmed.Next, we investigated behaviors of the coupled Chua's circuit whose parameter is forced into periodic varying associated with the period of an internal state value. From the investigation of bifurcations in the system, non-existence of odd order cycles and coexistence of different attractors are observed. From the investigation of synchronizations coexisting of many attractors whose synchronizations states are different are observed. Observed phenomena in the system is compared with the parametrically forced discrete-time system. Similar phenomena are confirmed between the parametrically forced discrete-time system and the parametrically forced Chua's circuit. It is worth noting that this facilitates to analyze parametrically forced continuous-time systems, because to analyze discrete-time systems is easier than continuous-time systems. Finally, we investigated behaviors of another coupled continuous-time system in which Chua's circuit is used, while, the motion of the switch controlling the parametric varying is different from the above system. Coexisting of many attractors whose synchronizations states are different are observed. Comparing with theabove system, the number of coexisting stable state is increased by the effect of the different switching motion

Dans de nombreux domaines industriels et scientifiques, en particulier dans les domaines du génie civil et de génie mécanique, des matériaux à l’échelle de la microstructure, un très hétérogène par rapport à la nature du comportement mécanique. Cette fonctionnalité peut faire la prédiction du comportement de la structure soumise à différents types de chargement, nécessaires pour la conception durable, assez difficile. Le contrôle du comportement des ouvrages de génie civil est très complexe en raison de la diversité de la charge à laquelle ils sont soumis. La construction est maintenant réglementée partout dans le monde: les normes sont plus strictes et pris en compte, jusqu’à un état limite, en raison de différentes charges, par exemple des charges sévères tels que l’impact ou tremblement de terre. Modèles de comportement des matériaux et des structures doivent inclure l’élaboration de ces critères de conception et deviennent plus complexe. Ces modèles sont souvent basées sur des approches phénoménologiques, sont capables de reproduire la réponse du matériau au niveau ultime. Réponses de contrainte-déformation des matériaux sous sollicitations cycliques, dont de nombreuses recherches ont été exécutées dans les années précédentes afin de caractériser et le modèle, sont définies par différents types de propriétés de plasticité cycliques tels que l’écrouissageue, l’effet rochet et de de relaxation. En utilisant les modèles de comportement existants, ces réponses mentionnées peuvent être simulés d’une manière raisonnable. Cependant, il peut y avoir échec dans certains simulation des réponses structurelles et la déformation locale et globale. Insuffisance de ces études peut être résolu par le développement de solides modèles de comportement à l’aide d’expériences et de la connaissance des principes de fonctionnement des différents mécanismes de comportement inélastique ensemble. Dans ce travail, nous présentons un modèle phénoménologique constitutive qui est capable de coupler deux principaux mécanismes de comportement inélastique, plasticité et endommagement. Le modèle vise les applications de chargement cycliques. Ainsi, dans une partie de plasticité ou de dommages, les effets de durcissement isotropes et linéaires cinématiques à la fois sont pris en compte. Le principal avantage de ce modèle est l’utilisation de la plasticité indépendante contre les critères de l’endommagement pour décrire les mécanismes inélastiques. Un autre avantage concerne la mise en oeuvre numérique d’un tel modèle fourni en hybride-stress variationnel, obtenu avec une précision très améliorée et calcul efficace du stress et des variables internes dans chaque élément. Plusieurs exemples sont présentés afin de confirmer l’exactitude et l’efficacité de la formulation proposée en application à un chargement cyclique. / In many industrial and scientific domains, especially in civil engineering and mechanical engineering fields, materials that can be used on the microstructure scale, are highly heterogeneous by comparison to the nature of mechanical behavior. This feature can make the prediction of the behavior of the structure subjected to various loading types, necessary for sustainable design, difficult enough. The construction of civil engineering structures is regulated all over the world: the standards are more stringent and taken into account, up to a limit state, due to different loadings, for example severe loadings such as impact or earthquake. Behavior models of materials and structures must include the development of these design criteria and thereby become more complex, highly nonlinear. These models are often based on phenomenological approaches, are capable of reproducing the material response to the ultimate level. Stress-strain responses of materials under cyclic loading, for which many researches have been executed in the previous years in order to characterize and model, are defined by different kind of cyclic plasticity properties such as cyclic hardening, ratcheting and relaxation. By using the existing constitutive models, these mentioned responses can be simulated in a reasonable way. However, there may be failure in some simulation for the structural responses and local and global deformation. Inadequacy of these studies can be solved by developing strong constitutive models with the help of the experiments and the knowledge of the principles of working of different inelastic behavior mechanisms together. This dissertation develops a phenomenological constitutive model which is capable of coupling two basic inelastic behavior mechanisms, plasticity and damage by studying the cyclic inelastic features. In either plasticity or damage part, both isotropic and linear kinematic hardening effects are taken into account. The main advantage of the model is the use of independent plasticity versus damage criteria for describing the inelastic mechanisms. Another advantage concerns the numerical implementation of such model provided in hybrid-stress variational framework, resulting with much enhanced accuracy and efficient computation of stress and internal variables in each element. The model is assessed by simulating hysteresis loop shape, cyclic hardening, cyclic relaxation, and finally a series of ratcheting responses under uniaxial loading responses. Overall, this dissertation demonstrates a methodical and systematic development of a constitutive model for simulating a broad set of cycle responses. Several illustrative examples are presented in order to confirm the accuracy and efficiency of the proposed formulation in application to cyclic loading.

