A indústria cosmética tem investido em tecnologias inovadoras na busca de maior eficácia de seus produtos. A Nanotecnologia tem sido utilizada com o propósito de desenvolver formulações de menor risco de irritação cutânea e que promovam a liberação modificada do componente ativo. Este trabalho teve como objetivo geral desenvolvimento, caracterização e avaliação de nanopartículas de ácido ursólico incorporadas em formulação cosmética. Nesta pesquisa, para determinar a eficiência de encapsulação do AU (ácido ursólico) livre e nas nanopartículas poliméricas, foi validada uma metodologia que empregou a CLAE (Cromatografia em fase Líquida de Alta Eficiência) e os resultados obtidos indicaram boa reprodutibilidade do método e concordância entre os resultados obtidos, sendo a metodologia empregada na avaliação do AU livre e nanoparticulado. As nanopartículas contendo AU apresentaram características de potencial estabilidade química, obtendo eficiência de encapsulação de 80% de AU para as nanopartículas poliméricas e 100% para os carreadores lipídicos nanoestruturados. A caracterização físico-química das nanopartículas poliméricas contendo AU foi realizada determinando-se diâmetro da partícula (353,4 ± 1,4 nm), índice de polidispersividade (0,106 ± 0,008) e potencial zeta (-35,6 ± 1,2 mV). Os resultados obtidos para os carreadores lipídicos nanoestruturados contendo AU nas formulações foram: tamanho de partícula entre 125,3±40,4 e 237,4±62,7 nm, índice de polidispersividade entre 0,01 e 0,38 e potencial zeta entre -20,5±9,2 e -50,7±9,5 mV. Os resultados obtidos indicaram estabilidade das nanopartículas desenvolvidas. O resultado relativo ao planejamento fatorial para otimização dos agentes tensoativos revelou modelo matemático de segunda ordem para a previsão de valores de potencial zeta em função das concentrações de SDS. Dessa forma, foi possível a preparação de carreador lipídico nanoestruturado contendo reduzida concentração de SDS e valor de potencial zeta menor que -40 mV. Por meio das técnicas de TG/DTG e DSC, observou-se que o AU se manteve estável nas diversas formas de apresentação. Formulações cosméticas contendo ácido ursólico livre (AUL), e incorporados a nanopartículas polméricas (AUE) e carreadores lipídicos nanoestruturados (AUC) foram submetidas a Avaliação Preliminar da Estabilidade e ao Teste Estabilidade Normal. Observou-se que o AUC obteve melhor estabilidade físico-química em comparação ao AUL tanto na variação de viscosidade como na variação do pH, além de ter obtido melhor estabilidade em relação a AUE na variação de pH x tempo. A partir dos resultados obtidos, a Formulação 2 foi selecionada para o teste de penetração cutânea. A avaliação da penetração cutânea in vitro do AU não apresentou tendência para favorecer o transporte da substância ativa para a fase receptora. A maior concentração de AU na pele foi obtida das amostras de AU livre + emulsão (65%) seguidas das amostras de CLN + emulsão (33%) e das NP + emulsão (20%). A penetração cutânea obteve resultado ideal, pois, por se tratar de nanopartículas contendo um componente ativo antioxidante na superfície da pele, se associado a um filtro solar, atuaria contra os radicais livres resultando na maior proteção contra a radiação ultravioleta. / The cosmetic industry has invested in innovative technologies in search of greater effectiveness of their products. Nanotechnology has been used with this propose to reduce the risk of skin irritation by promoting the modified release of the active component. This study had as main objective development, characterization and evaluation of ursolic acid nanoparticles incorporated in cosmetic formulation. In this research, to determine the entrapment efficiency of UA (ursolic acid) free and in polymeric nanoparticles, a methodology was validated using HPLC (high performance liquid chromatography) and the results indicated good reproducibility of the method and agreement between the results, the methodology employed could be assessed in the evaluation of free and UA nanoparticles. Nanoparticles containing UA showed characteristics of potential chemical stability obtaining entrapment efficiency of 80% for UA polymer nanoparticles and 100% for the nanostructured lipid carriers. The physicochemical characterization of polymeric nanoparticles containing UA was accomplished by determining the particle diameter (353.4 ± 1.4 nm), polydispersity index (0.106 ± 0.008) and zeta potential (-35.6 ± 1.2mV). The results obtained for the nanostructured lipid carriers containing UA formulations were: particle size between 125.3±40.4 and 237.4±62.7 nm, polydispersity index between 0.01 and 0.38, and zeta potential between -20.5±9.2 and -50.7±9.5 mV. The results indicated stability of the developed nanoparticles. The result for the factorial design for optimization of surfactant revealed a quadratic effect of the independent variable sodium dodecyl sulfate in zeta potential. Thus, it was possible to prepare nanostructured lipid carrier containing reduced concentrations of SDS and zeta potential value of less than -40 mV. By means of the techniques of TG/DTG and DSC, was observed that the UA remained stable. Cosmetic formulations containing free ursolic acid (AUL) and incorporated in polymeric nanoparticles (AUE) and nanostructured lipid carriers (AUC) were submitted to Preliminary Assessment Stability and Normal Stability Test. It was observed that the AUC obtained better physical and chemical stability compared to AUL on the variation of viscosity as on the pH variation, besides having obtained a higher stability compared to the AUE in the pH variation versus time. From the results obtained Formulation 2 was selected for the realization of the skin penetration test. The evaluation of the in vitro penetration of UA showed that ursolic acid remained on the skin surface. The dermal penetration showed no tendency to favor the transport of active substance to the receptor phase. The highest concentration of UA in the skin samples was obtained UA + free emulsion (65%) followed samples NLC + emulsion (33%) and PN + emulsion (20%). The skin penetration achieved optimal outcome because, as it is nanoparticles containing antioxidant active compound on the skin surface, if associated with a solar filter would act against free radicals resulting in greater protection against ultraviolet radiation.

