Taking into account the technological demand for the controlled preparation of atomically precise graphene nanoribbons (GNRs) with well-defined properties, the present thesis is focused on the investigation of the role of the underlying metal substrate in the process of building GNRs using bottom-up strategy and on the changes in the electronic structure of GNRs induced by the GNR-metal interaction. The combination of surface sensitive synchrotron-radiation-based spectroscopic techniques and scanning tunneling microscopy with in situ sample preparation allowed to trace evolution of the structural and electronic properties of the investigated systems. Significant impact of the substrate activity on the growth dynamics of armchair GNRs of width N = 7 (7-AGNRs) prepared on inert Au(111) and active Cu(111) was demonstrated. It was shown that unlike inert Au(111) substrate, the mechanism of GNRs formation on Ag(111) and Cu(111) includes the formation of organometallic intermediates based on the carbon-metal-carbon bonds. Experiments performed on Cu(111) and Cu(110), showed that a change of the balance between molecular diffusion and intermolecular interaction significantly affects the on-surface reaction mechanism making it impossible to grow GNRs on Cu(110). It was demonstrated that deposition of metals on spatially aligned GNRs prepared on stepped Au(788) substrate allows to investigate GNR-metal interaction using angle-resolved photoelectron spectroscopy. In particular intercalation of one monolayer of copper beneath 7-AGNRs leads to significant electron injection into the nanoribbons, indicating that charge doping by metal contacts must be taken into account when designing GNR/electrode systems. Alloying of intercalated copper with gold substrate upon post-annealing at 200°C leads to a recovery of the initial position of GNR-related bands with respect to the Fermi level, thus proving tunability of the induced n-doping. Contrary, changes in the electronic structure of 7-AGNRs induced by the deposition of Li are not reversible.  It is demonstrated that via lithium doping 7-AGNRs can be transformed from a semiconductor into a metal state due to the partial filling of the conduction band. The band gap of Li-doped GNRs is reduced and the effective mass of the conduction band carriers is increased.

The Wing Trawling System (WTS) was tested as an alternative to traditional shrimp capture methods in the Gulf. Compared to an otter trawl, this trawl was conceived to reduce bycatch, retain shrimp catch, and minimize seafloor disturbance. Through seventy-one paired tows, the WTS was assessed against a standard otter trawl. The WTS was found to reduce bycatch by 63-65% and reduce shrimp catch by 30-35%. Additionally, I measured the depth of the scars produced by both trawls and quantified the turbidity of the plumes behind them. The scars left by the WTS and the otter trawl were between 9.9 cm-13.6 cm. The turbidity behind the WTS was 18.6 NTU, while the turbidity behind the otter trawl was 206.8 NTU. In conclusion, the WTS offers an alternative to an otter trawl that reduces bycatch and the impact trawling has on the seafloor but results in a significant amount of shrimp loss.

Microfranchising is emerging as a potentially powerful strategy for reaching the enormous markets at the base of the pyramid (BOP). Microfranchising also represents an effective and sustainable way to contribute to poverty alleviation and economic growth. However, we know little about how organizations maneuver contradictory forces as they use this innovative business model to engage the BOP. To address this gap, I offer a longitudinal case study of an emerging microfranchise effort by a successful Mexican agribusiness—one whose ambitions to continue growing were challenged by multinational agrochemicals suppliers. As this project shows, companies and BOP markets can realize mutual benefits from a value co-creation strategy. Specifically, I adopted a dialectical approach to analyze the tensions and competing forces that arose as business managers and local BOP distributors and producers collaborated in this emerging microfranchising venture. As a result, the research offers three contributions. First, it provides a detailed empirical account of how contradictory forces shaped the Mexican agricultural firm’s implementation of microfranchising to engage with BOP farmers. Second, it presents a conceptual synthesis that describes the major contradictory forces a company faces as it implements microfranchising as part of its BOP strategy. Finally, it offers lessons for how business managers can maneuver contradictory forces to co-create value with the BOP through microfranchising.