L’objectif de cette thèse était la modélisation numérique de la torche à plasma à couplage inductive. (ICP). Nous avons établi les bases de données nécessaires : composition, propriétés thermodynamiques et de transport appliqués aux mélanges d’argon, d’acide nitrique et d’eau. Le modèle hydrodynamique de la torche ICP (7 spires) considère le plasma à l'équilibre thermodynamique et couple les équations de Navier-Stokes pour décrire l'écoulement du plasma aux équations de Maxwell pour décrire l'évolution du champ électrique et du champ magnétique. / The purpose of the work was the numerical modeling of the inductive coupling plasma torch. (ICP). We have established the necessary databases: composition, thermodynamic and transport properties applied to argon mixtures of nitric acid and water. The hydrodynamic model of the ICP torch (7 coils) considers the plasma at thermodynamic equilibrium and uses the Navier-Stokes equations to describe the plasma flow and the Maxwell equations to describe the evolution of the electric field and the magnetic field.

Ligand-gated and ligand-modulated ion channel (IC) sensors have received increased attention for their ability to transduce ligand-binding events into a readily measurable electrical signal. Ligand-binding to an IC modulates the ion flux properties of the channel in label-free manner, often with single-molecule sensitivity and selectivity. As a result, ICs are attractive sensing elements in biosensoring platforms, especially for ligands lacking optical (e.g. fluorescent) or electrochemical properties. Despite the growing number of available ligand-gated and ligand-modulated ICs and artificial lipid bilayer platforms for IC reconstitution, significant work remains in defining the analytical performance capabilities of IC sensors. Particularly, few studies have described platforms for making measurements with rapid temporal resolution and high sensitivity. In this work, we describe an artificial lipid bilayer platform which enables rapid measurement of ion channel activity, a key parameter for developing IC sensors suitable for studying biological events, e.g. single cell exocytosis (Chapter 2 and 3). Additionally, we developed expression, purification, and reconstitution protocols for Kir6.2, a model ligand-gated ion channel, for use in sensor development (Chapter 4). The final goal is to reconstitute ion channel-coupled receptors (ICCRs), G protein-coupled receptor-Kir6.2 fusion proteins, into artificial lipid bilayers to detect small molecules and hormones targeting GPCRs. Towards this goal, we characterized the expression and function of two ICCRs, M2-Kir and D2-Kir, in HEK293 cells (Chapter 5).

