A soja geneticamente modificada tolerante ao herbicida glifosato tem sido a cultura derivada da engenharia genética mais cultivada atualmente no mundo. Como todo alimento GM a soja tem sido alvo de investigação em relação a sua Biossegurança. Novas estratégias têm sido desenvolvidas e aplicadas neste campo de pesquisa, sendo que métodos rápidos e eficientes de análise proteômica têm sido utilizados para avaliação e monitoramento da segurança e inocuidade alimentar, indicando mudanças no perfil protéico entre variedades convencionais e GM. O objetivo do presente trabalho foi avaliar os mapas protéicos de amostras de soja convencionais e suas derivadas geneticamente modificadas tolerantes ao herbicida glifosato, utilizando técnicas de análise proteômica com ênfase para inocuidade alimentar. Foram utilizadas seis amostras de soja, sendo três convencionais parentais e três derivadas GM, cultivadas entre 2004-2005, em Goiás. O extrato bruto protéico foi submetido à análise por eletroforese unidimensional e bidimensional. A eletroforese 2D, foi realizada utilizando tiras com gradiente de pH de 3-10 e 4-7. As imagens dos mapas protéicos das seis variedades, produzidas em replicatas, foram analisadas pelo software ImageMaster 2D Platinum. O potencial alergênico do extrato protéico bruto foi avaliado para todas as variedades utilizando soro de pacientes alérgicos à soja através de immunoblotting. Nos resultados obtidos observou-se a presença das principais frações protéicas da soja pela eletroforese unidimensional sem alteração significativa entre as amostras parentais e GM, exceto para uma banda de 115 kDa presente nas amostras parentais, mas ausente nas amostras GM. A partir da análise por eletroforese 2D foram identificadas as formas peptídicas correspondentes às frações de β-conglicinina e glicinina bem como diversas outras proteínas encontradas na soja como o inibidor de tripsina e a lipoxigenase. Através do software foi possível observar que um spot apresentou diferença estatística entre as amostras analisadas, expresso em maior concentração nas amostras GM do que nas parentais. Nos testes de alergenicidade, os extratos protéicos das variedades GM demonstraram reatividade similar em relação as suas respectivas variedades parentais. A proteína de 115 kDa foi sequenciada e identificada como a proteína precursora da cadeia α da β-conglicinina e o spot das amostras GM que apresentou diferença estatística significativa foi identificado como a proteína precursora de G4 glicinina. A diferença observada entre as variedades parentais e GM para as subunidades α de β-conglicinina e G4 glicinina pode ter ocorrido devido a variações normais observadas entre diferentes variedades de soja. Os resultados demonstram a viabilidade de aplicação das ferramentas proteômicas na identificação de alterações de perfis protéicos de amostras de soja parentais e GM. Pelos dados obtidos podemos concluir que as diferenças apresentadas não comprometem a inocuidade alimentar das amostras de soja GM em relação a suas respectivas variedades parentais. / Genetically modified soya-tolerant to the herbicide glyphosate culture has been derived from the more cultivated genetic engineering in the world today. As GM soya beans whole food has been investigated in relation to your biosafety. New strategies have been developed and applied research in this field, and fast and efficient methods of analysis proteomics have been used for assessment and monitoring of food security and safety, indicating changes in own protein profile between conventional and GM varieties. The aim of this work was to assess the maps soy protein samples of conventional and genetically modified their derived to the herbicide glyphosate-tolerant, using Proteomics analysis techniques with emphasis on food safety. Six samples were used for conventional soya, three and three derived from GM parental, grown between 2004-2005. The crude protein extract own was subjected to analysis by electrophoresis one-dimensional and two-dimensional. 2D electrophoresis using Strip was held with pH gradient of 3-10 and 4-7. Protein maps images of six varieties produced in replicates have been analysed by the 2D Platinum software ImageMaster. The potential allergenic in crude protein extracts was evaluated for all varieties using allergic patient serum soya by immunoblotting. In the results obtained noted the presence of the main protein fractions of soya by one-dimensional electrophoresis without significant change between parental and GM samples, except for a band of 115 parental kDa present in the sample, but absent in GM samples. From the analysis by 2D electrophoresis peptides forms were identified corresponding to fractions of β-conglicinina and glicinina as well as several other proteins found in soy as trypsin inhibitor and lipoxygenase. Through the software has been possible to observe that a spot presented statistical difference between the samples tested, expressed in greater concentration in the samples GM in parenting. In tests of allergenicity, GM varieties protein extracts showed similar reactivity in respect of their parental varieties. 115 KDa protein was sequenced and identified as the protein precursor of α subunit of β-conglicinina and the spot that GM samples presented significant statistical difference was identified as the G4 glicinina protein precursor. The difference between parental and GM varieties for subunits α of β-conglicinina and G4 glicinina may have occurred due to normal variation between different varieties of soy. The results demonstrate the viability of applying the tools Proteomics in identification of protein profiles changes of soya samples parental and GM. By data obtained can be concluded that the differences do not compromise the safety of food GM soybean samples with regard to their parental varieties.