La spectrométrie de masse est une méthode d’analyse qui permet de travailler sur une large gamme d’échantillons. Elle est utilisée dans de nombreux domaines de recherche comme la chimie analytique, la protéomique, la lipidomique et la métabolomique…Dans un premier temps, mon travail s’est focalisé sur le développement d’une méthode indépendante d’analyse de données par spectrométrie de masse à transformée de Fourier bidimensionnelle. Pour augmenter la résolution en première dimension, une analyse FT-ICR 2D avec un échantillonnage non uniforme (NUS) a été développée. L’augmentation de la résolution dans la première dimension a permis l’obtention d’une haute résolution pour les ions précurseurs. La FT-ICR 2D a été utilisée avec succès pour l’analyse de triacylglycérols contenus dans du plasma mais aussi pour l’analyse d’échantillons archéologiques.Dans un second temps, une stratégie protéomique conjointe bottom-up et top-down a été appliquée à l’analyse d’échantillons archéologiques et paléontologiques à partir d’ossements ou de céramiques. Le développement d’une méthodologie bottom-up, a permis à partir d’ossements archéologiques d’espèces inconnues l’identification des protéines et leurs modifications chimiques. Cet ossement a pu être attribué comme appartenant à l’espèce Homo sapiens. Une analyse top-down a été utilisée pour l’analyse d’échantillons archéologiques. Pour la première fois, une protéine (la caséine de lait) a été identifiée dans un échantillon archéologique d’amphore de l’époque de l’empereur Claude (1er siècle de notre ère) grâce la détection de grands fragments de caséine. / Mass spectrometry is a method of analysis which works on a wide range of sample types. It is used in many research fields such as analytical chemistry, proteomics, lipidomics and metabolomics...Firstly, my work was dedicated to the development of an independent data analysis methodology based on two-dimensional Fourier transform mass spectrometry. For increasing the resolution on the first dimension a 2D FT-ICR analysis with non-uniform sampling was developed. The resolution increase in the first dimension leading to high resolution for the precursor ions. The 2D FT-ICR has been successfully applied for the analysis of triacylglycerol contained on plasma and also for archaeological samples. This methodology led to 2D maps allowing a rapid classification of plants or animals samples.Secondly, a joint bottom-up and top-down proteomics strategy was applied for the analysis of archaeological and paleontological samples from bones or ceramics. The development of a bottom-up methodology, allowed the identification of proteins and their chemical modifications from archeological bones. These bones have been attributed to Homo sapiens. The development of a top-down methodology was applied to the analysis of archaeological ceramic. For the first time, a protein (milk casein) was identified in an archaeological sample of an amphora from Claudius emperor era (1st century A.D) via the detection of large fragments of casein. This first application of the top down proteomics showed that new information can be provided such as the in situ molecular degradation.

A benthic environments classification system is devised from digital interpretations of multi-spectral IKONOS satellite imagery for 1,360 km2 of the carbonate platform and presented in a comprehensive digitized map. The classification scheme is designed as a 7th order hierarchical structure that integrates 5 Physiographic Realms, 24 Morphodynamic Zones, 11 Geoforms, 39 Landforms, 6 dominant surface sediment types, 9 dominant biological covers and 3 densities of biological covers for the description of benthic environments. Digital analysis of the high-resolution (4 m) IKONOS imagery employed ESRI's ArcMap to manually digitize 412 mapping units at a scale of 1:6,000 differentiated by spectral reflectance, color tones, and textures of seafloor topologies. The context of each morphodynamic zone is characterized by the content and areal distribution (in km2) of geomorphic forms and biological covers. Over 58% of the mapping area is occupied by sediment flats, and seagrasses are colonized in almost 80% of the topologies. / by Jacob Thomas Steinle. / Thesis (M.S.)--Florida Atlantic University, 2011. / Includes bibliography. / Electronic reproduction. Boca Raton, Fla., 2011. Mode of access: World Wide Web.

