Cette thèse est consacrée à l'étude de la décohérence de paquets d'onde mono-électroniques injectés dans un conducteur quantique balistique. Les paquets d'onde sont générés à l'aide d'une capacité mésoscopique, utilisée comme source d'électrons uniques, qui sont émis à la demande dans le canal de bord externe de l'effet Hall quantique entier. Deux telles sources indépendantes et synchronisées sont positionnées sur les bras d'entrée d'une lame séparatrice électronique. La mesure des fluctuations (bruit) du courant dans les bras de sortie permet de caractériser les interférences à deux électrons se produisant sur la lame séparatrice. De cette manière, on réalise l'analogue électronique de l'interféromètre de Hong-Ou-Mandel (HOM). Il apparaît que le contraste de la figure d'interférence dépend de la forme des paquets d'onde injectés. Cette perte de cohérence est imputée au couplage capacitif, dû à l'interaction coulombienne, entre le canal de bord externe et les autres canaux de bord co-propageants, qui constituent un environnement contrôlé pour le canal externe. Afin de valider cette hypothèse, une seconde expérience est réalisée. La capacité mésoscopique y est utilisée dans un autre régime de fonctionnement, dans lequel elle permet de générer une excitation collective de la densité de charge du canal externe, appelée magnéto-plasmon de bord. En caractérisant la propagation du magneto-plasmon de bord en fonction de la fréquence d'excitation, on peut sonder l'interaction Coulombienne entre deux canaux de bord. Ces mesures montrent que cette interaction est responsable de l'apparition de deux modes propres de la propagation : un mode "chargé" rapide et un mode "neutre" lent. Elles permettent de caractériser quantitativement la vitesse de propagation du mode neutre. Les résultats de cette seconde expérience sont ensuite utilisés pour établir que la perte de contraste, observée dans l'expérience HOM, est essentiellement due à l'interaction entre canaux de bord. Ce couplage est responsable de la destruction des quasi-particules injectées par la source, un électron se séparant (ou fonctionnalisant) en deux pulses de charge e/2 au fil de sa propagation. Durant le processus de fractionnalisation, l'état généré dans le canal de bord externe s'intrique avec son environnement (canaux de bord co-propageants) entraînant la réduction du contraste dans l'expérience HOM. Ces observations ouvrent la voie à de nouvelles expériences plus complexes telles que la tomographie de l'état du paquet d'onde sur la lame séparatrice (pour valider complètement le scénario de destruction des quasi-particules) ou la protection de la cohérence de l'état dans le canal de bord externe. / This manuscript is devoted to the study of the decoherence of single electronic wavepackets injected in a balistic quantum conductor. The single electrons are emitted on-demand using a mesoscopic capacitor in the outer edge channel of the integer quantum Hall effect. Two independent and synchronized sources are located on the input arms of an electronic beam-splitter. The measurement of the current fluctuations (noise) in the output arms allows for the characterization of two-electron interferences occuring on the beam-splitter. This realizes the electronic analog of the Hong-Ou-Mandel (HOM) interferometer. It appears that the contrast of the interference pattern depends on the shape of the emitted wavepackets. This loss of electronic coherence is caused by the capacitive coupling, due to the Coulomb interaction, between the outer edge channel and the other channels, which constitute a controlled environment for the outer channel. In order to validate this scenario, a second experiment has been realized. The mesoscopic capacitor is used in a different regime, in which it generates a collective charge density wave called edge magnetoplasmon. By characterizing the propagation of the edge magnetoplasmon as a function of frequency, one can probe the Coulomb interaction between the channels. The measurements show that this interaction is responsible for the appearance of two propagating eigenmodes: a fast charge mode and a slow neutral mode, and provide the determination of the slow mode velocity. The results of this second experiment are then used to establish that the reduction of the contrast observed in the HOM experiment is caused by this interchannel interaction. It is responsible for the destruction of the quasiparticles emitted by the source which fractionalize in charge pulses of charge e/2 along propagation. During the fractionalization process, the state generated in the outer channel gets entangled with the environment (other channels), hence reducing the contrast in the HOM experiment. More complex experiments, such as the tomography of the emitted electornic wavepacket to validate the full decoherence scenario, or the implementation of decoherence protection schemes can be envisioned in the future.