Cette thèse a été conduite afin d’explorer le potentiel d’une nouvelle méthodologie utilisant la pyrolyse, la chromatographie gazeuse et la spectrométrie de masse pour la caractérisation et l’identification des fibres papetières utilisées dans la fabrication des papiers asiatiques traditionnels à partir de la caractérisation des métabolites de ces fibres. Cette méthodologie utilise un processus d’échantillonnage facilité nécessitant une très petite quantité d’échantillons (de l’ordre de quelques dizaines de µg). Après la pyrolyse des échantillons de papiers et la séparation chromatographique des composés formés, des distributions caractéristiques pour les métabolites des fibres papetières (considérant leur présence et leur intensité) ont été observées dans une région définie comme région d’intérêt dans les chromatogrammes: ces distributions se sont révélées spécifiques pour la caractérisation des papiers fabriqués à partir de différents types de fibres et ont été utilisées pour distinguer l’origine des différentes fibres papetières couramment utilisées dans la fabrication de papiers asiatiques traditionnels. Premièrement, les problèmes rencontrés dans l’étude des papiers faits à la main ont été présentés, comme l’origine de la fabrication du papier, l’incohérence de certains résultats dans l’identification des fibres (reportés dans différentes études scientifiques), les limites de la microscopie pour l’identification des fibres papetières d’origines botaniques similaires et les risques d’imprécision dans le référencement des échantillons. Tous ces problèmes montrent la nécessité d’explorer de nouvelles méthodes pour (1) améliorer la fiabilité de l’identification des fibres papetières des papiers asiatiques traditionnels, (2) valider et confirmer les résultats obtenus par l’analyse microscopique. À cette fin, dans un premier temps, des papiers asiatiques de référence ont été étudiés. Les résultats expérimentaux ont montré que les différentes fibres papetières utilisées pour la fabrication des papiers étudiés montraient des différences dans les distributions de leurs marqueurs spécifiques : par exemple, les fibres d’origine de la famille Moraceae montrent une distribution caractéristiques de composés triterpèniques alors que les fibres d’origine de la famille Thymelaeaceae montrent une distribution caractéristiques de composés de type stigmastanes. De leur côté, les fibres des plantes appartenant au groupe Ma montrent peu de métabolites caractéristiques. Les différences observées dans la distribution de ces métabolites ont été attestées par la comparaison entre distributions obtenues à partir des fibres végétales et celles des papiers faits à la main attestant de l’origine commune de ces métabolites issus des tissus végétaux d’origine. Ainsi, la méthodologie étudiée se révèle prometteuse en tant que méthode de chimiotaxonomie pour l’identification des fibres inconnues de papiers faits à la main. Avec les exemples d'applications fournies au cours du travail expérimental, le couplage de la pyrolyse, de la chromatographie en phase gazeuse et de la spectrométrie de masse (avec l’utilisation de la Py-GC/MS et de la Py-GCxGC/MS) a montré sa capacité à distinguer les fibres d'une même famille (qui peuvent présenter des caractéristiques similaires en microscopie) et peut ainsi constituer une méthode efficace d'identification des fibres et de validation des résultats d'identification obtenus par l'observation microscopique. Dans la présente thèse, les caractéristiques de la chromatographie gazeuse intégralement bidimensionnelle GCxGC, ses avantages pour les applications dans le domaine du patrimoine culturel et son apport potentiel pour le traitement des données 1D ont été discutées (...) / This study was conducted to explore a new methodology for handmade fiber characterizationand identification using pyrolysis, gas chromatography and mass spectrometry. It employseasy sampling process with minor quantity of samples required. After pyrolysis of handmadepapers, a featured metabolites distribution patterns (presence plus intensity) eluting in the defined region of interest (ROI) was observed to be characteristic for handmade papers of different material origins. The method utilizes these metabolites distribution patterns as markers to discriminate different fiber origins. Firstly, the problems encountered in the investigation of handmade papers were introduced such as the origin of papermaking, the inconsistency in the fiber identification results sometimes gained by different scholars, the limits of microscopy in identifying fibers from similar species and the likely imprecision of the reference sample labeling. All these problems showed the necessity to explore a new