O reservatório de Biritiba-Mirim (SP), um dos reservatórios do Sistema Produtor Alto Tietê, fornece água para aproximadamente 4 milhões de habitantes, principalmente para o leste da Região Metropolitana de São Paulo. Por localizar-se em uma região com grande pressão antrópica, o presente estudo objetivou a determinação de parâmetros físicos e químicos de água e de sedimentos de fundo em duas áreas a leste do reservatório de Biritiba-Mirim (SP), uma com atividade antrópica agrícola e outra em área protegida por mata ciliar. As amostras foram realizadas em número que permitiram um diagnóstico seguro da condição dessa área do reservatório. Nos mesmos locais foram amostradas alíquotas de água e sedimentos de fundo para análises químicas totais do conteúdo de elementos, buscando associar com compostos de degradação de rocha versus compostos utilizados em atividade agrícola, cinco pontos na área antrópica agrícola, cinco pontos na área protegida por mata ciliar e dois pontos, próximos a nascente do ribeirão Biritiba-Mirim. Os parâmetros utilizados para delimitar o padrão de qualidade, foram balizados pelos critérios do CONAMA e CETESB. Os resultados obtidos evidenciaram diferenças significativas nos parâmetros físico-químicos da água e dos sedimentos de fundo, entre as amostras realizadas nas áreas. Para água, mesmo que alguns resultados se apresentaram acima do padrão de qualidade, no ponto com proteção da mata ciliar, é evidente a presença de valores mais elevados dos elementos químicos analisados na área de estudo denominada antrópica agrícola. Para sedimentos de fundo, nenhum elemento químico analisado ultrapassou os padrões máximos de qualidade estabelecidos pelas legislações, e também se apresentaram mais elevados na área denominada antrópica agrícola, comparados com a área com proteção de mata ciliar. Essa observação também é válida quando os dados são comparados pela média de cada área. Comprovando que mesmo alguns elementos químicos se encontram presentes na composição do solo do Complexo Embu e também nos agroquímicos, a importância da proteção da mata ciliar e desse estudo. / Mining projects require large amount of capital investment and most cases spend long periods of implementation, which make them extremely susceptible to several sources of uncertainty. Such uncertainties commonly tend to decrease along the project development. The present study aims to correlate the uncertainties associated to the grade model of the Sequeirinho copper mine with the amount of capital investment that has been spent along different geological surveys. Sequeirinho site is included in the context of Sossego Mine Complex, located in Canaã dos Carajás (PA, Brazil). Initially, 100 simulations were carried out for each lithologic domain in each drilling campaign (pre-1998, 1999, 2000, 2002 and 2003) using sequential Gaussian simulation conditioned to the sample, resulting in 1,400 possible scenarios. Three indexes were calculated for the uncertainty analysis: conditional variance, conditional coefficient variance and interquartile range. Finally, the evaluation of capital investment was elaborated from the costs estimated for drilling and chemical analysis. Since pre-1998 drilling campaign, deposit average grades have showed a trend to get closer to the possible real values observed in the final research surveys. In 2000, there was the biggest capital investment (about R$ 28 millions) and the uncertainty reduction has reached the maximum level of 15%. Investments performed in drilling programs after 2000 were around R$ 9 million (around 12,000 meters of drill holes), but the uncertainty reduction was not significant. Therefore, such investments might be used to discover new targets. Besides the correlation of uncertainty reduction and amount of capital investment, the main focus of this study, the uncertainty of geological model and the drillhole locations are important variables to be considered in investment analysis of geological survey.

Thesis advisor: John E. Ebel / This research describes a method to carry out quantitative analyses of sub-seabed sediments using high-resolution chirp seismic profiles in order to estimate the properties of subsurface sediments. The method identifies significant sedimentary interfaces, extracts them from the seismic record, and measures the inelastic attenuation coefficients (k) of the sedimentary layers. The k values and their variations with increasing depth of sediments are indicative of the amount of compaction of the sediment. The k values are correlated with borehole lithology to provide a relationship between k measurements and local borehole lithology. Once determined for an area, the correlation can be applied to other seismic records from the area to analyze sedimentary properties even if no borehole lithology is locally available. / Thesis (MS) — Boston College, 2016. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Earth and Environmental Sciences.