Cette thèse propose, décrit et utilise un ensemble de techniques basées sur la microscopie à force atomique sous ultravide pour la cartographie simultanée, à l'échelle nanométrique, de la topographie de surface et des dynamiques temporelles des photo-porteurs. Ainsi, en contrôlant la dépendance du photo-potentiel de surface moyen mesuré par microscopie à force de sonde Kelvin en fonction de la fréquence de répétition d'une source lumineuse externe d'excitation, le dispositif expérimental permet d’accéder aux dynamiques temporelles du photo-potentiel de surface qui, à leur tour, permettent d'étudier les dynamiques des photo-porteurs sur une large gamme d'échantillons. Afin de permettre le processus de nano-imagerie bidimensionnelle, ces mesures sont acquises de manière répétée en enregistrant des courbes spectroscopiques en chaque point d’une grille prédéfinie. En utilisant une procédure d'ajustement mathématique automatique, les dynamiques temporelles des photo-porteurs sont extraites à partir des données expérimentales.Cet ensemble de nouvelles méthodes est utilisé pour l’étude de plusieurs types d'échantillons issus de différentes technologies photovoltaïques telles que des couches minces en silicium poly-cristallin à petits grains, des cellules de troisième génération à nano cristaux de silicium, des cellules photovoltaïques organiques et des cellules à base de matériaux de structure pérovskite. Dans chaque cas, on décrit les processus de recombinaison des photo-porteurs ainsi que leur lien avec la morphologie et la structuration du matériau. Enfin, les aspects techniques de ces nouvelles méthodes d’analyse sont présentés, ainsi que leurs limites, notamment celles concernant l'interprétation des résultats. / This thesis is directed towards the proposition and demonstration of a set of novel advanced atomic force microscopy based techniques under ultra-high vacuum conditions, enabling to map simultaneously the surface topography and the photo-carrier dynamics at the nanometre scale. In fact, by monitoring the dependence of the average surface photo-voltage measured with Kelvin probe force microscopy, as a function of the repetition frequency of a modulated excitation source, we will access the built-up and decay dynamics of the surface photo-voltage response which in turn will allows us to study the photo-carrier dynamics over a wide range of samples. In order to enable the 2-dimensional nano-imaging process, Kelvin probe force microscopy under modulated illumination measurements are acquired repeatedly over each point of a predefined grid area over the sample acquiring a set of spectroscopy curves. Then, using an automatic mathematical fit procedure, spectroscopy curves are translated into pixels of the photo-carrier dynamic time-constant images.Moreover, these set of novel techniques will be used to investigate the surface photo-voltage dynamics in several kinds of photovoltaic samples from different technological branches such as small grain polycrystalline silicon thin films, silicon nanocrystal-based third generation cells, bulk heterojunction donor-acceptor organic photovoltaics and organic-inorganic hybrid perovskite single crystal cells, discussing in each case the photo-carrier recombination process and its relation with the material’s structuration/morphology. Finally, technical aspects of these novel techniques will be discussed as well as their limitations and remaining open question regarding results interpretation.