method in order to (i) make precise fiber identification of handmade papers and (ii) to validate or confirm the identification results obtained by microscopy. Then, modern reference handmade papers were firstly studied. The result revealed that different plant fibers used for papermaking have different marker distributions in the ROI, forinstance, the Moraceae family with a featured distribution of terpene compounds and theThymelaeaceae family with a featured distribution of stigmasta compounds. The fibers fromthe ma group usually revealed few compounds in the ROI. This metabolites difference in theROI was attested from the plant tissues with their similar distribution in handmade papers and plant raw fibers. Thus, the chosen methodology offers promise as a method of chemotaxonomy for unknown handmade paper fiber identification. With the examples ofapplications provided during the experimental work, the coupling of pyrolysis, gaschromatography and mass spectrometry (through the use of Py-GC/MS and Py-GCxGC/MS)showed its ability to distinguish fibers from the same plant family (that may present similar microscopic features) and thus, can constitutes an effective method for fiber identification as well as to validate the identification results of the microscopic observation. In the present thesis, the features of GCxGC and the benefits for cultural heritage applications and its help for the ID data treatment were discussed. The tested Py-GCxGC/MS methodology has been for the first time proposed in the cultural heritage field and it harbors the potential to promote the research in this domain, enhancing our capacity to handle small quantities of complex samples while providing an exhaustive response on its composition.

Dans cette thèse, nous nous intéressons à la croissance de boîtes quantiques par formation de nano-trous in-situ par « droplet-etching » ainsi qu’à la fabrication et caractérisation de dispositifs basés sur ces nanostructures. La thèse comporte sept chapitres. Le premier chapitre est une introduction au sujet et les méthodes expérimentales sont présentées dans le second chapitre. Les méthodes de fabrication ainsi que les résultats expérimentaux obtenus sont discutés dans le troisième chapitre.Nous montrons que l’utilisation in-situ de la méthode de droplet-etching permet de modifier localement l’épaisseur d’un puits quantique à modulation de dopage et créer des boîtes quantiques dans le puits où existe un gaz bidimensionnel d’électrons. Ces nanostructures constituent des diodes n-i Schottky que nous avons étudié. Les effets de ces boîtes quantiques non-contraintes et les fluctuations d’épaisseur à l’échelle nanométrique du puits quantique sur la mobilité du gaz bidimensionnel d’électrons sont discutés dans le quatrième chapitre et cinquième. Le sixième chapitre présente la fabrication d’une jonction p-n latérale basée sur l’échantillon de puits quantique avec des boîtes. Nous discutons les différentes étapes de fabrication et analysons leur influence sur le dispositif, ainsi que leurs propriétés optiques. En particulier, nous démontrons l’électroluminescence d’une boîte unique localisée dans une jonction p-n latérale. Finalement, le dernier chapitre conclue ce travail et en présente les perspectives. / In this thesis the formation of quantum dots (QD) via in-situ droplet nanohole etching, the fabrication and characterization of devices based on these nanostructures is described. The thesis consists of seven chapters. In the first chapter an introduction is given to present the topic to the reader. In the second chapter the experimental methods are presented. In the third chapter, the fabrication method is described and the experimental results obtained in this project are discussed. It will be shown the use of in-situ droplet etching to locally modify the thickness of a modulation doped quantum well, to create QDs embedded in a quantum well(QW) where a two dimensional electorn gas (2DEG) is confined by modulation doping and the embedding of these nanostructures in a n-i-Schottky diode. The effect of these strain-free dots, and the related nanoscale thickness fluctuations of the quantum well, on the 2DEG mobility are discussed in the fourth and in particular in the fifth chapter. In the sixth chapter, the fabrication of a lateral p-n junction based on the QW sample with embedded QD is presented. Following describing the fabrication stages and analysing the influence of each stage on the device, the optical properties of the junction will be discussed. In particular, it will be shown the electroluminescence of a single dot located at lateral the p-n junction. Finally, in the last chapter the conclusion of this work and the future projects are presented.

