We consider the finite two-dimensional Ising model on a lattice with periodic boundaryconditions. Kaufman determined the spectrum of the transfer matrix on the finite,periodic lattice, and her derivation was a simplification of Onsager's famous result onsolving the two-dimensional Ising model. We derive and rework Kaufman's resultsby applying representation theory, which give us a more direct approach to computethe spectrum of the transfer matrix. We determine formulas for the spin correlationfunction that depend on the matrix elements of the induced rotation associated withthe spin operator. The representation of the spin matrix elements is obtained byconsidering the spin operator as an intertwining map. We wrap the lattice aroundthe cylinder taking the semi-infinite volume limit. We control the scaling limit of themulti-spin Ising correlations on the cylinder as the temperature approaches the criticaltemperature from below in terms of a Bugrij-Lisovyy conjecture for the spin matrixelements on the finite, periodic lattice. Finally, we compute the matrix representationof the spin operator for temperatures below the critical temperature in the infinite-volume limit in the pure state defined by plus boundary conditions.

No description available.

Previous studies have demonstrated the sensitivity of the amplitude of the microwave radiation-induced magnetoresistance oscillations to the microwave polarization. These studies have also shown that there exists a phase shift in the linear polarization angle dependence. But the physical origin of this phase shift is still unclear. Therefore, the first part of this dissertation analyzes the phase shift by averaging over other small contributions, when those contributions are smaller than experimental uncertainties. The analysis indicates nontrivial frequency dependence of the phase shift. The second part of the dissertation continues the study of the phase shift and the results suggest that the specimen exhibits only one preferred radiation orientation for different Hall-bar sections. The third part of the dissertation summarizes our study of the Hall and longitudinal resistance oscillations induced by microwave frequency and dc bias at low filling factors. Here, the phase of these resistance oscillations depends on the contact pair on the device, and the period of oscillations appears to be inversely proportional to radiation frequency.

Graphene has unrivalled properties and is heralded as a revolutionary material for the 21^st century. Chemical vapour deposition (CVD) on metals is a promising method to produce large-area graphene. Controlling the properties of CVD graphene is vital for its integration in a wide-range of future applications. Many factors can influence the CVD growth of graphene and its properties, therefore further investigations will be beneficial to fully understand and control this technique. In this thesis I expand the knowledge about the growth of pure and heteroatom-doped graphene by low pressure chemical vapour deposition (LPCVD) and atmospheric pressure chemical vapour deposition (APCVD) on commercially available Cu and Pt foils. Using a range of characterisation techniques, I investigate the influence of the substrate’s properties and the synthesis conditions on the growth of graphene, in pursuit of improved, controlled or optimised production, which can promote high quality, large-area, single-layer graphene, or other as desired. By characterising the topography, surface roughness, crystallographic orientations, and chemical composition of six Cu foils, I find that their properties vary greatly and this influences the growth of CVD graphene. I elucidate that the commonly used 99.8 % Alfa Aesar Cu foil has a surface coating composed of calcium, chromium, and phosphorus, which detrimentally influences graphene growth. Cleaning Cu foils with CH₃COOH is shown to reduce the concentration of surface contaminants, consequently reducing the nucleation density and increasing the growth rate of CVD graphene. I also demonstrate that the shape, orientation, edge-geometry and thickness of CVD graphene domains can be controlled by the Cu crystallographic orientations. Single layer LPCVD graphene domains align with zigzag edges parallel to a single <101> direction on Cu{111} and Cu{101}, while bilayer domains align to two directions on Cu{001}. Hexagonal APCVD domains also preferentially align with edges parallel to the <101> direction(s). This discovery resolves a key challenge of controlling the orientation of individual graphene domains and opens a new avenue for tailored production of large-area CVD graphene with improved properties. By controlling the synthesis conditions of APCVD graphene on Pt foils I optimise production of ~0.5 mm single layer graphene domains with reduced nucleation density and increased growth rate of ~100 &mu;m/min by synthesis at 1150°C, a higher temperature than previously reported. The absence of large, hexagonal, single-crystal domains on pristine Pt foil, and observation of a reaction between quartz and Pt that promotes hexagonal domains, suggests that a silicon or platinum silicide surface layer may be advantageous for improved growth of graphene. Finally, I demonstrate that the dopant concentration of nitrogen-doped graphene is increased at lower synthesis temperatures and higher NH₃ concentration, up to 1.3 %, but with an associated decrease in the growth rate. Direct visualisation, elemental confirmation, and electronic characterisation of individual nitrogen atoms is shown for the first time using aberration corrected scanning transmission electron microscopy and electron energy loss spectroscopy. Boron-doped graphene is also synthesised. The implications of these findings, and many additional minor contributions, are wide-ranging and of considerable importance for the future understanding of CVD growth of graphene on metals, and more generally for the advancement of scientific knowledge for manufacturing large-area graphene. Collectively, these discoveries represent a significant body of work that can improve the efficiency of production and assist with controlling the properties of large-area CVD graphene.