Made available in DSpace on 2014-12-17T15:42:13Z (GMT). No. of bitstreams: 1 TiagoRC_DISSERT.pdf: 2194143 bytes, checksum: 2a20949c899c91ba3e574d7f71d319d4 (MD5) Previous issue date: 2012-04-11 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / Oxygen carriers are metal oxides which have the ability to oxidize and reduce easily by various cycles. Due to this property these materials are widely usedin Chemical-Looping Reforming processes to produce H2 and syngas. In this work supports based on MCM-41 and La-SiO2 were synthesized by hydrothermal method. After the synthesis step they were calcined at 550?C for 2 hours and characterized by TG, XRD, surface area using the BET method and FTIR spectroscopy. The deposition of active phase, in this case Nickel, took place in the proportions of 5, 10 and 20% by weight of metallic nickel, for use as oxygen carriers.The XRD showed that increasing in the content of Ni supported on MCM-41 resulted in a decrease in spatial structure and lattice parameter of the material. The adsorption and desorption curves of the MCM-41 samples exhibited variations with the increase of Ni deposited. Surface area, average pore diameter and wall density of silica showed significant changes , due to the increase of the active phase on the mesoporous material. By other hand, in the samples with La-SiO2 composition was not observed peaks characteristic of hexagonal structure, in the XRD diffractogram. The adsorption/desorption isotherms of nitrogen observed are type IV, characteristic of mesoporous materials. The catalytic test indicates that the supports have no influence in the process, but the nickel concentration is very important, because the results for minor concentration of nickel are not good. The ratio H2/O2 was close to 2, for all 15 cycles involving the test storage capacity of O2, indicating that the materials are effective for oxygen transport / Transportadores de oxig?nio s?o ?xidos met?licos que possuem a capacidade de oxidar e reduzir facilmente por diversos ciclos. Devido a essa propriedade estes materiais s?o bastante utilizados nos processos de Chemical-Looping Reforming para a produ??o de H2 ou g?s de s?ntese (H2 mais CO). Neste trabalho foram sintetizados os suportes MCM-41 e La-SiO2 pelo o m?todo hidrot?rmico. Os materiais resultantes foram calcinados a 550 ?C por 2 horas e, posteriormente, caracterizados por TG, DRX, ?rea superficial pelo m?todo BET e FTIR. Ap?s a caracteriza??o dos suportes foi feita a deposi??o da fase ativa (Ni) com as propor??es de 5, 10 e 20% em massa de n?quel met?lico, para aplica??o como transportadores de oxig?nio. As an?lises de DRX mostraram que o aumento do teor de Ni suportado em MCM-41 deu origem a uma diminui??o no ordenamento estrutural e no par?metro de rede do material. As amostras MCM-41 apresentaram varia??es quanto ?s curvas de adsor??o/dessor??o de nitrog?nio, ?rea superficial, di?metro m?dio de poros e espessura da parede de s?lica, em fun??o do aumento da fase ativa no material mesoporoso. Enquanto que nas amostras com La-SiO2 n?o se observou picos caracter?sticos da estrutura hexagonal, nos difratogramas de DRX. Entretanto, as curvas de adsor??o/dessor??o de nitrog?nio observadas s?o do tipo IV, caracter?stico de materiais mesoporosos. Os resultados dos testes dos transportadores indicam que o suporte n?o influenciou no processo catal?tico. A raz?o H2/O2 foi pr?xima de 2, durante todos os 15 ciclos envolvendo o teste de capacidade de armazenamento de O2 , indicando que os materiais s?o eficientes para o transporte de oxig?nio estrutural e no par?metro de rede do material. As amostras MCM-41 apresentaram varia??es quanto ?s curvas de adsor??o/dessor??o de nitrog?nio, ?rea superficial, di?metro m?dio de poros e espessura da parede de s?lica, em fun??o do aumento da fase ativa no material mesoporoso. Enquanto que nas amostras com La-SiO2 n?o se observou picos caracter?sticos da estrutura hexagonal, nos difratogramas de DRX. Entretanto, as curvas de adsor??o/dessor??o de nitrog?nio observadas s?o do tipo IV, caracter?stico de materiais mesoporosos. Os resultados dos testes dos transportadores indicam que o suporte n?o influenciou no processo catal?tico. A raz?o H2/O2 foi pr?xima de 2, durante todos os 15 ciclos envolvendo o teste de capacidade de armazenamento de O2 , indicando que os materiais s?o eficientes para o transporte de oxig?nio

A indústria cosmética tem investido em tecnologias inovadoras na busca de maior eficácia de seus produtos. A Nanotecnologia tem sido utilizada com o propósito de desenvolver formulações de menor risco de irritação cutânea e que promovam a liberação modificada do componente ativo. Este trabalho teve como objetivo geral desenvolvimento, caracterização e avaliação de nanopartículas de ácido ursólico incorporadas em formulação cosmética. Nesta pesquisa, para determinar a eficiência de encapsulação do AU (ácido ursólico) livre e nas nanopartículas poliméricas, foi validada uma metodologia que empregou a CLAE (Cromatografia em fase Líquida de Alta Eficiência) e os resultados obtidos indicaram boa reprodutibilidade do método e concordância entre os resultados obtidos, sendo a metodologia empregada na avaliação do AU livre e nanoparticulado. As nanopartículas contendo AU apresentaram características de potencial estabilidade química, obtendo eficiência de encapsulação de 80% de AU para as