Master of Science / Department of Architectural Engineering / Fred Hasler / Ground-coupled heat pump (GCHP) systems use the ground as a heat source or sink that absorbs heat from or rejects heat to the soil, respectively; this is referred to as the geothermal heat exchanger. Apart from the geothermal heat exchanger, there are two other main system components that make up a GCHP system: heat pumps and circulation pumps. This report studies four GCHP pumping systems and makes comparisons between the four using life-cycle cost analyses for six building models. The goal for this analysis was to discover commonalities between the models in order to provide designers insight into which pumping system is the most cost effective. The analysis was performed by first creating energy models to obtain system and zone load information, as well as system part-load data and geothermal heat exchanger performance. From the zone load information, heat pump selections were then performed to indicate the worst case piping path that is required for pump head calculations. Piping layouts were created to establish pipe lengths for the pump head calculations as well. Other piping components such as valves and fittings and the air separator pressure drops were also calculated. Once the pump head calculations were complete for each system, pump schedules were created. From there initial unit and installation costs were determined for each pump, as well as their replacement costs. The part-load data from the energy models were then used to obtain annual pump energy consumption and pump utility cost. Finally, assumptions were made to establish regular and preventative maintenance requirements for each pumping system. Initial and replacement unit costs, annual utility cost and regular and preventative maintenance costs were the components used in the life-cycle cost analysis. Each of these components was converted to 30-year projected costs and added to create a total life-cycle cost for each pumping system. Comparisons were then made and the results showed that a primary pumping system with VFD control and 100% redundancy was the most cost effective system. However, there are other considerations such as controllability, flexibility and availability that might persuade designers to choose one of the other alternate solutions.

M.Sc. / The origin of a wine plays a key role in establishing the quality and the price the consumer is prepared to pay. Fingerprinting techniques based on multi-element data combined with multivariate statistical analysis as well as isotope ratio data for certain elements such as boron (11B/10B) and strontium (87Sr/86Sr) are being developed and have been used for provenance determination of wine with varying degrees of success. The aim of this study was to develop a method to determine boron isotope ratios (11B/10B) with the required precision using ICP-MS (inductively coupled plasma mass spectrometry) in soil and wine samples and applying this method to establish the origin of South African wines. Analytical difficulties such as the boron memory effect, dead time, mass bias drift and matrix effects were investigated. Although the memory effect, dead time and mass bias drift were satisfactorily resolved, it was not possible to determine what the cause of all the observed matrix effects was during this study. The method was used to categorise wines from the Robertson, Swartland and Stellenbosch regions and an attempt was made to link the measured boron isotope ratios with that obtained from the corresponding provenance soils. The 11B/10B isotope ratios for the wine samples (Robertson: 4.202 ± 0.014, Swartland: 4.173 ± 0.013 and Stellenbosch: 4.174 ± 0.028) were, however, higher than the ratios obtained for the soil samples (Robertson: 4.108 ± 0.020, Swartland: 4.070 ± 0.023 and Stellenbosch: 4.124 ± 0.039). It was possible to distinguish, using the boron isotope ratios (wine and soil samples), between the Robertson area (Breede River region) and the Swartland area (Coastal region). The wine and soil 11B/10B isotope ratios obtained for the Stellenbosch area (Coastal region) overlapped with the 11B/10B isotope ratios of the Robertson and Swartland regions making it impossible to differentiate it from these two regions.

A study of magnetization dynamics experiments in nanostructured materials using the rf susceptibility tunnel diode oscillator (TDO) method is presented along with a extensive theoretical analysis. An original, computer controlled experimental setup that measures the change in susceptibility with the variation in external magnetic field and sample temperature was constructed. The TDO-based experiment design and construction is explained in detail, showing all the elements of originality. This experimental technique has proven reliable for characterizing samples with uncoupled magnetic structure and various magnetic anisotropies like: CrO2 , FeCo/IrMn and Co/SiO2 thin films. The TDO was subsequently used to explore the magnetization switching in coupled magnetic systems, like synthetic antiferromagnet (SAF) structures. Magnetoresistive random access memory (MRAM) is an important example of devices where the use of SAF structure is essential. To support the understanding of the SAF magnetic behavior, its configuration and application are reviewed and more details are provided in an appendix. Current problems in increasing the scalability and decreasing the error rate of MRAM devices are closely connected to the switching properties of the SAF structures. Several theoretical studies that were devoted to the understanding of the concepts of SAF critical curve are reviewed. As one can notice, there was no experimental determination of SAF critical curve, due to the difficulties in characterizing a magnetic coupled structure. Depending of the coupling strength between the two ferromagnetic layers, on the SAF critical curve one distinguishes several new features, inexistent in the case of uncoupled systems. Knowing the configuration of the SAF critical curve is of great importance in order to control its switching characteristics. For the first time a method of experimentally recording the critical curve for SAF is proposed in this work. In order to overcome technological limitations, a new way of recording the critical curve by using an additional magnetic bias field was explored.

