L'imagerie par résonance magnétique (IRM) est une modalité qui offre de bons contrastes et une bonne résolution spatiale, mais qui souffre d'un important problème de sensibilité. Pour répondre à cette problématique, le paradigme actuel est d'accroitre le champ magnétique des aimants d'IRM. Ceci mène toutefois à une explosion des coûts et à des contraintes accrues vis-à-vis des patients. L'approche que nous présentons est radicalement différente~: il s'agit de travailler à champ faible. Les antennes classiques n'étant pas assez sensibles pour recueillir le signal, l'idée est d'utiliser des SQIF. Ces derniers sont une nouvelle technologie d'antennes supraconductrices ultra-sensibles basées sur les réseaux de SQUID. Le projet vise à optimiser les capteurs SQIF et à les adapter pour la première fois à la RMN afin de mesurer un signal sur un aimant à 0.2~T.Pour ce faire, nous avons développé et étudié les performances de nouvelles architectures d'antennes SQIF afin de définir la géométrie la plus adaptée à la RMN. Nous avons également cherché à mieux comprendre comment le contexte d'utilisation de ces nouvelles antennes pouvait influencer leurs performances. Le jeu d'antennes le plus performant réalisé avait un facteur de transfert de 8.4~kVperT et un seuil de détection de 190~fTperHz. Il fut également observé que la présence d'un champ magnétique pendant le refroidissement de ces capteurs supraconducteurs dégradait leur réponse, phénomène à prendre en compte en RMN.Un Démonstrateur Super-QIF intégrant un SQIF dans l'IRM à 0.2~T fut conçu en tenant compte des contraintes géométriques et de l'environnement magnétique. Après sa fabrication, la température du cryostat était de 50~K, donc suffisante pour le bon fonctionnement des SQIF. Les premiers tests ont montrés que la présence du système ne perturbait pas le signal de RMN.Le démonstrateur est toujours en cours de développement et devrait permettre de mesurer un de RMN dans les mois à venir. À long terme, ces travaux pavent la voie à des applications des SQIF en IRM à champ terrestre. / Magnetic resonance imaging (MRI) is a modality that offers good contrasts and good spatial resolution, but suffers from a significant sensitivity problem. To address this issue, the current paradigm is to increase the magnetic field of MRI magnets. However, this leads to an explosion of costs and to increased constraints on patients. The approach we present is radically different: it involves working in a weak field. As conventional antennas are not sensitive enough to collect the signal, the idea is to use SQIF. These are a new ultra sensitive superconducting antenna technology based on SQUID networks. The project aims to optimize SQIF technology and adapt it to measure an NMR signal in a 0.2~T magnet.To do this, we developed and studied the performance of new SQIF antenna architectures in order to define the geometry most suitable for NMR. We also sought to better understand how the context of use of these new antennas could influence their performance. The best performing antennas set had a transfer factor of 8.4~kVperT and a detection threshold of 190~fTperHz. It was also observed that the presence of a magnetic field during the cooling of these superconducting sensors degraded their response, a phenomenon to be accounted for in NMR.The Super-QIF Demonstrator incorporating a SQIF in the 0.2~T MRI was designed considering the geometric constraints and the magnetic environment. After its assembly, the temperature of the cryostat was 50~K, therefore sufficient for the proper operation of SQIF. The first tests showed that the system presence did not disturb the NMR signal.The demonstrator is still under development and is expected to measure an NMR signal in the forthcoming months. In the long term, this work paves the way for applications of SQIF in Earth's field MRI.