nanopartículas poliméricas e 100% para os carreadores lipídicos nanoestruturados. A caracterização físico-química das nanopartículas poliméricas contendo AU foi realizada determinando-se diâmetro da partícula (353,4 ± 1,4 nm), índice de polidispersividade (0,106 ± 0,008) e potencial zeta (-35,6 ± 1,2 mV). Os resultados obtidos para os carreadores lipídicos nanoestruturados contendo AU nas formulações foram: tamanho de partícula entre 125,3±40,4 e 237,4±62,7 nm, índice de polidispersividade entre 0,01 e 0,38 e potencial zeta entre -20,5±9,2 e -50,7±9,5 mV. Os resultados obtidos indicaram estabilidade das nanopartículas desenvolvidas. O resultado relativo ao planejamento fatorial para otimização dos agentes tensoativos revelou modelo matemático de segunda ordem para a previsão de valores de potencial zeta em função das concentrações de SDS. Dessa forma, foi possível a preparação de carreador lipídico nanoestruturado contendo reduzida concentração de SDS e valor de potencial zeta menor que -40 mV. Por meio das técnicas de TG/DTG e DSC, observou-se que o AU se manteve estável nas diversas formas de apresentação. Formulações cosméticas contendo ácido ursólico livre (AUL), e incorporados a nanopartículas polméricas (AUE) e carreadores lipídicos nanoestruturados (AUC) foram submetidas a Avaliação Preliminar da Estabilidade e ao Teste Estabilidade Normal. Observou-se que o AUC obteve melhor estabilidade físico-química em comparação ao AUL tanto na variação de viscosidade como na variação do pH, além de ter obtido melhor estabilidade em relação a AUE na variação de pH x tempo. A partir dos resultados obtidos, a Formulação 2 foi selecionada para o teste de penetração cutânea. A avaliação da penetração cutânea in vitro do AU não apresentou tendência para favorecer o transporte da substância ativa para a fase receptora. A maior concentração de AU na pele foi obtida das amostras de AU livre + emulsão (65%) seguidas das amostras de CLN + emulsão (33%) e das NP + emulsão (20%). A penetração cutânea obteve resultado ideal, pois, por se tratar de nanopartículas contendo um componente ativo antioxidante na superfície da pele, se associado a um filtro solar, atuaria contra os radicais livres resultando na maior proteção contra a radiação ultravioleta. / The cosmetic industry has invested in innovative technologies in search of greater effectiveness of their products. Nanotechnology has been used with this propose to reduce the risk of skin irritation by promoting the modified release of the active component. This study had as main objective development, characterization and evaluation of ursolic acid nanoparticles incorporated in cosmetic formulation. In this research, to determine the entrapment efficiency of UA (ursolic acid) free and in polymeric nanoparticles, a methodology was validated using HPLC (high performance liquid chromatography) and the results indicated good reproducibility of the method and agreement between the results, the methodology employed could be assessed in the evaluation of free and UA nanoparticles. Nanoparticles containing UA showed characteristics of potential chemical stability obtaining entrapment efficiency of 80% for UA polymer nanoparticles and 100% for the nanostructured lipid carriers. The physicochemical characterization of polymeric nanoparticles containing UA was accomplished by determining the particle diameter (353.4 ± 1.4 nm), polydispersity index (0.106 ± 0.008) and zeta potential (-35.6 ± 1.2mV). The results obtained for the nanostructured lipid carriers containing UA formulations were: particle size between 125.3±40.4 and 237.4±62.7 nm, polydispersity index between 0.01 and 0.38, and zeta potential between -20.5±9.2 and -50.7±9.5 mV. The results indicated stability of the developed nanoparticles. The result for the factorial design for optimization of surfactant revealed a quadratic effect of the independent variable sodium dodecyl sulfate in zeta potential. Thus, it was possible to prepare nanostructured lipid carrier containing reduced concentrations of SDS and zeta potential value of less than -40 mV. By means of the techniques of TG/DTG and DSC, was observed that the UA remained stable. Cosmetic formulations containing free ursolic acid (AUL) and incorporated in polymeric nanoparticles (AUE) and nanostructured lipid carriers (AUC) were submitted to Preliminary Assessment Stability and Normal Stability Test. It was observed that the AUC obtained better physical and chemical stability compared to AUL on the variation of viscosity as on the pH variation, besides having obtained a higher stability compared to the AUE in the pH variation versus time. From the results obtained Formulation 2 was selected for the realization of the skin penetration test. The evaluation of the in vitro penetration of UA showed that ursolic acid remained on the skin surface. The dermal penetration showed no tendency to favor the transport of active substance to the receptor phase. The highest concentration of UA in the skin samples was obtained UA + free emulsion (65%) followed samples NLC + emulsion (33%) and PN + emulsion (20%). The skin penetration achieved optimal outcome because, as it is nanoparticles containing antioxidant active compound on the skin surface, if associated with a solar filter would act against free radicals resulting in greater protection against ultraviolet radiation.