Resumo: O presente trabalho teve como objetivo investigar a presença de selênio em spots protéicos de amostras de plasma, músculo e fígado de tilápia do Nilo (Oreochromis niloticus) obtidos após separação das proteínas por eletroforese em gel de poliacrilamida em segunda dimensão (2D-PAGE) e posterior avaliação qualitativa por fluorescência de raios-X com radiação síncrotron (SR-XRF). A análise dos espectros de fluorescência obtidos indicaram a presença de selênio em oito proteínas do plasma, seis proteínas do músculo e cinco proteínas do fígado. Observou-se que o selênio está distribuído em sua maioria em proteínas com massa molar menor que 50 kDa. Proteínas acima de 50 kDa foram encontradas somente no plasma. / Abstract: An investigation was made into selenium in protein spots of samples of plasma, muscle and liver of Nile tilapia (Oreochromis niloticus) obtained after protein separation by two-dimensional polyacrylamide gel electrophoresis (2D-PAGE) and subsequent qualitative evaluation by synchrotron radiation X-ray fluorescence (SR-XRF). An analysis of the fluorescence spectra indicated the presence of selenium in eight plasma proteins, six muscle proteins, and five liver proteins. Selenium was found to be distributed mainly in proteins with a molar mass smaller than 50 kDa. Proteins with a molar mass higher than 50 kDa was found only in the plasma. / Orientador: Pedro de Magalhães Padilha / Coorientador: Marco Aurélio Zezzi Arruda / Banca: Paulo Roberto Rdrigues Ramos / Banca: Ricardo de Oliveira Orsi / Banca: Gustavo Rocha de castro / Banca: Paulo dos Santos Roldan / Doutor

Orientador: Pedro de Magalhães Padilha / Banca: Paulo Roberto Ramos / Banca: Lincoln Carlos de Oliveira / Resumo: No presente trabalho foi feito uma análise qualitativa de cálcio, ferro e zinco em spots de proteínas de amostras de tecido hepático de tilápia do Nilo (Oreochromis niloticus) por Fluorescência de Raios-X de Radiação Síncroton, após a separação das proteínas por Eletroforese Bidimensional em Gel de Poliacrilamida (2D-PAGE). Os espectros de fluorescência obtidos indicaram a presença de cálcio, ferro e zinco em doze, seis e oito spots protéicos das amostras de fígado, respectivamente. Os íons metálicos detectados nas amostras estão distribuídas principalmente em proteínas de massa molar menor que 45 kDa e com pI na faixa de 4,5 a 9,0. Além do cálcio, ferro e zinco foram detectados a presença de enxofre e fósforo, elementos não metálicos, que podem ser constituintes da estrutura das proteínas. As concentrações de cálcio, ferro e zinco ligados às proteínas foram determinadas por FAAS após a mineralização ácida dos spots protéicos, encontrando-se concentrações na faixa de 1,08 a 5,80 mg g-1, 2,02 a 8,03 mm g-1 e 1,60 a 8,55 mg g-1, respectivamente / Abstract: An investigation was made into calcium, iron and zinc in protein spots in samples of Nile tilapia (Oreochromis niloticus) liver tissue obtained after protein separation by two-dimensional polyacrylamide gel electrophoresis (2D-PAGE) and subsequent qualitative and quantitative evaluation by synchrotron radiation X-ray fluorescence (SRXRF) and graphite furnace atomic absorption spectrometry (FAAS). An analysis of the fluorescence spectra indicated the presence of calcium, iron and zinc in twelve, six and eight liver protein spots, respectively. The metal ions found were distributed mainly in proteins with a molar mass of less than 40.00 kDa and more than 12.00 kDa, with pI in the range of 4.70 to 9.40. The only exception was a spot presenting protein with a molar mass of 10.10 kDa. In addition to calcium, iron and zinc, sulfur and phosphorus - which are non-metals that may be part of the protein structure, were also detected. After microwave-assisted acid mineralization of the proteins spots, a FAAS estimation of the concentration of calcium, iron and zinc bound to these proteins indicated a range of 1.08 to 5.80 mg g-1, 2.02 to 8.03 mg g-1 e 1.60 to 8.55 mg g-1, respectively / Mestre