The study investigated the impact of computer simulations on the teaching and learning of electromagnetism in grade 11. Electromagnetism is a section of the Physical Science curriculum. Two grade 11 classes in the Mgwenya circuit in Mpumalanga province of South Africa were used as a case study. Using a pre-test, post-test non-equivalent control group design, it was found that learners in the experimental group (n = 30) who were taught using the simulations achieved significantly higher scores on the post-test than learners in the control group (n = 35) who were taught using traditional teacher-centred teaching method; (t statistic = 3.582, df = 56, p<0.05). Learners were more active during the lessons, predicting, observing, discussing and explaining concepts. The use of simulations also provided support (scaffolding) that the learners need to enhance learning. The Hake’s normalized gain for the experimental group <g> = 0.32 compared to <g> = 0.18 for the control group confirmed conceptual improvement. Both teachers and learners indicated that they accept the use of computer simulations in teaching and learning of electromagnetism. / Science and Technology Education / M. Sc. (Mathematics, Science and Technology Education)

This MSc report discusses the attributes of W Ursae Majoris (W UMa) stars and an investigation into the Minimum Entropy (ME) method, a digital technique applied to the determination of their periods of variability. A Python code programme was written to apply the ME method to photometric data collected on W UMa stars by the All Sky Automated Survey (ASAS). Starting with the orbital period of the binaries estimated by ASAS, this programme systematically searches around this period for the period which corresponds to the lowest value of entropy. Low entropy here means low scatter (or spread) of data across the phase-magnitude plane. The ME method divides the light curve plot area into a number of elements of the investigators choosing. When a particular orbital period is applied to this photometric data, the resulting distribution of this data in the light curve plane corresponds to a speci c number of data points in each element into which this plane has been divided. This data spread is measured and calculated in terms of entropy and the lowest value of entropy corresponds to the lowest spread of data across the light curve plane. This should correspond to the best light curve shape available from the data and therefore the most accurate orbital period available. Subsequent to the testing of this Python code on perfect sine waves, it was applied, and its results compared, to the 62 ASAS eclipsing binary stars which were investigated by Deb and Singh (2011). The method was then applied to selected stars from the ASAS data base. / School of Environmental Sciences / M. Sc. (Astronomy)

Cavity ring-down spectroscopy (CRDS) and cavity enhanced absorption spectroscopy (CEAS) are two well-established absorption spectroscopic techniques originally developed for gas-phase samples. Condensed-phase applications of these techniques still remain rare, complicated as they are by additional background losses induced by condensed-phase samples as well as the intracavity components in which the sample is constrained. This thesis is concerned with the development and application of optical-cavity-based techniques in the condensed phase. Polarization-dependent evanescent wave CRDS (EW-CRDS) has been used to study the molecular orientation at the solid/air and solid/liquid interfaces. An increase in average orientation angle with respect to the surface normal has been observed for both methylene blue and coumarin molecules as a function of coverage at the fused silica/air interface. An orientation-angle-dependent photobleaching of pyridin molecules at the fused silica/methanol interface have also been observed. EW-CRDS has also been used to monitor slow in situ photobleaching of thin dye films deposited on the prism surface. The photobleaching dynamics is interpreted as a combination of first- and second-order processes. A significant fraction of this thesis has been devoted to studying magnetic field effects (MFEs) on the kinetics of the radical pair (RP) reactions in solution, in an effort to understand the ability of animals to sense the geomagnetic field. Two novel optical-cavity-based techniques – broadband CEAS (BBCEAS) and CRDS have been developed for this purpose. BBCEAS uses a supercontinuum (SC) source as the cavity light source and a CCD camera as photodetector, enabling simultaneous acquisition of absorption spectrum across the whole visible region (400 – 800 nm). In CRDS, a tunable optical parametric oscillator has been used as the cavity light source. Combined with the switching of external magnetic field (SEMF) method, this technique allows the decay kinetics of the geminate RPs to be monitored, with nanosecond resolution. Both BBCEAS and CRDS provide sensitivity superior to single-pass transient absorption (TA), a technique traditionally used in the MFE studies. A series of photochemical systems have been studied by BBCEAS and CRDS, respectively, among which, the MFEs of drosophila melanogaster cryptochrome has been observed. Importantly, this is the first time an MFE has been observed in an animal cryptochrome, and provides key supporting evidence for the cryptochrome hypothesis of magnetoreception in animals. Besides the optical-cavity-based techniques, a novel fluorescence detection method of MFEs has also been demonstrated. This technique proved ultrahigh sensitivity when applicable.