A técnica geofísica da eletrorresistividade adaptada para ambientes aquáticos, com a tecnologia que hoje temos à disposição, mostra-se bastante promissora e de grande produtividade tanto na coleta dos dados de campo como no reconhecimento de feições de interesse do substrato, possibilitando ainda a liberdade de se adquirir tais informações em perfis subaquáticos contínuos em quaisquer trechos navegáveis de rios e lagos e, eventualmente de mares. Neste contexto, esta dissertação abordou a aplicabilidade desta técnica, com a utilização de modernos equipamentos e acessórios adaptados para trabalhos em lâmina d\'água, onde foram executados e estudados os procedimentos de campo, processamentos e integração dos dados coletados, além da verificação da consistência dos resultados obtidos através da realização de linhas de estudos paralelas e também ortogonais. Os testes de aplicação da técnica foram realizados nas águas do rio São Francisco, mais precisamente em seu trecho que faz divisa dos estados da Bahia e Pernambuco, região nordeste do Brasil, local este que também tem sido objeto de estudos para o Projeto do Aproveitamento Hidrelétrico Riacho Seco, pertencentes à empresa Companhia Hidro Elétrica do São Francisco (CHESF), responsável por diversos estudos e desenvolvimentos desta região, notadamente dos recursos hídricos do baixo São Francisco. Os trabalhos de campo lançaram mão do uso de embarcação para transportar e arrastar, na superfície da água, um cabo multi-eletrodo de imageamento geoelétrico, especialmente desenvolvido para tais fins, bem como todos os equipamentos integrados a saber: equipamento GPS de navegação em ambientes aquáticos, eco-batímetro de dupla freqüência adaptado na embarcação, eletrorresistivímetro multicanal e notebook com software específico para o gerenciamento de todas as operações e dados. Os resultados mostraram que foi possível mapear a fisiografia do leito do rio bem como identificar e delimitar anomalias geofísicas compatíveis a prováveis ocorrências de depósitos de sedimentos assim como feições típicas de contatos litológicos e mesmo de estruturas do tipo alteração/fraturamento no interior dos materiais do subfundo do rio. / The electric tomography geophysical technique adapted for aquatic environment, with the modern technology available nowadays, reveals itself sufficiently promising and of great productivity both in the field data collection and in the recognition of aspects of interest of the substratum. It is possible to make the data acquiring in any navigable stretches of rivers, lakes and some seas. In this context, this paper approached the applicability of this technique, with the use of modern equipment and accessories for works in the water. The field procedures, the data processing and integration of the data collection are discussed considering the acquisition of a great amount of data both parallel and orthogonal to the river. The application tests of the technique were conducted in the river San Francisco, in the region of the border of the states of Bahia and Pernambuco, northeast region of Brazil. This area was selected because it has been subject of studies to install a hydroelectric plant (Riacho Seco), owned by the Companhia Hidro Elétrica do São Francisco (CHESF). To perform the field works a boat was used to carry and drag, in the surface of the water, a multi-electrode cable of electric tomography, especially developed for such purposes, as well as all the integrated equipment namely: GPS especially designed for navigation in aquatic environments, adapted fathometer of double frequency in the boat, multichannel eletrorresistivímeter and notebook with specific software that managed all the operations and data. The results had shown that it was possible to map the fisiography of the riverbed as well as identifying and delimiting geophysical anomalies compatible to the probable occurrences of deposits of sediments as well as typical lithologic contacts and structures like weathering and fractures in the underground materials in the bottom of the river.