Magister Scientiae (Medical Bioscience) - MSc(MBS) / Mercury (Hg) is an example of a toxic metal that is not essential for nutrition. It exists in organic and inorganic forms in seafood and vapour from dental amalgam fillings respectively. Elemental mercury (Hg0) from dental amalgam was the focus of this study. Dental amalgam is one of the most commonly used dental filling materials and has been used for over 150 years. It is composed of Hg0 (approximately 50%) combined with other metals such as copper and zinc (Zn). These fillings give off Hg0 vapour throughout their existence, and is further enhanced by activities such as chewing, grinding of teeth and drinking hot liquids. Mercury consumption can lead to Zn loss or deficiency, and is reported to displace Zn and copper. Several European nations have outlawed the use of amalgam as a restorative material due to controversies regarding its safety in children, women of childbearing age and individuals with renal disease. Moreover, various studies have reported correlations between the number of amalgam fillings and Hg concentration in blood plasma, urine, faeces, saliva and different organs. Blood, urine, and hair mercury levels are used to predict possible health effects that may be caused by the different forms of Hg. Urine Hg is used to test exposure to metallic Hg0 vapour and inorganic Hg forms. This study aimed to evaluate the effects of Hg0 from dental amalgam restorations on the status of Zn in the urine. This was done by determining the concentrations of Hg0 in urine, buccal cells and the oral cavity, and its relationship with urinary Zn concentrations in the same individuals. Samples of urine, buccal tissues, chewing gum and completed questionnaires were collected from the participants (women and men) at the dental clinics in Tygerberg Hospital (TBH), Cape Town. Samples were analyzed using inductively coupled plasma mass spectrometer (ICP-MS). Findings from this study show that there was a correlation between levels of urinary Hg0 and urinary Zn (p=0.02). However, urinary Hg0 did not predict the amount of urinary Zn. Also, no relationship was found between levels of Hg0 in buccal swab or the chew test samples and urinary Zn level. There was a significant difference between females and males in the level of urinary Zn, men had higher levels of Zn excreted in the urine than females (p=0.05). However, there was no significant difference in the level of urinary Hg0 between males and females. The number of fillings (4-7) and age of fillings were significantly associated with urinary Hg0 level (p˂0.05), while smoking ˃15 cigarettes/day increased the level of Hg0 in buccal swab samples (p=0.002). We were not able to demonstrate a causal effect of Hg0 leaching on urinary zinc levels.

Indigo N,N’-diarylimine (Nindigo) and indigo N-arylimine (Mindigo) are redox-active ligands which exhibit near-infrared absorption and can accommodate up to five ligand charge states. This dissertation explores the coordination chemistry of these ligands to further understand the role that metal-ligand combinations play on ligand-centered properties, which include electrochemical potentials, UV-Vis-NIR absorption, pKa values, hydricities, and NH bond strengths at different ligand charge states. A series of cis-Nindigo palladium complexes containing acetylacetonate (acac) and hexafluoroacetylacetonate (hfac) ligands were synthesized. The acac complexes were easier to oxidize by 0.11 to 0.16 V and absorbed at lower wavelengths compared to their hfac analogues. Complexes using indigo bis(4-methylphenylimine) were more easily reduced than complexes of indigo bis(2,6-dimethylphenylimine). Cis- and trans-Mindigo complexes of palladium acac and hfac were synthesized as the first coordination complexes of Mindigo. Trans-Mindigo complexes were more difficult to reduce by 0.33 to 0.37 V and absorbed at lower wavelengths than their cis-Mindigo counterparts. Cis-Mindigo complexes were easier to reduce and harder to oxidize than the corresponding cis-Nindigo complexes. The NH bond strengths of cis-Nindigo complexes containing Pd(acac) and Ru(bipy)2 (bipy = 2,2’-bipyridyl) fragments were determined through a potential-pKa diagram in tetrahydrofuran and acetonitrile, respectively. The NH bond strength and hydricity values of the Pd(acac) complex were comparable to the values of diaryl amines. The NH bond strength and hydricity of the Ru(bipy)2 complex were substantially smaller due to the lower oxidation potentials of this complex. In both cases, the ligand’s NH bond strengths were not affected greatly by the ligand’s charge state. Ru(acac)2 complexes of neutral, aprotic cis-Nindigo and cis-Mindigo ligands were synthesized. The Nindigo/Mindigo ligand could be protonated, and the resulting complexes demonstrated substantial temperature dependence of some of their 1H NMR chemical shifts. The NH bond strengths and hydricities of the Ru(acac)2 complexes were determined using cyclic voltammetry and pKa measurements. The NH bond strengths and hydricities of these complexes are substantially smaller than the Pd(acac) and Ru(bipy)2 complexes. Collectively, these results show that Nindigo and Mindigo can act as both a proton and electron reservoirs, and the thermodynamics of proton and electron transfer can be tuned through the choice of metal and ligand combinations. / Graduate / 2020-07-17

