From the Proceedings of the 1972 Meetings of the Arizona Section - American Water Resources Assn. and the Hydrology Section - Arizona Academy of Science - May 5-6, 1972, Prescott, Arizona / An average of 6 to 13 streamflows from intense summer convective storms occurs annually in the walnut gulch experimental station, 58 square miles in southeastern Arizona. Flows last generally less than 6 hours, and the channels are dry 99 percent of the time. The limiting factors imposed by the geology and geomorphology of the channel to transmission losses of a 6 square mile channel in the station are described. The Precambrian to quaternary geology is outlined, and geomorphology of the channels are described. Volume, porosity and specific yield of alluvium were determined. There is 106 acre-feet of alluvium with a mean specific yield of 28 percent, and a maximum water absorbing capacity of 29 acre-feet or 7 acre-feet per mile of reach. Channel slope is insensitive to changes in geological material beneath it or to changes in flow regime. Channel cross section is highly sensitive to geology and flow regime. Transmission losses were highly correlated to volume of inflow.

No description available.

In this thesis, a number of mathematical models of haptotactic cell migration are developed. The modelling of haptotaxis is presented in two distinct parts - the first comprises an investigation of haptotaxis in pre-necrotic avascular tumours, while the second consists of the modelling of adhesion-mediated haptotactic cell migration within tissue, with particular attention paid to the biological appropriateness of the description of cell-extracellular matrix adhesion. A model is developed that describes the effects of passive and haptotactic migration on the cellular dynamics and growth of pre-necrotic avascular tumours. The model includes a description of the extracellular matrix and its effect on cell migration. Questions are posed as to which cell types act as a source of the extracellular matrix, and the model is used to simulate the possible effects of different matrix sources. Simulations in one-dimensional and spherically symmetric geometry are presented, displaying familiar results such as three-phase tumour growth and tumours comprising a rim of proliferating cells surrounding a non-proliferating region. Novel effects are also described such as cell population splitting and tumour shrinkage due to haptotaxis and appropriate extracellular matrix construction. The avascular tumour model is then extended to describe the internalisation of labelled cells and inert microspheres within multicell tumour spheroids. A novel model of adhesion-receptor mediated haptotactic cell migration is presented and specific applications of the model to tumour invasion processes are discussed. This model includes a more biologically realistic description of cell adhesion than has been considered in previous models of cell population haptotaxis. Through assumptions of fast kinetics, the model is simplified with the identification of relationships between the simplified model and previous models of haptotaxis. Further simpli.cations to the model are made and travelling wave solutions of the original model are then investigated. It is noted that the generic numerical solution routine NAG D03PCF is not always appropriate for the solution of the model, and can produce oscillatory and inaccurate solutions. For this reason, a control volume numerical solver with .ux limiting is developed to provide a better method of solving the cell migration models.