The interplay of thermodynamic properties of strongly interacting matter and its emission of photons is investigated. For this purpose the Lagrangian of the quark meson model (in the literature also dubbed "linear sigma model" or "linear sigma model with quarks") is extended by an electromagnetic sector. Based on this extended Lagrangian both the grand-canonical potential and the generating functional of correlation functions are calculated in a consistent manner. From the former, the phase structure and various thermodynamical properties are determined. Especially, the dependence of certain landmarks (critical point, intersections of the phase boundary with the coordinate axes, etc.) of the phase diagram with respect to the model parameters is investigated in detail. With the help of the generating functional in turn, the photon propagator can be computed whose imaginary part is connected to the emission rate of photons. The leading order of the result with respect to the number of participating particles and the power of the quark-meson coupling is expressed in terms of tree level diagrams, which are calculated likewise. On this basis, the photon emissivity with respect to temperature, chemical potential and photon frequency is calculated and analyzed addressing various questions. The dependence of the particle masses with respect to temperature and chemical potential leaves notable imprints on the emissivities of the individual production processes. Especially a first-order phase transition can easily be identified, since, there, the emissivity may jump - depending on the temperature - by a factor of about ten. Contrarily, within our analysis, we do not find signatures in the photon emissivities that specifically mark a critical end point. Moreover, it is investigated on which parameters the photon emission rate depends in the low- and high-frequency regions. With these results the behavior of the emissivity with respect to temperature and chemical potential can be understood and many peculiarities of the emissivities can be explained. / Das Zusammenspiel der thermodynamischen Eigenschaften von stark wechselwirkender Materie und deren Emission von Photonen wird untersucht. Dazu wird die Lagrangedichte des Quark-Meson-Modells (auch: Linear-Sigma-Modell oder Linear-Sigma-Modell mit Quarks) um einen elektromagnetischen Sektor erweitert. Aus der so erweiterten Lagrangedichte werden auf konsistente Weise sowohl das großkanonische Potential als auch das erzeugende Funktional der Korrelationsfunktionen ermittelt. Aus ersterem werden die Phasenstruktur des Modells sowie zahlreiche thermodynamische Eigenschaften berechnet. Insbesondere wird die Abhänigkeit einiger Orientierungspunkte (kritischer Punkt, Schnittpunkte der Phasengrenze mit den Koordinatenachsen usw.) des Phasendiagramms von den Modellparametern detailiert untersucht. Mit Hilfe des erzeugenden Funktionals wiederum kann der Photonenpropagator bestimmt werden, dessen Imaginärteil mit der Emissionsrate von Photonen zusammenhängt. Die führende Ordnung in einer Entwicklung nach der Anzahl der beteiligten Teilchen und der Potenz der Quark-Meson-Kopplung lässt sich durch Baumgraphen-Diagramme darstellen, die ebenfalls berechnet werden. Auf dieser Basis wird die Photon-Emissivität in Abhängigkeit von Temperatur, chemischem Potential und Photon-Frequenz berechnet und unter verschiedenen Gesichtspunkten analysiert. Die Abhängigkeit der Teilchenmassen von Temperatur und chemischem Potential hinterlässt teilweise ausgeprägte Signaturen in den Emissivitäten der einzelnen sub-Prozesse. Insbesondere ein Phasenübergang erster Ordnung zeigt sich deutlich, da an diesem die Emissivität - abhänging von der Temperatur - um einen Faktor der Größenordnung zehn springen kann. Jedoch finden wir im Rahmen dieser Analyse keine spezifischen Signaturen in den Photonen-Emissivitäten, die einen kritischen Punkt auszeichnen. Des weiteren wird untersucht von welchen Parametern die Photonen-Emissionsrate in den Bereichen niedriger oder hoher Photonen-Frequenzen abhängt. Mit diesen Ergebnissen kann das Verhalten der Emissivität in Abhängigkeit von Temperatur und chemischem Potential gut verstanden und zahlreiche Auffälligkeiten in den Emissivitäten erklärt werden.