Thesis advisor: Marc A.T. Muskavitch / Malaria is a life-threatening infectious disease caused by inoculation of the apicomplexan Plasmodium parasite into vertebrate hosts. Transmission of the parasite is mediated by the Anopheles mosquito, which has the capacity to efficiently transmit the parasite from host to host, as the disease vector. There are many factors that make anopheline mosquitoes competent vectors for disease transmission. The hematophagous (blood-feeding) behavior of the female mosquito is one of most fundamental factors in physical transmission of parasites, because the ingestion of blood from an infected host allows parasite entry into the mosquito and the completion of parasite sexual reproduction. In addition to this blood-feeding behavior, there are a host of biological (i.e., parasite replication) and behavioral factors (i.e., mosquito chemosensation, host preference) that contribute to the high vectorial capacity of these vector species. There are over four hundred Anopheles species worldwide, approximately forty of which are considered epidemiologically critical human malaria vectors. Anopheles gambiae, the primary vector in malaria-endemic sub-Saharan Africa, is responsible for the largest number of malaria cases in the world and is therefore one of the most important vectors to study and target with control measures. Currently, vector-targeted control strategies remain our most effective tools for reduction of malaria transmission and incidence. Although control efforts based on the deployment of insecticides have proven successful in the past and are still widely used, the threat and continuing increases of insecticide resistance motivate the discovery of novel insecticides. In this thesis, I provide evidence that G protein-coupled receptors (GPCRs) may serve as “druggable” targets for the development of new insecticides, through the modulation of developmental and sensory processes. In Chapter II, “A critical role for the Drosophila dopamine 1-like receptor Dop1R2 at the onset of metamorphosis,” I provide evidence supporting an essential role for this receptor in Drosophila melanogaster metamorphosis via transgenic RNA interference and pharmacological methods. In An. gambiae, we find that the receptor encoded by the mosquito ortholog GPRDOP2 can be inhibited in vitro using pharmacological antagonists, and that in vivo inhibition with such antagonists produces pre-adult lethality. These findings support the inference that this An. gambiae dopamine receptor may serve as a novel target for the development of vector-targeted larvicides. In Chapter III, “RNAi trigger delivery into Anopheles gambiae pupae,” I describe the development of a method for injection directly into the hemolymph of double strand RNA (dsRNA) during the pupal stage, and I demonstrate that knockdown of the translational product of the SRPN2 gene occurs efficiently, based on reductions in the levels of SRPN2 protein and formation of melanized pseudo-tumors, in SRPN2 knockdown mosquitoes. This method was developed for rapid knockdown of target genes, using a dye-labeled injection technique that allows for easy visualization of injection quality. This technique is further utilized in Chapter IV, “Uncovering the Role of an Anopheles gambiae G Protein-Coupled Receptor, GPRGR2, in the Detection of Noxious Compounds,” where the role for GPRGR2 in the detection of multiple noxious compounds is elucidated. We find that pupal stage knockdown of this receptor decreases the ability of adult Anopheles gambiae to identify multiple noxious compounds. While these findings provide a strong link between GPRGR2 and a very interesting mosquito behavior, they may also provide opportunities to develop better field-based strategies (i.e., insecticides baited traps) for vector control. The goal of this thesis is to understand the functional roles of selected mosquito GPCRs that may serve as targets for the development of new vector-targeted control strategies. Exploiting these GPCRs genetically and pharmacologically may provide insights into novel vector control targets that can be manipulated so as to decrease the vectorial capacity of An. gambiae and other malaria vectors in the field, and thereby decrease the burden of human malaria. / Thesis (PhD) — Boston College, 2015. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Biology.