This study explored social workers’ perceptions of their role in providing palliative care to patients with life-limiting illnesses in six hospitals across Namibia. A qualitative grounded theory approach was use in which in-depth interviews were conduct with twenty (20) social workers. Several key findings are presented: First, the emerging constructivist grounded theory of social workers’ multi-dimensional roles in providing palliative include identities of advocate, assessor, broker, counsellor, educator, facilitator, patient liaison, mediator, discharge planner and manager of in-country referrals. Second, several participants’ uncertainties of what palliative care entails offered insight that they are in need of palliative care education and training. Third, healthcare professionals do not understand the role of the social workers and therefore social workers receive inadequate support from them. Fourth, there is a lack of in-service training and continuous education in palliative care. Fifth, there are inadequate practice opportunities in palliative care for undergraduate social work students. Finally, the well-being of social workers is another concern with limited debriefing opportunities available. Further research needs to be conducted and policy guidelines established to identify ways to improve the field of palliative care social work. In achieving this, formal education and palliative care practice opportunities for social workers need to be established, providing continuing education and establishing a Centre of Excellence on palliative care provision. This study argues that the social work profession is well positioned to draw upon its values, culture and experiences (particularly from their clients) to get involved in creating a constructivist grounded theory of social workers’ roles in providing palliative care. / Sociology / D. Phil. (Sociology)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Mechanization significantly increased the productivity, quality and cost reduction for forests cultivation. However, it may be responsible for environmenral impacts, such as soil compaction, which is a result of traffic, mostly during wood harvesting operations. The objectives of this research were to evaluate the physical quality, trafficability and soil compaction due to traffic of wood harvesting machines of Eucalyptus sp. and developing functions to estimate physical and mechanical properties. The research was conducted in soils coming from implantation areas of Eucalyptus sp., and from an operational area of harvesting of Eucalyptus saligna Sm, belonging to CMPC Celulose Riograndense. To answer the hypotheses and meet the objectives, this work was divided into two studies. In Study I, five forest soils with different textural compositions were evaluated, determining physical quality indicators, trafficability indicators coming from the Proctor Normal test and uniaxial compression, and Atterberg consistency limits. The main results showed that both indicators of physical and trafficability were related to textural composition of soil, being estimated from these, as well as being influenced by different states of compaction. Furthermore, it was found that changing the bearing capacity has resulted in alteration of least limiting water range, which are related and, in this way, allowed to estimate the critical pressure for the plants growth. In Study II, we assessed the effect of different traffic intensities of a Harvester and a Forwarder on a Haplic Cambissol with sandy loam texture in Eucalyptus saligna Sm. stands, by determining the machines contact area and ground pressure exerted on soil, bulk density, pore size distribution, water retention curve, available water content, saturated hydraulic conductivity, air permeability, penetration resistance, compressibility, degree of compaction and shear strength. Were also evaluated the relationship of these properties and parameters. The main results indicated that few machines passes (one pass of Harvester and the four more of Forwarder) resulted in great part in soil deformation and changing in all evaluated properties and parameters. Mostly effects occurred until the depth of 20 cm. However, increasing the number of passes also caused changes in the deeper layers of soil. In general, the effects were higher in the area below within tracks, but, even so, effects occurred in areas between the wheels tracks and outside the areas of machines tracks. It was concluded that actions to minimize the compaction of forest soils should be associated with moisture conditions, traffic intensity and soil type. / A mecanização possibilitou aumento da produtividade, qualidade e redução de custos das atividades para o cultivo de florestas. Entretanto, tem sido responsável por impactos ambientais, destacando-se a compactação do solo, a qual é resultado do tráfego intenso de máquinas, principalmente nas operações de colheita. Os objetivos desta pesquisa foram avaliar a qualidade física, trafegabilidade e a compactação de solos, em função do tráfego de máquinas de colheita da madeira de Eucalyptus sp. e desenvolver funções para a estimativa de propriedades físicas e mecânicas. A pesquisa foi desenvolvida em solos advindos de áreas de implantação de povoamentos de Eucalyptus sp., e de uma área operacional de colheita de Eucalyptus saligna Sm., pertencentes à empresa CMPC Celulose Riograndense. Para responder as hipóteses e atender aos objetivos, o trabalho foi dividido em dois estudos. No Estudo I, foram avaliados cinco solos de uso florestal de diferentes composições texturais, determinando-se os indicadores de qualidade física, indicadores de trafegabilidade advindos do ensaio de Proctor Normal e compressão uniaxial, e limites de consistência. Os principais resultados mostraram que os indicadores de qualidade física e de trafegabilidade foram relacionados aos atributos texturais, podendo ser estimados a partir destes, além de serem influenciados por diferentes estados de compactação. Além disso, constatou-se que a alteração da capacidade de suporte resultou na alteração do intervalo hídrico ótimo, sendo estes relacionados, permitindo, assim, ser estimada a pressão crítica para o crescimento de plantas. No Estudo II, foi avaliado o efeito de diferentes intensidades de tráfego de um Harvester e um Forwarder sobre um Cambissolo Háplico de textura franco-arenosa em povoamentos de Eucalyptus saligna Smith, por meio da determinação da área de contato, pressão exercida pelas máquinas sobre o solo, densidade, distribuição de tamanho de poros, curva de retenção de água, conteúdo de água disponível, condutividade hidráulica do solo saturado, permeabilidade ao ar, resistência do solo à penetração, compressibilidade, grau de compactação e resistência ao cisalhamento. Foram avaliadas, também, as relações dessas propriedades e parâmetros. Os principais resultados indicaram que poucas passadas das máquinas (uma do Harvester e quatro do Forwarder) foram responsáveis em grande parte pela deformação e alteração de todas as propriedades e parâmetros. Os efeitos foram maiores até os 20 cm de profundidade. Entretanto, o aumento do número de passadas também causou alterações nas camadas mais profundas do solo. Em geral, os efeitos foram maiores na zona abaixo da trilha dos rodados, porém, ainda ocorreram efeitos nas zonas entre os rodados e fora da trilha dos rodados das máquinas. Conclui-se que as ações para minimização da compactação de solos florestais devem estar associadas às condições de umidade, intensidade de tráfego e tipo de solo.