Many previous studies have demonstrated that gold compounds possess successful results in catalysis and in medicinal chemistry. The central aim of this dissertation is the design and synthesis of novel gold (I) acyclic diamino carbene complexes as a chemotherapeutic agent for triple-negative breast cancer (TNBC) and for catalysis. In this study, a series of chiral neutral and cationic gold (I) acyclic diamino carbene (ADC) complexes and neutral gold (I) bis- ADC complexes have been synthesized. As the chiral neutral gold (I) ADCs, four diastereomers of S binaphthyl L proline tertiary butyl ester gold (I) chloride, S binaphthyl D proline tertiary butyl ester gold (I) chloride, R binaphthyl L proline tertiary butyl ester gold (I) chloride, and R binaphthyl D proline tertiary butyl ester gold (I) chloride have been synthesized and characterized. Different chiral gold (I) ADC complexes with bulky chiral binaphthyl group and with different amine groups of morpholine, chiral proline methyl ester, and benzyl ester have been synthesized and characterized. After that four diastereomers of the nitrile adduct of cationic binaphthyl proline tertiary butyl ester nitrile and four diastereomers of the isonitrile versions of it have been synthesized and characterized. A series of gold (I) cationic bis ADC complexes have been synthesized and characterized. All these novel gold ADC complexes were tested for biological activity against TNBC cell line MDA-MB-231 and cationic S binaphthyl D proline ester isonitrile adduct, S binaphthyl D proline ester isonitrile adduct and R binaphthyl D proline ester isonitrile adduct gave promising inhibition rates. According to Lipinski's rule, lipophilicity determines the effectiveness of the drug absorption to the body through the lipid membrane. To determine the drug-likeness of the gold ADC complexes, log P values were calculated for some of the synthesized complexes using a modified shake flask method. Gold (I) ADC complexes have been renowned for their ability in catalysis, but enantioselective catalysis is not that well studied. A3 coupling reaction is a well-known reaction for the synthesis of propargyl amines. Here, A3 coupling reaction with a chiral amine has been performed using the previously synthesized four diastereomers of binaphthyl proline tertial butyl ester gold (I) ADCs (SL, RD, RL, SD) as the catalyst expecting four different diastereomers of the product. The reaction exhibited reasonable yields but with a low enantiomeric excess (ee%). However, it gave proof of the principle that asymmetric induction is possible with the synthesized novel chiral gold (I) ADC complexes.

Natural products are teeming with potential therapeutic agents. One group of compounds, polyphenols, from plants, exhibit anti-cancer, anti-inflammatory and anti-oxidant activities. Four polyphenolic compounds and their enantiomers were investigated in this thesis; the stilbene, 3-methoxypterostilbene, a structural analog of resveratrol, and the chiral prenylflavonoids from hops (Humulus lupulus L.); 8-prenylnaringenin, 6-prenylnaringenin and isoxanthohumol. A high performance liquid chromatography method for 3-methoxypterostilbene and enantiospecific liquid chromatography-mass spectrometry assays for the three prenylflavonoids were developed and validated. The methods allowed for quantification of these four polyphenols in biological samples and plant-based materials. Content analysis studies of 3-methoxypterostilbene and the three prenylflavonoids in traditional Chinese medicinal plants and hops-containing nutraceuticals were carried out, respectively. The pharmacokinetics of these four compounds were delineated through intravenous and oral administration in rats. 3-Methoxypterostilbene demonstrated greater bioavailability in rats than reported values for resveratrol. Enantiomeric differences in disposition parameters were observed for the three prenylflavonoids along with differences between compounds despite only small structural differences. The in vitro pharmacodynamics of these four compounds were elucidated including anti-oxidant, anti-inflammatory, anti-diabetic and cytochrome P450 modulation activities. All four compounds demonstrated a range of bioactivities related to chronic diseases and potential drug-botanical interactions. Further studies of polyphenols, especially clinical studies, are needed along with enantiospecific study when applicable to continue delineating the importance of bioactivity, pharmacokinetics and safety. Natural products are further developed into nutraceuticals and sold over-the-counter for both human and veterinary use but are not currently required to demonstrate efficacy prior to marketing. In the final section of this thesis, Phycox®, a multi-component veterinary nutraceutical for joint health was investigated for pharmacological activity in an in vitro model of canine osteoarthritis along with select constituents. A pilot single-dose pharmacokinetic study in dogs was also undertaken. Two liquid chromatography tandem mass spectrometry methods were developed and validated to detect constituents in serum. In vitro study results indicated that Phycox® was able to reduce inflammatory mediators similar to the NSAID, carprofen, and acute pharmacokinetic results revealed that detectable concentrations of glucosamine were evident in serum. It is suggested that further clinical studies of Phycox® are warranted to optimize its usage. / May 2016