Este trabalho apresenta o estudo do desempenho analógico do transistor SOI MOSFET com tensão de limiar dinamicamente variável (DTMOS). Esse dispositivo é fabricado em tecnologia SOI parcialmente depletado (PD). A tensão de limiar desta estrutura varia dinamicamente porque a porta do transistor está curto-circuitada com o canal do mesmo, melhorando significativamente suas características elétricas quando comparadas aos transistores PD SOI MOSFET convencionais. Entre as características principais desse dispositivo, pode-se citar a inclinação de sublimiar praticamente ideal (60 mV/dec), devido ao reduzido efeito de corpo, resultando num aumento significativo da corrente total que corresponde à soma da corrente do transistor principal com a corrente do transistor bipolar parasitário inerente à estrutura. Diversas simulações numéricas bidimensionais, utilizando o simulador ATLAS, foram executadas a fim de se obter um melhor entendimento do dispositivo DTMOS, quando comparado com o SOI convencional. As características elétricas analisadas através da simulação numérica bidimensional apresentam a corrente de dreno em função da polarização da porta considerando VD baixo e alto (25 mV e 1V). O canal teve uma variação de 1 até 0,15 µm. Através dessas simulações foram obtidos as principais características elétricas e parâmetros analógicos para estudo do DTMOS em comparação com o SOI convencional como: transcondutância (gm), tensão de limiar (VTH), inclinação de sublimiar (S). Considerando a polarização de dreno em 1V foi obtido a transcondutância e a inclinação de sublimiar. Na etapa seguinte foi feito simulações para obter as curvas características de IDS x VDS, onde a tensão aplicada na porta variou de 0 a 200 mV (VGT), onde se obteve a tensão Early (VEA), a condutância de saída (gD) dos dispositivos, bem como o ganho intrínseco de tensão DC (AV) e a freqüência de ganho unitário (fT). Os resultados experimentais foram realizados em duas etapas: na primeira, extraíram-se todas as curvas variando o comprimento do canal (L) de 10 à 0,15 µm e na segunda, manteve-se um valor fixo do comprimento do canal (10 µm), variando somente a largura do canal (W) entre 10 e 0,8 µm, para identificar quais seriam os impactos nos resultados. A relação da transcondutância pela corrente de dreno do DTMOS foi 40 V-1 na média, independentemente do comprimento do canal e observou-se um aumento de 14 dB no ganho intrínseco quando usado o comprimento de canal de 0,22 µm, em comparação com SOI convencional. Foi verificado uma melhora na performance dos parâmetros analógicos do DTMOS quando comparado com o PDSOI e têm sido muito utilizado em aplicações de baixa tensão e baixa potência. / This work presents the study of analog performance parameters of PDSOI (Partially-depleted) transistor in comparison with a Dynamic Threshold MOS transistor (DTMOS). The DTMOS is a partially-depleted device with dynamic threshold voltage. This variation of threshold voltage is obtained when the gate is connected to the silicon film (channel) of the PDSOI device, improving the electrical characteristics of a conventional SOI. The characteristics of this device is an ideal subthreshold slope (60mV/dec), due to the reduced body effect and improved current drive. When the gate voltage increases in DTMOS (body tied to gate), there is a body potential increase, which results in a higher drain current due to the sum of the MOS current with the bipolar transistor (BJT) one. Several two-dimensional numerical simulations were done with the ATLAS Simulator to obtain a better knowledge of DTMOS device to compare with PDSOI. The electrical characteristics analyzed through two-dimensional numerical simulations are the drain current as a function of (VGS) with drain bias fixed at 25 mV and 1 V. The channel length varied from 10 to 1 um. Through these simulations the main electrical characteristics and the analog performance parameters were obtained of DTMOS in comparison with conventional SOI, as: transconductance (gm), threshold (VTH) voltage, and subthreshold slope (S). Considering the drain bias of 1V, transconductance and subthreshold voltage were obtained. In the next step, the characteristics curves of drain current (IDS) as a function of (VDS), where the gate bias varied from 0 to 200 mV of (VGT), to obtain the Early voltage (VEA) and output conductance (gD), the intrinsic gain DC (AV) and a unit-gain frequency to both devices were simulated. The experimental results were measured in two steps: in the first step all electrical characteristics and parameters considering a channel length (L) variation were obtained and in the second step a channel length was fixed and varied the width (W) was varied to study if this variation had any effects on the results. The gm/IDS ratio of DTMOS was 40 V-1 , independent of channel length and a increase of 14 dB in intrinsic gain, when using a channel length of 0,22 µm, compared with the conventional SOI was obtained. Improvement was observed in the performance of analog parameters when compared whit conventional SOI and DTMOS has been widely used in Low-Power- Low-Voltage applications.