Essa dissertação teve como objetivo principal comparar parâmetros físicos e químicos da água e sedimentos de fundo em dez pontos delimitados do reservatório de Biritiba-Mirim, uma próxima à atividade agrícola e outra em que havia proteção de mata nativa. Como objetivo secundário, avaliar o uso e ocupação do solo no entorno do reservatório, utilizando imagens obtidas por sensoriamento remoto e também, discutir os parâmetros utilizados para delimitar a qualidade da água e sedimentos de fundo balizados pelos critérios do CONAMA, CETESB e MINISTÉRIO DA SAÚDE. A qualidade da água e sedimentos de fundo do reservatório foi determinada com base na coleta e análise laboratorial das amostras. Os resultados obtidos evidenciam variações nos parâmetros físico-químicos da água, pH e OD. As amostras CAL estão dentro dos valores referenciados pelos critérios estudados, mas algumas amostras CAS e os pontos de referência apresentaram os elementos alumínio, ferro e manganês em concentração acima do valor permitido pelas normativas em questão. As amostras CAL apresentaram-se mais com maior quantidade dos elementos químicos: fósforo, enxofre, potássio, manganês, cobre, zinco e chumbo do que as amostras CAS. Nas duas amostras retiradas do ponto de referência, o esperado era não encontrar os elementos químicos fósforo, enxofre e cobre. A análise das imagens de uso e ocupação do solo por sensoriamento remoto exibiu um aumento considerável da área de horticultura, ao mesmo tempo que apresentou diminuição das áreas cobertas de vegetação. Conclui-se que a alteração do pH e OD, assim como a presença de alumínio, ferro e manganês em concentrações acima do valor permitido na amostras CAS e ponto referência da água, pode estar relacionado ao despejo de aditivos agrícolas. Pode ser que devido a presença e quantidade de elementos químicos presentes no sedimento de fundo não haja comprometimento ambiental. Para evitarmos o comprometimento da água e solo dos reservatórios destinados a captação de água e, consequentemente, o desabastecimento das grandes cidades, como o que vem acontecendo nos anos de 2014 e 2015, deve haver uma melhor gestão dos recursos hídricos, que proiba o manejo inadequado do solo e que proteja as áreas de mananciais e a mata ciliar do entorno dos reservatórios. / This dissertation aimed to compare physical and chemical parameters of water and bottom sediments in ten delimited points Biritiba-Mirim reservoir, one next to agriculture and one where there were native forest protection. As a secondary objective, to evaluate the use and occupation of land around the reservoir, using images obtained by remote sensing, and also discuss the parameters used to define the quality of water and bottom sediments marked by CONAMA criteria, CETESB and MINISTRY OF HEALTH. The water quality and bottom sediments was determined based on the collection and laboratory analysis of samples that were sent for chemical analysis. The results show variations in physical and chemical parameters of water, pH and OD. The CAL samples are within the range referenced by the criteria studied, but some CAS samples and reference samples presented the elements aluminum, iron and manganese in concentrations above the amount permitted by the regulations in question. The CAL samples that had become more enriched by chemical elements phosphorus, sulfur, potassium, manganese, copper, zinc and lead than CAS samples. In both samples taken from the reference point, it wasn\'t expected to find chemical elements phosphorus, sulfur and copper. The analysis of land use and occupation by remote sensing images showed a considerable increase in the horticultural area, while presented decrease in areas covered by vegetation. It is concluded that the change in pH and OD, as well as the presence of aluminum, iron and manganese in concentrations above the permitted value in the CAS sample and reference point of water, may be related to the presence of agricultural additives. It may be that due to the presence and amount of chemical elements present in the bottom sediment there is no environmental impairment. To avoid compromising the water and soil of the reservoires intended for the abstraction of water and hence the shortage of large cities such as what happened in the years 2014 and 2015, there should be a better management of water resources, which prohibit inadequate management of soil and protect the watershed areas and riparian forest surrounding the reservoirs.

Recent language policy and planning research reveals how policy-makers endorse the interests of dominant social groups, marginalise minority languages and perpetuate systems of sociolinguistic inequality. In the Castilian-dominated Galician linguistic landscape, this study examines the rise of grassroots level actors or agents (i.e. parents, family members, and other speakers of minority Galician) who play a significant role in interpreting and implementing language policy on the ground. The primary focus of this study is to investigate the impact of top-down language policies inside home domain, it looks at how the individual linguistic practices and ideologies of Galician parents act as visible and/or invisible language planning measures influencing their children’s language learning. However, these individual linguistic ideologies and language management decisions are difficult to detect because they are implicit, subtle, informal, and often hidden from the public eye, and therefore, frequently overlooked by language policy researchers and policy makers. Drawing from multiple ethnographic research methods including observations, in-depth fieldwork interviews, focus group discussions and family language audits with thirty-two Galician parents, this study attempts to ascertain whether these parents can restore intergenerational transmission of Galician and if their grassroots level interrogation of the dominant discourse could lead to bottom-up language policies.