The field of organic chemistry is divided into many subfields, which include polymer design and synthesis, transition metal catalysis and organocatalysis among a variety of others. Challenges in polymer design and synthesis can be highlighted pointedly in the use of photoresists for lithographic processing. Recent challenges in development of shorter wavelength sources has led to the need to develop new photoresist materials that can be exposed twice without any development steps in between. Two methods for addressing double exposure materials will be presented. Additionally, the areas of catalysis, whether transition metal or organic in nature, are important methods in organic synthesis. The mechanism of the addition of Gilman reagents to enones has been the subject of debate, and efforts to elucidate this mechanism will be presented. Finally, organocatalysis has expanded its scope into a variety of reactions previously only conducted with transition metal catalysts. Work towards an enantioselective allylic amination reaction using organocatalysis as well as absolute stereochemistry of the product will be explored. / text

Although gas and liquid chromatography have emerged as dominant separation techniques in environmental analytical chemistry, these methods do not allow for the concurrent analysis of chemically diverse groups of persistent organic pollutants (POPs). There are also a small number of compounds which are not easily amenable to either of these traditional separation techniques. The main objective of this thesis was to address these issues by demonstrating the applicability of packed column supercritical fluid chromatography (pSFC) coupled to mass spectrometry (MS) in various aspects of environmental chemistry. First, pSFC/MS analytical methods were developed for legacy POPs (PCDDs, PCDFs, and PCBs) as well as the emerging environmental contaminant Dechlorane Plus (DP), and issues relating to the ionization of target analytes when pSFC was coupled to MS were explored. Novel APPI and APCI reagents (fluorobenzene and triethylamine) were optimized and real samples (water and soil) were analyzed to demonstrate environmental applicability. The possibility of chiral and preparative scale pSFC separations was then demonstrated through the isolation and characterization of thermally labile hexabromocyclododecane (HBCDD) stereoisomers. The analytical pSFC separation of the α-, β-, and γ-HBCDD enantiomers as well as the δ and ε meso forms was shown to be superior to results obtained using a published LC method. Finally, technical mixtures of phosphorus flame retardants (RBDPP, BPA-BDPP, and DOPO; a group of related compounds which are challenging to analyze concurrently) were examined using multiple analytical techniques and pSFC was found to be the only method which facilitated the accurate determination of the components of all 3 mixtures. This thesis confirms the potential of pSFC/MS as a fast, green, and cost effective means of separating and analyzing environmental contaminants.

We solve a random matrix ensemble called the chiral Ginibre orthogonal ensemble, or chGinOE. This non-Hermitian ensemble has applications to modelling particular low-energy limits of two-colour quantum chromo-dynamics (QCD). In particular, the matrices model the Dirac operator for quarks in the presence of a gluon gauge field of fixed topology, with an arbitrary number of flavours of virtual quarks and a non-zero quark chemical potential. We derive the joint probability density function (JPDF) of eigenvalues for this ensemble for finite matrix size N, which we then write in a factorised form. We then present two different methods for determining the correlation functions, resulting in compact expressions involving Pfaffians containing the associated kernel. We determine the microscopic large-N limits at strong and weak non-Hermiticity (required for physical applications) for both the real and complex eigenvalue densities. Various other properties of the ensemble are also investigated, including the skew-orthogonal polynomials and the fraction of eigenvalues that are real. A number of the techniques that we develop have more general applicability within random matrix theory, some of which we also explore in this thesis.

Thèse numérisée par la Direction des bibliothèques de l'Université de Montréal.