We study correlated two-level quantum impurity models coupled to a metallic conduction band in the hope of gaining insight into the physics of nanoscale quantum dot systems. We focus on the possibility of formation of a spin-1 impurity local moment which, on coupling to the band, generates an underscreened (USC) singular Fermi liquid state. By employing physical arguments and the numerical renormalization group (NRG) technique, we analyse such systems in detail examining in particular both the thermodynamic and dynamic properties, including the differential conductance. The quantum phase transitions occurring between the USC phase and a more ordinary Fermi liquid (FL) phase are analysed in detail. They are generically found to be of Kosterlitz-Thouless type; exceptions occur along lines of high symmetry where first-order transitions are found. A `Friedel-Luttinger sum rule' is derived and, together with a generalization of Luttinger's theorem to the USC phase, is used to obtain general results for the $T=0$ zero-bias conductance --- it is expressed solely in terms of the number of electrons present on the impurity and applicable in both the USC and FL phases. Relatedly, dynamical signatures of the quantum phase transition show two broad classes of behaviour corresponding to the collapse of either a resonance or antiresonance in the single-particle density of states. Evidence of both of these behaviours is seen in experimental devices. We study also the effect of a local magnetic field on both single- and two-level quantum impurities. In the former case we attempt to resolve some points of contention that remain in the literature. Specifically we show that the position of the maximum in the spin resolved density of states (and related peaks in the differential conductance) is not linear in the applied field, showing a more complicated form than a simple `Zeeman splitting'. The analytic result for the low-field asymptote is recovered. For two-level impurities we illustrate the manner in which the USC state is destroyed: due to two cancelling effects an abrupt change in the zero-bias conductance does not occur as one might expect. Comparison with experiment is made in both cases and used to interpret experimental findings in a manner contrary to previous suggestions. We find that experiments are very rarely in the limit of strong impurity-host coupling. Further, features in the differential conductance as a function of bias voltage should not be simply interpreted in terms of isolated quantum dot states. The many-body nature of such systems is crucially important to their observed properties.

Un modèle numérique d’un arc électrique diffus dans un disjoncteur à vide à champ magnétique axial (AMF) a été développé dans le but de mieux comprendre à terme la transition d’un mode de fonctionnement diffus de l’arc vers un mode plus concentré. Le comportement du plasma d’arc a été simulé depuis la sortie de la zone de mélange cathodique jusqu’à l’entrée de la gaine anodique. Le modèle bidimensionnel est basé sur un système d’équations hydrodynamiques à deux fluides non magnétisés (ions et électrons), incluant les équations de conservation d’énergie ionique et électronique. Il est démontré que les processus d’ionisation et de recombinaison et les effets visqueux sont négligeables. Les transferts radiatifs ne sont pas considérés en première approximation. Outre les forces dues au champ AMF, le modèle inclut les forces dues aux trois composantes du champ magnétique induit par l’arc. Deux régimes d’écoulement des ions, supersonique (aux faibles densités de courant) et subsonique (aux fortes densités de courant), sont considérés. Près de la cathode, les conditions aux limites sont spécifiées à partir de résultats de la littérature. A proximité de l’anode, elles sont basées sur une description simplifiée de la gaine anodique. Les résultats de simulation présentés mettent en évidence une constriction du courant et un comportement différent des ions aux faibles et aux fortes densités de courant, et renseignent sur l’influence de divers paramètres (intensité du courant, distance interélectrode). Ce travail présente également une étude expérimentale, basée sur des visualisations par vidéo rapide de l’arc et des mesures pyrométriques de la température de la surface de l’anode / A model of a diffuse arc in a vacuum circuit breaker with an axial magnetic field (AMF) has been developed with the ultimate aim to better understand the transition of the arc from a diffuse