Made available in DSpace on 2015-04-22T22:02:09Z (GMT). No. of bitstreams: 1 Paula C S Barbosa.pdf: 2096071 bytes, checksum: 806dcd37f1a3dcf13e97a1623194db6e (MD5) Previous issue date: 2012-06-25 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / As árvores do gênero Copaifera (Leguminosae), conhecidas popularmente como copaibeiras, exsudam um óleo-resina extensamente utilizado na medicina popular e por indústrias farmacêuticas e de cosméticos, devido às suas atividades cicatrizante e anti-inflamatória. Quimicamente, esses óleos se caracterizam pela presença de hidrocarbonetos sesquiterpênicos, sesquiterpenos oxigenados e ácidos diterpênicos. No entanto, a composição química desses óleos-resina é variável e ainda não se tem conhecimento dos fatores que as determinam, embora vários fatores bióticos e abióticos sejam considerados fontes dessa variação. Essa variação dificulta a padronização da composição química desses óleos, comprometendo seu controle de qualidade e consequentemente a qualidade dos produtos a que darão origem, fato que tem causado um grande entrave à sua maior aplicação e comercialização. Essa variabilidade em sua composição química já é bastante conhecida e relatada na literatura, mas a maioria dos estudos realizados têm se restringido a caracterizar quimicamente o óleo-resina e poucos tem se preocupado em estudar as causas dessas variações. O objetivo deste trabalho foi padronizar a composição química dos óleos de copaíba por meio de técnicas de cromatografia em fase gasosa acoplada à detectores de ionização de chama (CG-DIC) e espectrometria de massas (CG-EM) e cromatografia em fase gasosa bidimensional abrangente (CGXCG); analisar estatisticamente a influência de fatores abióticos como sazonalidade, tipo de solo e diâmetro à altura do peito (DAP), além da infestação por cupins, sobre a composição química desses óleos. Além disso, foram comparados 5 métodos de esterificação dos ácidos diterpênicos presentes nos óleos de copaíba envolvendo catálise ácida, que utilizam BF3/MeOH, H2SO4/MeOH e HCl/MeOH, levando-se em consideração suas eficiências e frequências analíticas, além do consumo e toxicidade dos reagentes utilizados, relação custo benefício e, principalmente, a possibilidade de alteração/degradação da estrutura dos constituintes quando aplicados em óleos de copaíba. Para isso foram obtidos óleos de copaíba de 3 coletas: em novembro de 2004 e novembro de 2005 (épocas consideradas secas) e em maio de 2005 (época considerada chuvosa). No total, 43 amostras de óleo-resina de copaíba foram coletadas na Reserva Ducke (Manaus-AM), de 33 espécimes diferentes, que possuíam diferentes DAP s e se encontravam em diferentes tipos de solo. As análises por CG-DIC e CG-EM permitiram a identificação de 35 constituintes: sendo 22 hidrocarbonetos sesquiterpênicos, 9 sesquiterpenos oxigenados e 4 ácidos diterpênicos. Enquanto a análise por CGxCG permitiu a identificação de outros 13 sesquiterpenos, além de 7 monoterpenos, inéditos em óleos-resina de copaíba. O β-cariofileno e seu óxido foram os constituintes majoritários em 29 e 11 amostras, respectivamente. As análises hierárquica por agrupamento (HCA) e de componentes principais (PCA) evidenciaram a existência de dois grupos distintos com diferentes perfis cromatográficos, em que foi comprovada apenas a influência do tipo de solo, sobre a composição química desses óleos. Outros fatores analisados como sazonalidade, DAP e infestação por cupins, não tiveram influência sobre a composição química dos óleos-resina de copaíba. Quanto aos métodos de esterificação, as análises das 5 metodologias testadas, apesar de terem sido reprodutíveis, não se mostraram eficientes, ao passo que não permitiram a identificação dos constituintes formados e levaram à formação de artefatos.