Denna studie syftar till att undersöka vilka förändringar som förväntas av en inkorporering av Förenta Nationernas barnkonvention i svensk lagstiftning. Sveriges riksdag röstade sommaren år 2018 igenom regeringens förslag om att inkorporera barnkonventionen, vilket innebär att konventionen blir svensk lag. Sverige har sedan ratificeringen år 1990 varit tvungna att följa barnkonventionens bestämmelser, dock har konventionen inte fått det genomslag som förväntats i landet. Regeringen anser att barnkonventionen genom en inkorporering kommer bidra till ett tydliggörande för barnens rättigheter. Studien kommer även granska och identifiera hur barnkonventionen ska inkorporeras, vilka insatser som regeringen har beslutat om och hur dessa ska genomföras. En inkorporering är dels önskvärd men även kritiserad, därför ska studien även analysera för vilka utmaningar och svårigheter som finns vid en inkorporering. Huvudproblemet som studien syftar till att diskutera är om inkorporeringen av barnkonventionen kommer vara tillräcklig för att luckorna i det barnrättsliga arbetet i Sverige ska tillgodoses. Syftet har besvarats genom intervjuer med sex personer som har kunskap om barnens rättigheter och information om dels den kommande inkorporeringen, dels de insatser som beslutats om samt de utmaningar som finns vid inkorporeringen av barnkonventionen. Resultatet visar att de förändringarna som intervjupersonerna förväntade sig av en inkorporering av barnkonventionen var både positiva och negativa. De positiva förväntningarna är att barnkonventionen får mer genomslag. Att barnets bästa kommer att prövas och att dem kommer att komma till tals i större utsträckning än tidigare. Ytterligare en positiv förändring är att Barnkonventionens kan bidra till en synvända för alla människor i samhället. Det vill säga, hur vi ser på barn, behandlar barn och pratar med barn. De negativa förväntningarna och utmaningarna vid en inkorporering är att konventionen kan uppfattas vag och att den i sig inte utgör en beslutsgrund. Det är därför viktigt att barnkonventionens bestämmelser fortsätts transformeras in i nationell lagstiftning. I intervjuerna uttrycktes även en oro för att regeringens ansvar i att se till att barnkonventionen följs förflyttas till rättstillämparen och att arbetet med att transformera konventionens bestämmelser stannar av. Studien identifierar även behovet av övriga insatser i form av kunskapslyft i skolan där barnen får lära sig om barnkonventionen och deras rättigheter och behovet av att regeringen fattar ett beslut om att tillträda tilläggsprotokoll 3. Det frivilliga tilläggsprotokollet utgör en möjlighet för barn att överklaga beslut som fattats i ärenden som rör dem till FN:s barnrättskommitté. / This study aims to investigate what changes are expected of the incorporation of the United Nation Convention on the Rights of the Child into Swedish legalisation. The Swedish Parliament voted in the summer of 2018 through the Government's proposal to incorporate the Convention into Swedish legislation through incorporation. Since the ratification in 1990, Sweden has had to comply with the provision of the Convention, but the Convention has not had the impetus that was expected in the country. The Government believes that the Convention of the Rights of the Child, through incorporation, will introduce a symbolic clarification of the rights of the children. The study will also research and identify how the convention will be incorporated, what interventions the government has decided on and how these will be implemented. Incorporation is partly desirable, but also criticized, therefore, the study will also analyse the challenges and difficulties encountered in the incorporation of the convention of the Rights of the Child into Swedish legislation. The main problem that the study aims to discuss is whether the incorporation of the Convention of the Rights of the Child will be sufficient to accommodate the gaps in child justice in Sweden.     The aim of the study as well as the research questions has been answered through interviews with six individuals who are experts in the children's rights and who have information on the upcoming incorporation, they also have knowledge about the interventions that have been made and the challenges involved in the incorporation of the Convention of the rights of the child.      The result of the study shows that the expected changes that the interviewees had from incorporating the Convention of the Rights of the Child into Swedish legalisation were both positive and negative. The positive expectation is that the Convention will get more impact. That the best interests of the child will be tested in decisions that concern them and that they will be able to express an opinion to a greater extent than before. The negative expectations and challenges of incorporation are that the convention can be perceived undetermined and in itself does not constitute a basis for decision-making. It is therefore important that the provisions of the Convention continue to be transformed into national law. The interviewees also expressed a concern that the government's responsibility to ensure compliance with the Convention might transferred to the legal experts and that the work on transforming the Convention's provisions contingently stops.     The study also identifies the need of knowledge of the Convention of the Rights of the Child among the children. This will contribute to the positive effect that children will understand that they are carriers of rights. Furthermore the interviewees criticise the government’s decision to not incorporate the third additional protocol, optional protocol of the convention on the rights of the child on a communication procedure.