mode to a more confined mode. The interelectrode plasma is simulated from the exit of the mixing region on the cathode side to the entrance of the anode sheath. The two-dimensional model is based on the solution of a system of two-fluid (ions and electrons) hydrodynamic equations, including in particular the energy balance equations relative to both the ions and the electrons, which are treated as non-magnetized particles. It is demonstrated that ionisation and recombination processes, as well as viscous effects, can be neglected. Radiation losses are not taken into account in a first approximation. In addition to the forces due to the AMF, the model considers the forces created by the three components of the magnetic field induced by the arc current. The possibility of both supersonic (at low current density) and subsonic (at high current density) ionic flow regimes is considered. On the cathode side, the boundary conditions are specified using results from the literature. On the anode side, they are based on a simplified description of the anode sheath. The simulation results presented show a constriction of the current lines, emphasize the differences in the behaviour of the ions at low and high current densities, and provide some insight on the influence of various operating parameters (arc current, gap length). The present work comprises also an experimental study, based on high-speed camera visualisations of the arc and measurements of the temperature at the anode surface

This thesis describes the development and application of condensed-phase cavity-based spectroscopic techniques - namely cavity ring-down spectroscopy (CRDS); cavity enhanced absorption spectroscopy (CEAS); broadband cavity enhanced absorption spectroscopy (BBCEAS) and evanescent wave (EW) variants of all three. The recently-developed cavity technique of EW-broadband cavity enhanced absorption spectroscopy (EW-BBCEAS) has been used—in combination with a supercontinuum source (SC) and a sensitive, fast readout CCD detector—to record of the full visible spectrum (400–700 nm) of a silica-liquid interfacial layer (with an effective thickness ca. 1 µm), at rapid acquisition rates (> 600 Hz) that are sufficient to follow fast kinetics in the condensed phase, in real time. The sensitivity achieved (A_min= 3.9 x 10^-5) is comparable with previous EW-CRDS and EW-CEAS studies, but the spectral region accessed in this broadband variant is much larger. The study of liquid|air interfaces using EW cavity-based techniques is also illustrated for the first time. The first application of BBCEAS to the analysis of microfluidic samples, flowing through a microfluidic chip, is illustrated. Proof-of-principle experiments are presented, demonstrating the technique’s ability to provide full visible broadband spectral measurements of flowing microfluidic droplets, with both high detection sensitivity (α_min < 10^-2 cm^-1) and excellent spatial and temporal resolution: an SC light source and sensitive, fast readout CCD allowed measurement repetition rates of 273 Hz, whilst probing a very small sample volume (ca. 90 nL). A significant portion of this thesis is devoted to demonstrating the powerful capabilities of CEAS, CRDS and BBCEAS in monitoring radical recombination reactions and associated magnetic field effects (MFEs) in solution. The efficacy of CEAS as a high-sensitivity MFE detection method has been established in a proof-of-principle study, using narrow band CEAS in combination with phase-sensitive detection: MFE-induced absorbance changes of ca. 10^-6 could be detected using the modulated CEAS technique and the data are shown to be superior to those obtained using conventional transient absorption (TA) methods typically employed for MFE measurements. The powerful capabilities of CRDS in monitoring radical recombination reactions and associated MFEs are also demonstrated. In particular, a pump-probe CRDS variant allows not only high sensitivity (A_min on the order 10^-6), but also sub-microsecond time-resolution. Combined, these features represent significant advantages over TA. Finally, SC-BBCEAS is used to measure full visible spectra of photoinduced reactions and their MFEs. The applicability of this approach to in vitro MFE studies of Drosophila cryptochrome is demonstrated—the results mark the first in vitro observation of a magnetic field response in an animal cryptochrome, a key result supporting the hypothesis that cryptochromes are involved in the magnetic sense in animals.