This thesis presents several experiments, generally aiming at visualising the ballistic and topological transport on the high-mobility graphene/boron nitride heterostructure using the scanning gate microscope. For the first experiment, we use the scanning gate microscopy to map out the trajectories of ballistic carriers in high-mobility graphene encapsulated by hexagonal boron nitride and in a weak perpendicular magnetic field. We employ a magnetic focusing transport configuration to image carriers that emerge ballistically from an injector, follow a cyclotron path due to the Lorentz force from an applied magnetic field, and land on an adjacent collector probe. The local potential generated by the scanning tip in the vicinity of the carriers deflects their trajectories, modifying the proportion of carriers focused into the collector. By measuring the voltage at the collector while scanning the tip, we are able to obtain images with arcs that are consistent with the expected cyclotron motion. We also demonstrate that the tip can be used to redirect misaligned carriers back to the collector. For the second experiment, we investigate the graphene van der Waals structures formed by aligning monolayer graphene with insulating layers of hexagonal boron nitride which exhibit a moiré superlattice that is expected to break sublattice symmetry. However, despite an energy gap of several tens of millielectronvolts opening in the Dirac spectrum, electrical resistivity remains lower than expected at low temperature and varies between devices. While subgap states are likely to play a role in this behaviour, their precise nature is still unclear in the community. We therefore perform a scanning gate microscopy study of graphene moiré superlattice devices with comparable activation energy but with different charge disorder levels. In the device with higher charge impurity ($\sim$ 10$^-$ cm$^{-2}$) and lower resistivity ($\sim$ 10 k$\Omega$) at the Dirac point we observe scanning gate response along the graphene edges. Combined with simulations, our measurements suggest that enhanced edge doping is responsible for this effect. In addition, a device with low charge impurity ($\sim$ 10$^{9}$ cm$^{-2}$) and higher resistivity ($\sim$ 100 k$\Omega$) shows subgap states in the bulk. Our measurements provide alternative model to the prevailing theory in the literature in which the topological bandstructures of the graphene moiré superlattices entail an edge currents shunting the insulating bulk. In the third experiment, we continue our study in the graphene moir$\acute e$ superlattices with the newly reported non-local Hall signals at the main Dirac point. It has been associated with the non-zero valley Berry curvature due to the gap opening and the nonlocal signal has been interpreted as the signature of the topological valley Hall effects. However, the nature of such signal is still disputed in the community, due to the vanishing density of states near the Dirac point and the possible topological edge transport in the system. Various artificial contribution without a topological origin of the measurement scheme has also been suggested. In connection to the second experiment, we use the scanning gate microscope to image the non-local Hall resistance as well as the local resistance in the current path. By analysing the features in the two sets of images, we find evidence for topological Hall current in the bulk despite a large artificial components which cannot be distinguished in global transport measurement. In the last experiment, we show the development of a radio-frequency scanning impedance microscopy compatible with the existing scanning gate microscopy and the dilution refrigerator. We detailed the design and the implementation of the radio-frequency reflectometry and the specialised tip holder for the integration of the tip and the transmission lines. We demonstrate the capability of imaging local impedance of the sample by detecting the mechanical oscillation of the tip, the device topography, and the Landau levels in the quantum Hall regime at liquid helium temperature and milli-Kelvin temperature.