Fundulus is a diverse and widespread genus of small teleost fish of North America. Due to its high tolerance for physiochemical variation (e.g. temperature, oxygen, salinity), Fundulus is a model organism to study physiological and molecular adaptations to environmental stress. The thesis focuses on patterns of protein expression in Fundulus heteroclitus and F. grandis.The patterns of protein expression were investigated using traditional methods of enzyme activity measurements and recent proteomic approaches. The findings of the study can be used to guide future studies on the proteomic responses of vertebrates to environmental stress. Chapter 2 focuses on measurement of the temporal effects of oxygen treatments on the maximal specific activities of nine glycolytic enzymes in liver and skeletal muscle during chronic exposure (28d) of Fundulus heteroclitus. The fish was exposed to four different oxygen treatments: hyperoxia, normoxia, moderate hypoxia, and severe hypoxia. The time course of changes in maximal glycolytic enzyme specific activities was assessed at 0, 8, 14 and 28 d. The results demonstrate that chronic hypoxia alters the capacity for carbohydrate metabolism in F. heteroclitus, with the important observation that the responses are both tissue- and enzyme-specific. Chapter 3 studies the effect of tissue storage on protein profile of tissues of F. grandis. The technique of one dimensional gel electrophoresis (1D-SDS-PAGE) was used to assess the effects of tissue sampling, flash frozen in liquid nitrogen versus immersion of fresh tissue in RNA later, for five tissues, liver, skeletal muscle, brain, gill, and heart, followed by LC-MS/MS to identify protein bands that were differentially stabilized in gill and liver. The study shows that, in F. grandis, the preferred method of preservation was tissue specific. xi Chapter 4 focuses on the use of advanced 2DE-MS/MS to characterize the proteome of multiple tissues in F. grandis. Database searching resulted in the identification of 253 non-redundant proteins in five tissues: liver, muscle, brain, gill, and heart. Identifications include enzymes of energy metabolism, heat shock proteins, and structural proteins. The protein identification rate was approximately 50 % of the protein spots analyzed. This identification rate for a species without a sequenced genome demonstrates the utility of F. grandis as a model organism for environmental proteomic studies in vertebrates.

Les travaux présentés dans ce manuscrit portent sur la croissance de réseaux 2D covalents nanoporeux sur des substrats métalliques monocristallins en conditions ultravide. La réalisation de tels réseaux bidimensionnels nanostructurés met en jeu l’assemblage de briques élémentaires par des réactions de polymérisation sur surface qui sont ensuite caractérisées par microscopie à effet tunnel. La réaction étudiée est la condensation par déshydratation des groupes acides boroniques de l’acide 1,4-benzènediboronique conduisant à la formation d’un réseau aux pores hexagonaux de 15Å. L’étude se focalise spécifiquement sur l’influence de la fonctionnalisation du monomère (l’ajout de substituants ou d’hétéroatomes sur le cycle aromatique) sur les propriétés de la molécule et son impact sur la croissance du réseau. Une seconde famille de molécule fonctionnalisée a été étudié à partir de l’acide 1-bromo-4-benzèneboronique, qui par la substitution d’un acide boronique par un brome permet de modifier le mécanisme de polymérisation et ainsi de ralentir la cinétique de réaction. Les travaux réalisés portent sur la synthèse des deux familles de molécules, sur la caractérisation de l’évolution de leurs propriétés (polymérisation, dégradation) et sur leur capacité à former des réseaux covalents 2D ordonnés. Il a ainsi été possible de déterminer de manière qualitative les paramètres critiques qui gouvernent l’assemblage des molécules pour optimiser la croissance de réseaux fonctionnalisés. / The work presented in this thesis relates to the growth of 2D covalent organic frameworks on single crystal metal substrates in UHV conditions. The realization of such nanostructured two-dimensional networks involves the assembly of building blocks by polymerization reactions on surface that are characterised by scanning tunnelling microscopy. The chosen reaction is the condensation by dehydration of boronic acid groups from the 1,4-benzenediboronique acid leading to the formation of a nanoporous network with 15 Å hexagonal pores. The study focuses specifically on the effect of the monomer functionalization (addition of substituents or hetero atoms on the aromatic ring) regarding the molecule properties and its impact on the network growth. A second functionalized molecule family has also been studied from the 1-bromo-4-benzene boronic acid in which a boronic acid is substituted by a bromine group. This allows kinetic control of the polymerization. The work done relates to the synthesis of the two kind of functionalized molecules, the characterization of the evolution of their properties (polymerization, degradation) and their ability to form ordered 2D covalent networks. It was thus possible to determine qualitatively the critical parameters that govern the assembly of molecules to optimize the growth of functionalized networks.