De nos jours, il est bien accepté que le cycle magnétique de 11 ans du Soleil est l'oeuvre d'une dynamo interne présente dans la zone convective. Bien qu'avec la puissance de calculs des ordinateurs actuels il soit possible, à l'aide de véritables simulations magnétohydrodynamiques, de résoudre le champ magnétique et la vitessse dans toutes les directions spatiales, il n'en reste pas moins que pour étudier l'évolution temporelle et spatiale de la dynamo solaire à grande échelle, il reste avantageux de travailler avec des modèles plus simples. Ainsi, nous avons utilisé un modèle simplifié de la dynamo solaire, nommé modèle de champ moyen, pour mieux comprendre les mécanismes importants à l'origine et au maintien de la dynamo solaire. L'insertion d'un tenseur-alpha complet dans un modèle dynamo de champ moyen, provenant d'un modèle global-MHD [Ghizaru et al., 2010] de la convection solaire, nous a permis d'approfondir le rôle que peut jouer la force électromotrice dans les cycles magnétiques produits par ce modèle global. De cette façon, nous avons pu reproduire certaines caractéristiques observées dans les cycles magnétiques provenant de la simulation de Ghizaru et al., 2010. Tout d'abord, le champ magnétique produit par le modèle de champ moyen présente deux modes dynamo distincts. Ces modes, de périodes similaires, sont présents et localisés sensiblement aux mêmes rayons et latitudes que ceux produits par le modèle global. Le fait que l'on puisse reproduire ces deux modes dynamo est dû à la complexité spatiale du tenseur-alpha. Par contre, le rapport entre les périodes des deux modes présents dans le modèle de champ moyen diffère significativement de celui trouvé dans le modèle global. Par ailleurs, on perd l'accumulation d'un fort champ magnétique sous la zone convective dans un modèle où la rotation différentielle n'est plus présente. Ceci suggère que la présence de rotation différentielle joue un rôle non négligeable dans l'accumulation du champ magnétique à cet endroit. Par ailleurs, le champ magnétique produit dans un modèle de champ moyen incluant un tenseur-alpha sans pompage turbulent global est très différent de celui produit par le tenseur original. Le pompage turbulent joue donc un rôle fondamental au sein de la distribution spatiale du champ magnétique. Il est important de souligner que les modèles dépourvus d'une rotation différentielle, utilisant le tenseur-alpha original ou n'utilisant pas de pompage turbulent, parviennent tous deux à produire une dynamo oscillatoire. Produire une telle dynamo à l'aide d'un modèle de ce type n'est pas évident, a priori. Finalement, l'intensité ainsi que le type de profil de circulation méridienne utilisés sont des facteurs affectant significativement la distribution spatiale de la dynamo produite. / It is generally agreed upon that the 11-year magnetic cycle of the Sun arises through the action of an internal dynamo operating in the convective zone, and perhaps also immediately beneath it. Although the computing power of current supercomputers is sufficient to allow fairly realistic magnetohydrodynamical simulations of this dynamo process, to study the temporal and spatial evolution of the large-scale solar magnetic field over long timescales, it remains advantageous to work with simpler models. Thus, to better understand the physical mechanisms at the origin and maintenance of the solar dynamo, we used a simplified formulation, known as a mean-field model. By using a complete alpha-tensor extracted from a global MHD model of solar convection [Ghizaru et al., 2010] as input to a kinematic axisymmetric mean-field dynamo model [Charbonneau & MacGregor, 1997], it becomes possible to study the effect of the electromotive force on the magnetic cycles produced by the global model. In this way, we are able to reproduce some of the observed characteristics of the Ghizaru et al., 2010 simulation, in particular magnetic cycles. The axisymmetric magnetic field produced by the mean-field dynamo model exhibits two distincts dynamo modes. These modes, with similar periods, are present and peak at substantially at the same radii and latitudes as the sonlly-averaged magnetic fields extracted from the global model. Thanks to the spatial complexity of the alpha-tensor, we can reproduce these two dynamo modes. In contrast, the ratio of the periods of the two modes present in the mean field model differs significantly from that found in the global model. In addition, the accumulation of strong magnetic fields at the base of the convective zone disappears in a model where differential rotation has been removed. This suggests that differential rotation plays a significant role in the accumulation of magnetic fields in this region. Furthermore, removing the turbulent pumping component of the alpha-tensor produces a very different magnetic field cycle. Therefore, turbulent pumping plays a crucial role in the spatial distribution of the magnetic field. It is important to underline that the models without differential rotation, with or without turbulent pumping, both succeed in producing an oscillatory dynamo using only the turbulent electromotive force. However, the dynamos materializing in these modified models are significantly different from that using the full alpha-tensor. Finally, both the intensity and form of meridional circulation profiles are significant factors affecting the dynamo modes.