La chromatographie en phase liquide bidimensionnelle est une technique à fort potentiel, offrant un grand pouvoir de séparation. Après avoir démontré son intérêt dans l’industrie pharmaceutique et présenté les enjeux liés à l’analyse quantitative, une attention particulière est portée sur le développement de méthodes. Dans l’idée de développer une stratégie d’analyse générique, la première étape est de sélectionner un set de trois systèmes 2D par le biais d’une approche développée au laboratoire. La deuxième étape est d’évaluer le potentiel de ces systèmes pour l’analyse quantitative. Ces deux étapes ont conduit à la proposition d’une stratégie d’analyse applicable à l’analyse pharmaceutique dans un contexte industriel. Enfin le potentiel du couplage RPLCxSFC est envisagé dans deux cas de figure différents. Premièrement, dans le but de comparer ce couplage aux séparations RPLCxRPLC développées dans le cadre d’une stratégie analytique générique, en termes de pouvoir de séparation. Deuxièmement, dans le cadre de l’analyse de composés chiraux, en développant un couplage sRPLCxSFC permettant une analyse achirale/chirale simultanée. Les avantages d’une telle approche ont été mis en avant en la comparant aux approches conventionnelles / Two-dimensional liquid chromatography (2D-LC) is a powerful technique considering its high separation power. After showing the advantage of 2D-LC in the pharmaceutical area and presenting the challenges related to quantitative analysis, special attention was paid to method development. With the aim of developing a generic analytical strategy for pharmaceuticals, the first step of our approach consisted in selecting a set of three 2D-systems with the help of a methodology previously developed. In a second step, the potential of these 2D-systems was evaluated for the purpose of quantitative analysis. An analytical strategy able to be applied to pharmaceutical analysis in an industrial context was proposed. Finally, the potential of RPLCxSFC was investigated in two different cases. Firstly, for comparing this on-line two dimensional technique to on-line RPLCxRPLC with respect of the separation power. Secondly, for chiral compounds by developing a selective RPLCxSFC method for simultaneous achiral-chiral analysis. The advantage of such method was highlighted by comparing to conventional approaches

O objetivo geral deste estudo é o de trabalhar o problema de corte bidimensional guilhotinado irrestrito e no-estagiado. Para tanto, foram revistas regras e heurísticas a serem utilizadas e foi sugerida uma combinação da regra de simetria com a heurística de geraçgo dos pontos de cortes possíveis. Uma abordagem em grafo-E/OU, com a utilizaçgo de uma estratégia híbrida, que combina as técnicas \"Hill-Climbing\" e \"Depth-First\" para a busca em grafo, foi utilizada para a resolução do problema. Finalmente, foram comparados os resultados obtidos com resultados apresentados na literatura. / The general purpose of this study is to deal with the non-staged unconstrained guilhotined cutting problem. For this, rules and heuristics in use are reviewed and a combination between simmetry rule and possible cutting points generation heuristics in suggested. An AND/OR-graph approach, with used a hibrid strategy that combines Hill-Climbing and Depth-First techniques, in order to serach the graph, was used to solve this problem. Finally, results from this study and results presented in the literature are compared.