De nombreuses propriétés étonnantes ont été récemment découvertes à l’interface de deux perovskites isolantes l’une polaire l’autre non polaire. La discontinuité de charge à l’interface LaAlO3/SrTiO3 engendre un gas d’électron quasi-bidimensionnel qui confère un caractère métallique à cette interface. Les mécanismes locaux et la quantification des propriétés ne font pas consensus car l’interdépendance de facteurs structuraux, chimiques et électroniques complexifie la résolution du problème posé. Une catastrophe polaire, des distorsions structurales, des lacunes d’oxygène, une interdiffusion cationique et une non stœchiométrie du film ont été séparément avancées pour expliquer cette conduction. Dans le cadre d’un programme international, nous avons reçu des héterointerfaces conductrices et isolantes élaborées par ablation laser pulsé (PLD). L’origine des porteurs de charge a été recherchée par une approche globale liant procédé, structure et propriétés électriques (mesurées dans le consortium). Nous avons systématiquement analysé les interfaces en combinant imagerie à haute résolution (STEM-HAADF) et spectroscopies électroniques (EELS) et ioniques (MEIS). Une non planéité des couches atomiques, une interdiffusion cationique et un transfert d’électrons permettent de réduire la divergence de potentiel, la catastrophe polaire n’a donc pas lieu. La formation de défauts donneurs à la surface du film devient favorable au-delà d’une épaisseur critique. Les électrons sont transférés à l’interface dans la bande de conduction du STO. Nous avons mis en évidence un mécanisme de compensation concurrentiel de la charge interfaciale par des lacunes de strontium chargées négativement, qui mettent le substrat en compression plane et s’opposent au confinement 2D électrons. La variation des paramètres procédés, tels que la durée du dépôt, la pression partielle en oxygène, la température et la stœchiométrie de la plume déplace l’équilibre des différents mécanismes mis en évidence. Ce travail démontre la relation complexe liant procédé, propriétés électriques et distribution des défauts autour de ces interfaces singulières. / Novel behavior at the interface between two insulating polar/non polar perovskites has been recently discovered. The polarization discontinuity at LaAlO3/SrTiO3 drives the formation of quasi two dimensional electron gas. Both the local mechanism and quantification of such behavior remain unclear due to interplay of structural, chemical and electronic factors. Several mechanisms have been proposed, such as the polar catastrophe, structural distortions, oxygen vacancies, cationic intermixing at the interface and film non-stoichiometry. In the frame of an international project conductive and insulating heterostrucutres have been synthetized by Pulsed-Laser Deposition. In this thesis, we have developed a comprehensive approach to investigate the origin of the charge carriers. The interfaces have been systematically analyzed by combining high resolution imaging (STEM-HAADF) to atomic resolved electron (EELS) and ion (MEIS) spectroscopies. The observed and quantified parameters have been related to the electrical properties of the interfaces measured in the consortium. Buckling of the atomic layers, intermixing and electron transfer reduce the polar divergence. This rules out the polar catastrophe scenario. The formation of donor defects at the film surface is favored above a critical film thickness. Electrons are transferred to interface in the STO conduction band. A competing compensation mechanism of the positive interfacial charge by negatively charged strontium vacancies has been demonstrated that generates an in plane compression of the STO, unfavorable for a strict 2D confinement of the charges. Varying the process parameters such as growth duration, oxygen partial pressure, temperature, and plume stoichiometry shift the equilibrium of the different mechanisms highlighted. This thesis emphasizes the complex relations between the process and the properties through the defects distribution around these singular interfaces.