Les stérosomes, des vésicules artificielles composées d’amphiphiles monoalkylés et d’un grand pourcentage de stérols, sont prometteurs dans plusieurs domaines comme les industries pharmaceutiques et alimentaires. Il existe des stérosomes chargés négativement, positivement et neutres. Dans ce mémoire, nous avons approfondi nos connaissances sur les propriétés physico-chimiques des stérosomes chargés : acide palmitique (PA)/stérol et stéarylamine (SA)/cholestérol (Chol). Premièrement, afin de mesurer la diffusion latérale de PA dans les membranes PA/stérol (30/70 mol/mol) par RMN à gradients pulsés, nous avons tenté de former des bicouches liquide-ordonnées (lo) orientées magnétiquement avec ce mélange. En s'inspirant de l’idée que l’ajout de 1,2-dihexanoyl-sn-glycéro-3-phosphocholine (DHPC), un lipide à courtes chaînes, dans le système 1,2-dimyristoyl-sn-glycéro-3-phosphocholine (DMPC) mène à la formation de bicouches orientées, nous avons étudié la formulation PA perdeutéré/acide hexanoïque (HA)/Chol avec une proportion molaire de 25/18/57 à plusieurs températures; aucune formation de bicouches orientées n’a été observée. Ce résultat pourrait être expliqué par la solubilisation partielle de HA en milieu aqueux. Alors, une quantité insuffisante serait insérée dans la bicouche pour induire son orientation. La formulation PA perdeutéré/DHPC/Chol n’a pas conduit, elle non plus, à des bicouches orientées magnétiquement à des températures et concentrations lipidiques variées. En étudiant le mélange DMPC/DHPC/Chol (67/17/14), nous avons remarqué que la présence de Chol inhibait l'orientation magnétique des bicouches. Tandis que le mélange DMPC/DHPC/stigmastérol (SS) avec les proportions molaires 67/19/14 et 72/21/7 conduisait à des bicouches orientées avec leur normale (n) perpendiculaire au champ magnétique à 40 °C et 50 °C. Ces résultats suggèrent que le mélange PA/SS avec une proportion de lipide à courtes chaînes, HA et DHPC, pourrait mener à des bicouches orientées magnétiquement. Le mélange PA/Chol avec un lipide à courtes chaînes pourrait aussi être étudié en présence des lanthanides. Deuxièmement, nous avons examiné la possibilité de moduler la libération de matériel encapsulé dans des liposomes essentiellement composés de PA et d’un stérol. Il est connu que le mélange PA/Chol (30/70) à pH ≥ 7,5 forme des liposomes très peu perméables. Il est avantageux de pouvoir moduler la perméabilité pour avoir un contrôle sur le temps de libération de leur contenu, qui est un paramètre de grande importance pour les formulations liposomales de médicaments. D’abord, il a été montré que l’acide oléique (OA)/Chol (30/70) est capable de former des vésicules, ce qui n’avait jamais été prouvé auparavant. Par contre, les bicouches OA/Chol (30/70) ne sont pas plus perméables que les bicouches PA/Chol (30/70). L’ajout de 1-palmitoyl-2-oléoyl-sn-glycéro-3-phosphatidylcholine (POPC) dans le mélange PA/Chol n’augmente pas plus la perméabilité. En effet, les cinétiques de relargage de calcéine des vésicules PA/POPC/Chol (15/27.5/57.5), POPC/Chol (40/60) et POPC étaient très semblables à celle de PA/Chol (30/70). Il a été remarqué que les études littéraires se contredisent à propos de la perméabilité à la calcéine des bicouches de phosphatidylcholine (PC). L’explication de ces divergences est inconnue pour le moment. En remplaçant la moitié de la proportion molaire de Chol par le cholate de sodium (SC) dans le mélange PA/Chol (30/70), la membrane n’était pas plus apte à libérer son contenu. Il se pourrait que le SC se retrouvant dans la bicouche n’induit pas une diminution d’empilement. Il est aussi possible que le SC ne s'insère pas dans la membrane à cause de son hydrophilie considérable et il pourrait alors former seul des micelles. En remplaçant complètement le Chol par le sulfate de cholestérol (SChol), un stérol chargé négativement, et en préparant les vésicules à un bas pH, la formulation PA/SChol (30/70) mène à une très grande perméabilité à pH 7.5; le relargage est provoqué par un saut de pH. Nos travaux suggèrent qu'il serait possible de moduler la perméabilité des liposomes en les préparant avec le mélange PA/SChol/Chol en variant les proportions entre 30/63/7 à 30/70/0. Le diagramme pH-composition du mélange PA/SChol/Chol indique que ces proportions conduisent, à pH 7.4, à la coexistence de phases solide et lo en différentes proportions, ce qui pourrait moduler la perméabilité membranaire. Troisièmement, les résultats de perméabilité