Le sujet de cette thèse est l’analyse de la fiabilité des transistors bipolaires à hétérojonction SiGe:C et descircuits intégrés associés. Dans ce but, un modèle compact prenant en compte l’évolution des caractéristiquesdes transistors SiGe:C a été développé. Ce modèle intègre les lois de vieillissement des mécanismes dedéfaillance des transistors identifiés lors des tests de vieillissement. Grâce aux simulations physiques TCADcomplétées par une analyse du bruit basses fréquences, deux mécanismes de dégradations ont été localisés. Eneffet, selon les conditions de polarisation, des porteurs chauds se retrouvent injectés aux interfaces dutransistor. Ces porteurs chauds ont suffisamment d’énergie pour dégrader l’interface en augmentantprogressivement leurs densités de pièges. L’une des deux interfaces dégradées se situe au niveau del’’’espaceur’’ émetteur-base dont l’augmentation de la densité de piège dépend des porteurs chauds créés parionisation par impact. L’autre interface dégradée se situe entre le silicium et le STI dont l’augmentation dedensité de pièges dépend des porteurs chauds générés par ionisation par impact et/ou par génération Auger.En se basant sur ces résultats, une loi de vieillissement a été incorporée dans le modèle compact HICUM. Enutilisant ce modèle, l’étude de l’impact des mécanismes de défaillance sur un circuit amplificateur faible bruit aété menée. Cette étude a montré que le modèle compact intégrant les lois de vieillissement offre la possibilitéd’étudier la fiabilité d’un circuit complexe en utilisant les outils de conception standard permettant ainsi dediminuer le temps de conception global. / The SiGe:C HBT reliability is an important issue in present and future practical applications. To reduce the designtime and increase the robustness of circuit applications, a compact model taking into account aging mechanismactivation has been developed in this thesis. After an aging test campaign and physical TCAD simulations, onemain damage mechanism has been identified. Depending on the bias conditions, hot carriers can be generatedby impact ionization in the base-collector junction and injected into the interfaces of the device where trapdensity can be created, leading to device degradation. This degradation mechanism impacting the EB/spacerinterface has been implemented in the HICUM compact model. This compact model has been used to performreliability studies of a LNA circuit. The CPU simulation time is not impacted by the activation of the degradationcompact model with an increase in computation time lower than 1%. This compact model allows performing areliability analysis with conventional circuit simulators and can be used to assist the design of more robustcircuits, which could help in reducing the design time cycle. / L’affidabilità dei transistori a eterogiunzione SiGe:C è un aspetto molto importante nella progettazione circuitale,sia per le tecnologie attuali che per quelle in fase di sviluppo. In questo lavoro di tesi è stato sviluppato un modellocompatto in grado di descrivere i principali meccanismi di degrado, in modo da contribuire alla progettazione dicircuiti relativamente più robusti rispetto a tali fenomeni, ciò che potrebbe favorire una riduzione dei tempi diprogetto. A seguito di una campagna sperimentale e di un’analisi con tecniche TCAD, è stato identificato unmeccanismo principale di degrado. In particolari condizioni di polarizzazione, i portatori ad elevata energiagenerati per ionizzazione a impatto nella regione di carica spaziale, possono raggiungere alcune interfacce deldispositivo e ivi provocare la formazione di trappole. Solo la generazione di trappole relativa allo spaceremettitore-base è stata considerata nella formulazione del modello, essendo il fenomeno più rilevante. Ilmodello è stato utilizzato per effettuare alcuni studi di affidabilità di un amplificatore a basso rumore. Il tempocomputazionale non è significativamente influenzato dall’attivazione del modello di degrado, aumentando solodell’1%. Il modello sviluppato è compatibile con i comuni programmi di simulazione circuitale, e può essereimpiegato nella progettazione di circuiti con una migliore immunità rispetto ai fenomeni di degrado,contribuendo così a un riduzione dei tempi di progetto.

Transport across the membrane of a cell is of crucial importance for cellular functions. The solute carrier family,SLC38 is a family of membrane proteins that transports various substances through the membrane and thusperforms many physiologically important functions, for example, transport of glutamine from astrocyte toneurons in the central nervous system. In this paper, we demonstrate that one of the transporters in this familynamed SLC38A6 forms several protein complexes with a variety of proteins in the membrane and in synapticvesicles, suggesting that SLC38A6 is involved in the synaptic release of neurotransmitters in synapses. Weperformed sensitive protein interaction analysis between the protein of interest and a variety of proteinsexpressed at different sites in the neuronal cell. We showed that SLC38A6 interacts with proteins in the cellmembrane as well as in the membrane of synaptic vesicles. The current theory is that SLC38A6 interact withthese proteins when the synaptic vesicles are in close proximity with the cell membrane during the release of theneurotransmitters.