Small chiral molecules are very important building blocks in the synthesis of biologically active compounds. These building blocks include nitrogen and oxygen-containing heterocycles such as 2-oxazolidinones, 1,3-oxazinan-2-ones, 2-oxazolines, oxazines, morpholine and morpholinones. Because of their interesting properties, chiral heterocycles have stirred great interest in the synthetic chemist community to develop useful and efficient strategies to these molecules. In this dissertation, the design and syntheses of various heterocyclic building blocks are presented, as well as the testing of their biological activities as antibacterial. Another very interesting family of heterocycle-containing molecules are the Aeruginosins. They are a family of marine natural products isolated from a blue-green algae, which display inhibitory activity against serine proteases such as thrombin, trypsin, and factor VIIa. Most aeruginosins contain an heterocyclic moiety called the 2-carboxy-6-hydroxyoctahydroindole (Choi) ring; this Choi moiety is a rigid bicyclic unnatural amino acid and is the core structure in the aeruginosins, indispensable to their biological activity. A synthesis of a ring-oxygenated variant of the Choi from D-mannose is reported in this dissertation. The ring-oxygenated variant of 2-carboxy-6-hydroxyoctahydroindole can potentially be used as a surrogate of Choi in the design and synthesis of aeruginosin-based thrombin inhibitors.

A presente tese propõe-se a investigar a discussão que ocorre na literatura hadrônica de baixas energias com relação à renormalização de teorias efetivas não-perturbativas, no caso particular do sistema nucleon-nucleon. Os detalhes que tornam o problema não-trivial são a existência do potencial tensor devido à troca de um píon e o aspecto não-relativístico tanto da equação dinâmica (Lippmann-Schwinger ou Schrödinger) quanto da derivação do potencial. A teoria de perturbação quiral (PT), desenvolvida por Gasser e Leutwyler, tem se mostrado como a mais fiel representação da QCD em baixas energias. A extensão da PT para o setor envolvendo poucos nucleons foi realizada por Weinberg, através de um esquema de contagem de potências quiral (power counting). O power counting de Weinberg tem sido severamente criticado na literatura devido à sua não-renormalizabilidade, que possui estreita relação à divergência da troca de um píon. Recentemente, Staporoli estudou a inclusão de campos auxiliares capazes de absorver as divergências provenientes da troca de um píon. A natureza desses campos são escolhidas por critérios de grande número de cores na QCD. Neste trabalho, mostramos que a inclusão de um campo auxiliar vetorial na teoria efetiva, em ordem dominante, é um ingrediente capaz de absorver as divergências de curto alcance e fornecer resultados com muito boa concordância com as análises de ondas parciais do grupo de Nijmegen (PWA93). Desta maneira, este estudo instaura a renormalizabilidade do sistema de dois nucleons, ausente na proposta de Weinberg, além de ser uma alternativa de maior apelo físico e com menos procedimentos ad hoc, como na promoção de contra-termos sugerida por Nogga, Timmermans e van Kolck. / The present work aims at investigating the current discussion in the literature of low-energy hadron physics, concerning the non-perturbative renormalization of effective field theories, in particular, the case of a system with two nucleons. The details that make this issue non-trivial are the existence of a tensor potential due to the exchange of one pion, as well as the non-relativistic aspects of both the dynamical equation (Lippmann-Schwinger or Schrödinger) and the derivation of the nucleon-nucleon potential. Chiral perturbation theory (PT), developed by Gasser and Leutwyler, has been shown to be the most faithful representation of low energy QCD. The extension of PT to the sector involving few- nucleons was performed by Weinberg, through a power counting scheme. Weinberg\'s power counting has been severely criticized in the literature for its non-renormalizability, which is closely related to the divergence of the one-pion exchange. Recently, Staporoli studied the inclusion of auxiliary fields capable of absorbing divergences from the exchange of a pion. The nature of these fields are chosen by criteria of large number of colors in QCD. In this work, we show that the inclusion of a vector auxiliary field in the effective theory, at dominant order, is an ingredient capable of absorbing the short-range divergences and provides results with very good agreement with the partial wave analysis of the Nijmegen group (PWA93). In this way, this study establishes the renormalizability of the two nucleon system, absent in the Weinberg\'s proposal, besides of being an alternative with larger physical appealing and with less ad hoc procedures, as the promotion of counter-terms suggested by Nogga, Timmermans and van Kolck.