obtenus avec la calcéine et les difficultés survenues lors de l’extrusion des vésicules encapsulant cette sonde nous ont amené à nous demander si la calcéine interagit avec les bicouches chargées. L’impact de certains anions, dont la calcéine, a été examiné sur les bicouches chargées positivement SA/Chol (50/50). La calorimétrie différentielle à balayage (DSC, de l’anglais differential scanning calorimetry), indique qu’il n’y a aucune transition entre 25 et 90 °C pour les liposomes SA/Chol (50/50) à pH = 7.4. L’ajout de chlorure de sodim (375 mM) n’a pas mené à la formation d’agrégats et aucune transition n’a été observée sur le thermogramme. La formation d’agrégats macroscopiques instantanément après l’ajout d’hydrogénophosphate de sodium (125 mM), de sulfate de sodium (125 mM) et de calcéine (3 mM) a été observée. Une transition a été observée sur les thermogrammes en présence de ces sels. Les agrégats observés pourraient être associés à la transition de phase. L’effet des anions sur la température et l’enthalpie de transition suivent le même ordre que la série d’Hofmeister : sulfate > hydrogénophosphate > chlorure (pas de pic). La calcéine avait l’impact le plus prononcé sur l’agrégation; ceci illustre que la calcéine n’est pas une sonde fluorescente inerte avec le mélange SA/Chol. Elle pourrait être un chaotrope volumineux. De plus, les interactions SA-calcéine plus fortes, menant à l’agrégation des vésicules, que les interactions PC-calcéine pourraient s’expliquer par le fait que la SA est chargée positivement. / Sterosomes are artificial vesicles that are composed of monoalkylated amphiphiles and a large percentage of sterols. They are promising in areas such as pharmaceutical and food industries. Sterosomes can be found in anionic, cationic and neutral form. The work of this master’s thesis focuses on gaining additional knowledge on the physicochemical properties of charged sterosomes such as palmitic acid (PA)/sterol and stearlyamine (SA)/cholesterol (Chol). Our first aim was to find an approach to form liquid-ordered (lo) bilayers that can orient in a magnetic field with the PA/sterol (30/70 mol/mol) mixture. This will allow us to study the lateral diffusion of PA. It has been demonstrated that mixing 1,2-diheptanoyl-sn-glycero-3-phosphocholine (DHPC), a short chain lipid, with 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) results in bilayers that orient with their normal (n) perpendicular to the magnetic field. Therefore, perdeuterated PA/hexanoic acid (HA)/Chol (25/18/57) mixture was studied at different temperatures; however, results showed no bilayer orientation. It was suggested that this could be due to the partial solubility of HA in aqueous phase. Consequently, an insufficient quantity of HA was available to induce bilayer orientation. Furthermore, perdeuterated PA/DHPC/Chol mixture was studied at different temperatures and lipid concentrations, which also led to no bilayer orientation. While studying DMPC/DHPC/Chol (67/17/14) formulation, it was understood that Chol inhibits bilayer orientation. On the other hand, two different molar proportions of DMPC/DHPC/stigmasterol (SS) (67/19/14 and 72/21/7) led to bilayers that orient with their n perpendicular to the magnetic field at 40 °C et 50 °C. These results suggest that by adding a short chain lipid such as HA and DHPC to PA/SS mixture could lead to oriented bilayers. Another interesting track would be to work with PA/short chain lipid/Chol mixture in the presence of lanthanides. Our second aim was to find different formulations of vesicles, containing at least PA and a sterol, with distinctive permeability. It has already been established that PA/Chol (30/70) bilayers are in lo phase as long as PA is deprotonated (pH ≥ 7,5) and have a very limited permeability. The ability to modulate permeability would allow control over the release time of an encapsulated product, which is an important parameter in the development of novel liposomal drug delivery systems. It was proven that oleic acid (OA)/Chol (30/70) mixture is able to form bilayers, which has not been shown previously. However, OA/Chol (30/70) bilayers were not much more permeable than PA/Chol (30/70) bilayers. Adding 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) in PA/Chol system did not lead to higher permeability either. Results of calcein release kinetics from PA/POPC/Chol (15/27.5/57.5), POPC/Chol (40/60) and POPC vesicles were not very different from the one found for