This thesis focuses on decision support for regional LTL carriers. The basic operating characteristics of regional LTL carriers are similar to those of national LTL carriers, i.e., they operate linehaul networks with satellites, breakbulks, and relays to consolidate freight so as to be able to cost-effectively serve their customers. However, there are also key differences. Most importantly, because the area covered by a regional carrier is smaller, a regional carrier handles less freight (sometimes significantly less) and therefore typically has fewer consolidation opportunities, which results in higher handling and transportation costs per unit of freight. Consequently, competing with national carriers on price is difficult. Therefore, to gain or maintain market share, regional carriers have to provide better service. To be able to provide better service, regional carriers have to be more dynamic, e.g., they have to be able to deviate from their load plan when appropriate, which creates challenges for decision makers. Regional carriers deliver about 60% of their shipments within a day and almost all of their shipments within two days. Furthermore, most drivers get back to their domicile at the end of each day. Therefore, the focus of the thesis is the development of effective and efficient decision models supporting daily operations of regional LTL carriers which provide excellent service at low cost. This thesis presents an effective solution approach based on two optimization models: a dynamic load planning model and a driver assignment model. The dynamic load planning model consists of two parts: an integer program to generate the best paths for daily origin-destination freight volumes and an integer program to pack freight into trailers and trailers into loads, and to determine dispatch times for these loads. Techniques to efficiently solve these integer program solution are discussed in detail. The driver assignment model is solved in multiple stages, each stage requiring the solution of a set packing models in which columns represent driver duties. Each stages determines admissible driver duties. The quality and efficiency of the solution approach are demonstrated through a computational study with real-life data from one of the largest regional LTL carriers in the country. An important "technique" for reducing driver requirements is the use of meet-and-turn operations. A basic meet-and-turn operation involves two drivers meeting at a location in between terminals and exchange trucks. A parking lot or a rest area suffices as a meet-and-turn location. This ensures that drivers return to the terminal where they started. More sophisticated meet-and-turn operations also exist, often called drop and hook operations. In this case, drivers do not exchange trucks, but one of their trailers. The motivation in this case is not to get drivers back to their domicile, but to reduce load- miles. The thesis presents analytical results quantifying the maximum benefits of using meet and turn operations and optimization techniques for identifying profitable meet-and-turn opportunities.

This dissertation investigates the relationship of competition and firms' price responses, by analyzing: i) whether new entry reduces price discrimination, ii) when incumbents reduce price discrimination preemptively in response to the threat of entry, and iii) how competition increases prices. The dissertation consists of three independent essays addressing each of the above questions. The first two essays present an empirical analysis of the airline industry and the third essay presents a theoretical analysis of the credit card industry. In the empirical study of the relationship between competition and firms' pricing in the airline industry, I emphasize the importance of distinguishing the equilibrium behaviors with respect to different market characteristics. Major airlines can price discriminate differently in a market where they compete with low-cost carriers comparing to in another market where they don't, and also they can respond dfferently to the threat of entry depending on whether they are certain about the rival's future entry. The study reveals that competition has a positive effect on price discrimination in the routes where major airlines compete against one anther. In these routes, competition reduces lower-end prices to a greater extent than upper-end prices. In contrast, an entry by low-cost carriers results in a significant negative relationship between competition and price discrimination. Thus, the opposite results in the literature are both evident in the airline industry, and it is very important to identify the different forces of competition on price discrimination. Firms can respond to potential competition as well as actual competition. So, I extend the study to the relationship of potential competition and price discrimination, specially in cases where major airlines compete against one another while facing Southwest's threat of entry. I also attempt to suggest major airlines' motives of reducing price discrimination preemptively. The results of the study suggest that incumbents reduce price dispersion when it is possible to deter the rival's entry and that the potential rival discourages incumbents from deterring entry by announcing before its beginning service. Finally, I examine when competition can increase prices in a market, by analyzing the issuing side of the credit card industry. This industry is characterized by a two-sided market with a platform. Under the no-surcharge rule that restricts merchants to set the same price for cash and card purchases, the equilibrium interchange fee increases with competition. This occurs because issuers can compensate losses from competing on the issuing side by collectively increasing the interchange fee. As a result, limiting competition may improve social welfare when the interchange fee is higher than the social optimal level. In contrast, in the absence of the no-surcharge rule, the analysis shows that competition always improves social welfare by lowering the price of the market.