Ce manuscrit présente une étude expérimentale d'un gaz de 87Rb ultra-froid confiné à deux dimensions et en présence de désordre. Dans une première partie, nous mettons en place les outils expérimentaux développés pour manipuler les gaz confinés. Après un état de l'art sur l'apport de la communauté des atomes froids aux gaz de Bose 2D, nous détaillons notre expérience, en l'absence de désordre, qui par une comparaison fine avec des simulations Monte-Carlo quantique et grâce à une thermométrie en temps de vol très précise, a permis de quantifier l'apparition de la cohérence autour la transition de phase superfluide Berzinskii-Kosterlitz-Thouless (BKT). La seconde partie est dédiée à l'effet d'un potentiel désordonné généré optiquement et corrélé microscopiquement sur les propriétés de transport et de cohérence du gaz 2D en interaction. Cette partie suit la progression de l'expérience du régime de transport classique, dans lequel nous avons mesuré la dépendance du coefficient de diffusion classique en fonction de l'énergie de la particule, jusqu'au transport quantique, que nous avons atteint grâce à une ultime méthode de ralentissement. Sur la route entre ces deux régimes, nous observons un décalage vers les faibles entropies de l'établissement de la cohérence autour de la transition BKT provoqué par l'ajout adiabatique d'une quantité modérée de désordre ainsi que sa suppression pour un désordre de l'ordre de la température du nuage. Ce travail est une étape vers une étude expérimentale de la transition quantique vers le verre de Bose mettant en jeu à la fois désordre et interactions. / This manuscript shows an experimental study of a disordered ultra-cold 87Rb gas confined in two dimensions.In the first part, we set up the experimental tools used to manipulate the confined gases. After a state of the art in ultracold 2D Bose gases, we describe our disorder-free experiment from which, by a comparison with quantum Monte-Carlo calculations and thanks to an accurate time-of-flight thermometry, we are able to quantify the emergence of coherence around the Berezinskii-Kosterlitz-Thouless superfluid phase transition. The second part is devoted to the effect of a micrometer-range optically generated disordered potential on the transport and coherence properties of the interacting 2D gas. This part follows the experimental road from the regime of classical transport, in which we have measured the energy dependence of the classical diffusion coefficient, to the regime of quantum transport we have just reached thanks to a last cooling step. On the road between those two regimes, we observe a shift towards lower entropy of the emergence of coherence close to the BKT transition as a response of an adiabatic addition of a moderate amount of disorder. It is strongly suppressed for an amount of disorder of the order of the cloud temperature. This work is a first step to an experimental study of the quantum transition to the Bose-Glass phase involving disorder and interaction.

Neste trabalho, apresentamos estudos de magnetotransporte em um sistema quase tridimensional de elétrons produzido em amostras contendo poços quânticos parabólicos (PQW, Parabolic Quantum Well ) formados em heteroestruturas de AlGaAs crescidos sobre substratos de GaAs pela técnica de epitaxia por feixe molecular (MBE). Na primeira parte do nosso trabalho realizamos medidas de magnetoresistência, efeito Hall e efeito Shubnikov-de Haas em PQWs com larguras de 1000 Å a fim de investigar as propriedades eletronicas tais como a concentração e a mobilidade dos elétrons nas amostras. Através de cálculos autoconsistentes determinou-se os perfis de potencial, os níveis de energia e as concentrações de cada uma das sub-bandas ocupadas no poço. Uma análise através da transformada de Fourier também permitiu determinar as concentrações eletrônicas nas sub-bandas. Em uma segunda parte estudou-se a influência da aplicação de potenciais externos através de uma porta metálica com barreira em uma amostra contendo um PQW de largura 3000 Å na presença de campos magnéticos perpendicular e paralelo à superfície da amostra. Encontrou-se que para uma tensão de porta de Vg = 0, 55V forma-se uma barreira de potencial ainda sem ter depleção de cargas no poço. Apresenta-se a idealização do dispositivo transistor válvula de spin, a partir do fato que aplicando uma tensão de porta é possível deslocar espacialmente os elétrons e mudar a sua orientaçãp de spin. / Results from magnetic transport studies made on quasi-three-dimensional electron systems are presented in this work. AlGaAs heterostructures grown on GaAs subtrates through molecular beam epitaxy (MBE) enable the existence of this type of systems by means of parabolic quantum wells (PQW) formation. This work was developed in two main parts. First, we studied magnetoresistence phenomena, such as Hall effect and Shubnikov-de Haas, on 1000 Å width PQWs. This permits to know the electronic concentration and mobility values of this type of samples, among other electrical properties. Then, self-consistent calculations gave an outline of the size and shape of the potentials, and gave the values for the energy levels and the electronic concentration on each occupied sub-band of the quantum well. Through Fourier transform analysis was also possible to obtain and confirm the electronic concentrations of the occupied sub-bands. In the second part of the work, we studied the effects of applying an external potential through a barrier gate to a 3000 Å width PQW sample in the presence of magnetic fields parallel and perpendicular to the sample surface. For a V g = 0, 55 V gate voltage, it was found that a potential barrier was formed even without charge depletion in the well. An idealization for the spin valve transistor device, based on the fact that applying a gate potential spatially dislocates the electrons and changes their spin orientation, is presented.