PA/Chol (30/70) vesicles. It was noted that contradictory results were found in the literature regarding calcein permeability from phosphatidylcholine (PC) membranes. For the moment, explanations related to these divergences have yet to be given. Furthermore, no increase in membrane permeability was found after substituting half of the molar proportion of Chol by sodium cholate (SC) in PA/Chol (30/70) mixture. One suggestion would be that SC insertion in the bilayer does not induce a reduction in the packing of lipids. Another suggestion would be that SC does not insert in PA/Chol bilayers due to its considerable hydrophilic character and forms micelles on its own. Highly permeable membrane was found when Chol was completely replaced by cholesterol sulfate (SChol), a negatively charged sterol, and vesicle preparation was done at low pH. The pH-triggered release method was used. Our work suggests that by varying the molar proportion of PA/SChol/Chol mixture between 30/63/7 and 30/70/0, it would be possible to obtain different vesicle formulations with distinctive permeability. In between these molar proportions, the pH-composition diagram of PA/SChol/Chol shows the coexistence of solid and lo phases in different proportions at pH 7.4, which could modulate the permeability. Some ambiguous calcein release results and struggles arising from the extrusion of calcein-encapsulated liposomes led us to wonder if this dye interacts with charged bilayers. The impact of some anions, including calcein, was examined on SA/Chol (50/50) charged bilayers. Thermodynamic studies were done by differential scanning calorimetry (DSC). SA/Chol (50/50) mixture showed no transition between 25 and 90 °C at pH 7.4. In the presence of sodium chloride (375 mM), there was no indication of aggregation or the appearance of a transition on the thermogram. Macroscopic aggregates were instantly observed after addition sodium hydrogenphosphate (125 mM), sodium sulphate (125 mM) and calcein (3 mM). Furthermore, a phase transition was also noticed on the thermograms in the presence of these salts. It is suggested that the appearance of the transition can be associated with the formation of aggregates. The effect of anions on the transition temperature and enthalpy follows the Hofmeister series: sulfate > hydrogenphosphate > chloride (no peak). Calcein had the highest impact on the formation of aggregates. This indicates that calcein is not a good candidate to be used as a fluorescent dye with SA/Chol mixture. It was suggested that calcein could be a large chaotrope anion. In contrast to PC-calcein interactions, SA-calcein interactions led to the aggregation of vesicles probably due to stronger interactions in the presence of positively charged SA.

Dans le cadre d'une approche Higher Tamm Dancoff Approximation notée HTDA, nous avons étudié les corrélations vibrationnelles de type quadrupole, avec et sans appariement. Le champ moyen a été déterminé dans le cadre d'une approche microscopique utilisant l'interaction effective de Skyrme. Une interaction résiduelle schématique de type delta plus quadrupole-quadrupole, tenant compte en particulier de l'appariement neutron-proton T=0 et T=1 a été utilisé. Les résultats obtenus pour la résonance géante quadrupolaire isoscalaire du noyau Ca40 ont été comparés aux données expérimentales et à d'autres résultats théoriques. Nous avons également étudié un gaz de fermions piégés dans un potentiel d'oscillateur harmonique à 2D, et à température nulle, en présence d'un champ magnétique uniforme. Les expressions exactes des quelques grandeurs thermodynamiques ont été dérivées à partir de la matrice densité de Bloch. / Within the framework of the so-called Higher Tamm Dancoff Approxiamtion (HTDA), we have studied the quadrupole vibrational correlations with and without pairing correlations. The mean field has been determined within a microscopic approach using the Skyrme effective interaction. A schematic residual interaction of the delta plus quadrupole-quadrupole type, allowing in particular neutron-proton T=0 and T=1 pairing, has been used. The results which have been obtained for the isoscalar quadrupole giant resonance of the Ca40 have been compared with the experimental data. A fermion gaz trapped in a 2D harmonic oscillator well at zero temperature and in the presence of a uniform magnetic field has been investigated. Exact expressions of some thermodynamic quantities have been derived from the Bloch density matrix.