Functional Dendritic Structures from Bile Acids: Supramolelcular Hosts, Light Harvesters and Drug Carriers Chapter 1. An Overview of Functional Dendrimers. Dendrimers are welldefined, hyperbranched macromolecules that are prepared by highly controlled iterative methodologies. The ability to modulate the size, molecular weight, chemical functionalities and the position and number of functional groups in dendrimers make them promising candidates for a wide variety of applications. In this chapter, three areas 1) hostguest chemistry 2) light harvesting and 3) drug delivery, where dendrimers are increasingly finding applications, are discussed with selected examples. Chapter 2. Hydroxyl Terminated Dendritic Oligomers from Bile Acids: Synthesis and Properties. Bile acids are excellent building blocks for dendritic construction because of their many interesting features. They are readily available, chiral, facial amphiphiles with complementary functionalities. Moreover, due to the large size of the bile acid units, a dendritic structure consisting of only a few such repeat units can have an extended structure with multiple functionalizable groups. (figure 1) The high reactivity of the chloroacetyl group has been exploited for the synthesis of bile acid based first and second-generation dendrons with glycolate linkers and multiple hydroxyl groups. The synthesis involves only a few steps and avoids the use of protecting groups for the terminal hydroxyl groups. The synthesis of a bile acid tetramer is shown here as an example (Figure 1). Carboxyl protected cholic acid was reacted with chloroacetylchloride to generate the trischloroacetylated derivative. This compound on reaction with excess of sodium cholate generated the tetramer with nine hydroxyl groups via displacement of the chlorides. In order to synthesize higher generation dendritic structures, perchloroacetylated firstgeneration dendrons were first synthesized. These were subsequently reacted with excess of sodium deoxcholate to generated secondgeneration dendrons with multiple hydroxyl groups (Figure 2). All the compounds were characterized by H NMR, C NMR, IR, ESIMS/MALDI-TOF, HPLC and elemental analysis(wherever possible) Figure 2. Structure of tridecamer. These dendritic structures with facially amphiphilic bile acid backbones on the periphery were able to solubilize cresol red, a hydrophilic dye, in a nonpolar solvent, thus exhibiting reverse micellar characteristics. Chapter 3. Multiple Naproxen Appended Bile Acid Dendrimers as Light Harvesters and Drug Carriers. Part I. Synthesis and Characterization. Using the same synthetic strategy as in Chapter 2, bile acid based dendritic structures appended with multiple bioactive (S)naproxens were generated as potential drug carriers. The construction of these dendrimers was accomplished using per(chloroacetylated) bile acid dendrons and conveniently displacing all the chlorides with naproxen units. Since naproxen is photoactive with a high fluorescence quantum Figure 3. Structures of secondgeneration dendrimers and a monomer with multiple naproxens. yield, the photophysical properties of these multichromophoric dendrimers could be further explored (Figure 3). By functionalizing the carboxyl group on the side chain with an anthracenyl moiety the energy transfer properties of these dendrimers could be studied. In this section the synthesis of first and secondgeneration dendritic structures with multiple naproxen units at the periphery and benzyl/anthracenyl moiety on the side chain are described (Figure 3). Model compounds using monomeric bile acid units were synthesized for comparison with the dendritic structures. All the compounds were characterized by H NMR, C NMR, IR, ESIMS/MALDITOF, HPLC and elemental analysis (wherever possible). Part II: Absorption, Fluorescence and Intramolelcular Energy Tranfer Studies. Absorption studies showed that the molar extinction coefficients increase linearly with increasing number of naproxen units and the absorption spectra of anthracenyl moiety remain unchanged in all the dendritic systems. These indicated the absence of ground state interaction between the chromophores. In the 275-290 nm absorption region, the molar extinction coefficient of naproxen is much greater than that of the 9-anthracenylmethyl chromophore. Hence excitation in this region would mainly excite the naphthalene chromophore. Upon excitation at 275 nm, there was predominant emission from the anthracenyl moiety in the dendritic structures (containing both chromophores) and the fluorescence intensity increased with increasing number of naproxens(Figure4). This indicated that the dendrimers act as efficient light harvesters with energy transfer from naproxen to anthracene (intramolecular nature of the energy transfer was confirmed through control experiments). (Figure 4: Refer PDF File) The fluorescence and energy-transfer properties were further investigated by time-resolved fluorescence spectroscopy. The presence of fast decay component(s) in the naproxen decay in dendritic structures (containing both chromophores) indicates that its fluorescence is quenched in the presence of anthracene due to energy transfer ((λex 275 nm, λem 350 nm (Figure 5). This was further confirmed by monitoring the fluorescence of the sensitized anthracenyl chromophore (λex 275 nm, λem 436 nm) which exhibited a fast rise comparable to he quenched naproxen lifetime(s). The efficiency of energy transfer was estimated by donor quenching by both steadystate and timeresolved techniques. The dendritic structures exhibited high energy transfer efficiencies (~ 70 – 90 %) with the net efficiency decreasing from the first to second-generation. Part III. In vitro Study of Hydrolysis of Naproxen Appended Bile Acid Prodrugs by Chemical and Enzymatic Methods. The naproxen appended bile acid dendrimers consist of hydrolyzable ester and glycolate linkers. Hence the chemical stability and enzymatic degradation with possible release of naproxen was studied. Two compounds, monomer appended with two naproxens and trimer with four naproxens have been used for the initial investigations (Figure 6). The compounds were found to be highly stable towards chemical hydrolysis and did not show any hydrolysis in phosphate buffer, pH = 7.4 even after 7 days. Since the compounds were not soluble in water, Arabic gum and TritonX were used for emulsification. Figure 6. Structures of monomer and trimer. (Refer PDF File) The enzymatic hydrolysis of the compounds was then studied using Candida Rugosa Lipase. In both cases, there was slow hydrolysis of the substrate and intermediates were formed (with release of free naproxen) which were detected by HPLC (reverse phase column with a UV detector). The trimer underwent much slower hydrolysis compared to the monomer. The intermediates were characterized by absorption and mass (ESIMSQTOF) spectrometry.