Este projeto teve como objetivo principal realizar um estudo proteômico diferencial aplicado às amostras de casca do caule de plantas cítricas sadias e infectadas pela morte súbita dos citros. Subsequentemente, a identificação de proteínas diferentemente expressas será de grande importância, uma vez que estas poderão servir não somente como candidatos a biomarcadores para a doenças, mas também auxiliarão no melhor compreensão da doença. À partir dos géis bidimensionais obtidos para amostras de porta-enxerto (limão cravo e limão volkameriano) e copa (laranja valência) foi possível verificar que existem dois conjuntos de proteínas sensivelmente sub-expressas em plantas doentes. Um desses conjuntos, constituído por 13 spots, apresenta valores de pI entre 4,5 e 5,2 e MM aproximadamente igual a 30 kDa. No outro conjunto, esse composto por 9 spots, valores de pI variando entre 6,1 e 9,6 e MM em torno de 20 kDa são observados. Por meio das técnicas de MALDI-TOF-TOF e LC-ESI-MS/MS, inúmeros spots foram inequivocamente identificados, incluindo os spots correspondentes às regiões diferentemente expressas. Os 13 spots correspondentes a região com valores de pI entre 4,5 e 5,2 e MM ~ 30 kDa foram todos identificados como sendo constituídos por três isoformas de quitinases. Por outro lado, os spots referentes a região com pI entre 6,1 e 9,6 e MM ~ 20 kDa foram identificados como proteína putativa similar a miraculina 2. A justificativa para o fato de diversos spots terem recebido a mesma identificação é atribuída às inúmeras e diferentes modificações pós-traducionais, comumente verificadas em plantas. Entretando, o aspecto mais relevante relacionado a essas identificações é o fato de que ambas as proteínas são conhecidas marcadoras de resistência de defesa em plantas e assim sendo, a priori, espera-se-ia que estivessem sendo super expressas em plantas doentes. Porém, um comportamento inverso foi verificado, o que reforça as evidências de que as quitinases não agem apenas como marcadores de defesa em plantas, possuindo assim outras funções. Além disso, no total, outras 19 proteínas puderam ser identificadas. / The main goal of this project was to perform a differential proteomic analysis of bark tissues of healthy and CSD (citrus sudden death)- affected citrus plants. Subsequently, the identification of differently expressed proteins will be of great importance since they can be used not only as biomarkers for CSD but also as basic information for improving the knowledge about the disease. According to the 2D gels, obtained for bark tissues of both rootstock (rangpur lime and volkamerian lemon) and scion samples, there are two sets of proteins remarkably under expressed in CSD-affected samples. One of these sets is composed by 13 proteins, which presents MW around 30 kDa and pI ranging from 4.5 to 5.2. The other set includes 9 proteins with pI ranging from 6.1 to 9.6 and MW around 20 kDa. By using two mass spectrometry approaches (MALDI-TOF-TOF and LC-ESI-MS/MS), several proteins have been unequivocally identified, including the differentially expressed ones. Thirteen spots have been identified as a mixture of three chitinase isoforms. These spots are relative to the region with pI ranging from 4.5 to 5.2 and MW ~ 30 kDa. On the other hand, the 9 spots referent to the region with MW ~ 20 kDa and pI between 6.1 and 9.6 were identified as putative miraculin-like 2 protein. Several spots have been identified as the same protein most probably due to the occurrence of different post-translational modifications. The most valuable point regarding the identity of these proteins is the fact that they are well-known plant pathogen-related proteins and then they should be over expressed in affected plants. However, the opposite behavior was verified, which may indicate that chitinases and putative miraculin-like 2 protein perform unknown functions, besides the established ones. In addition, other 19 constitutive proteins have been identified.