The objective of this research was to identify and analyze what were the internationalization strategies adopted by the agricultural cooperatives of coffee in the Região do Cerrado Mineiro. The paradigm adopted for this research was functionalist, with a qualitative approach and, to access the data, was used case studies, consisting of five agricultural cooperatives that sell coffee, affiliated to the Federação dos Cafeicultores do Cerrado (Federation of the Cerrado Coffee Growers), which is the owner of the brand Região do Cerrado Mineiro, and also the data of the federation itself. Among the five first cases, two of them are cooperatives that became internationalized, one of them ended its activities during the research and, the other three, are not internationalized. Data collection was through semi-structured interviews with managers of internationalized cooperatives, non-internationalized ones and the Federation of the Cerrado Coffee Growers and with cooperative associates from the internationalized cooperatives, which resulted in 16 interviews, besides the documents. The content analysis technique served to the analysis of the collected data, which enabled the identification of five categories, consisting of push, delaying or limiting factors to internationalization, also, for hybrid factors, that influenced the internationalization strategies of agricultural cooperatives of coffee in the Região do Cerrado Mineiro, which are: 1) add value; 2) relationship with business partners and competitors; 3) structure of the cooperative; 4) being part of the Região do Cerrado Mineiro; 5) being located in the Cerrado Mineiro. While theoretical contribution, two were presented. The first is the joint use of internationalization theories, Theory of Dynamic Capabilities and studies on agricultural cooperatives in the internationalization process of agricultural coffee cooperatives. The second, was the standardization of the names used to refer to the types of coffee, they are: a) commodities or undifferentiated; b) differentiated, higher, certificates or second-line; c) special, fine, first-rate, very fine or extra-thin. As a result of these theoretical contributions, practical contributions were recognized. Firstly, it was drafted the steps adopted by the internationalized cooperatives in order to meet the international market expectations and, in sequence, was presented nineteen specific internationalization strategies. Finally, the originality of this research comes from the use of theories of internationalization and the Theory of Dynamic Capabilities to understand the movement of agricultural coffee cooperatives internationalization. / O objetivo desta pesquisa foi identificar e analisar quais foram as estratégias de internacionalização adotadas pelas cooperativas agropecuárias de café da Região do Cerrado Mineiro. O paradigma de pesquisa adotado foi funcionalista, com abordagem qualitativa e, para acessar os dados, valeu-se de estudos de casos, de cinco cooperativas agropecuárias que comercializam café, filiadas à Federação dos Cafeicultores do Cerrado, que é a controladora da denominação de origem e marca Região do Cerrado Mineiro, além dos dados obtidos da própria federação. Dentre os cinco primeiros casos, dois deles são de cooperativas que se internacionalizaram, sendo que uma delas encerrou suas atividades no decorrer da pesquisa, e as outras três não se internacionalizaram. A coleta de dados foi conduzida por meio de entrevistas semiestruturadas com gestores das cooperativas internacionalizadas, não internacionalizadas e da Federação dos Cafeicultores do Cerrado e com cooperados associados às cooperativas internacionalizadas, o que resultou em 16 entrevistas, além de documentos. A técnica de análise de conteúdo serviu à análise dos dados coletados, a qual possibilitou identificar cinco categorias, constituídas por fatores impulsionadores, retardadores ou limitantes à internacionalização, ainda, por fatores híbridos, que influenciaram as estratégias de internacionalização das cooperativas agropecuárias de café da Região do Cerrado Mineiro, que são: 1) agregar valor; 2) relação com parceiros comerciais e concorrência; 3) estrutura da cooperativa; 4) fazer parte da Região do Cerrado Mineiro; 5) estar localizado no Cerrado Mineiro. Enquanto contribuição teórica, emergiram duas. A primeira é o uso conjunto das teorias de internacionalização, Teoria das Capacidades Dinâmicas e estudos sobre cooperativas agropecuárias no processo de internacionalização das cooperativas agropecuárias de café. A segunda, foi a padronização dos nomes utilizados para se referir aos tipos de cafés, são eles: a) commodities ou indiferenciados; b) diferenciados, superiores, certificados ou de segunda linha; c) especiais, finos, de primeira linha, finíssimos ou extrafinos. Em decorrência das contribuições teóricas, sobrevieram as contribuições práticas. Primeiramente, esboçou-se os passos adotados pelas cooperativas internacionalizadas ao atenderem o mercado internacional e, em sequência, apresentou-se dezenove estratégias de internacionalização específicas. Por último, a originalidade da pesquisa adveio do uso de teorias de internacionalização e da Teoria das Capacidades Dinâmicas, em conjunto, para compreender o movimento de internacionalização de cooperativas agropecuárias de café. / Mestre em Administração

La Physique des Hautes Densités d’Énergies (HEDP) est caractérisée par desécoulements multi-matériaux fortement compressibles. Le domaine contenant l’écoulementsubit de grandes variations de taille et est le siège d’ondes de chocs et dedétente intenses. La représentation Lagrangienne est bien adaptée à la descriptionde ce type d’écoulements. Elle permet en effet une très bonne description deschocs ainsi qu’un suivit naturel des interfaces multi-matériaux et des surfaces libres.En particulier, les schémas Volumes Finis centrés Lagrangiens GLACE (GodunovtypeLAgrangian scheme Conservative for total Energy) et EUCCLHYD (ExplicitUnstructured Cell-Centered Lagrangian HYDrodynamics) ont prouvé leur efficacitépour la modélisation des équations de la dynamique des gaz ainsi que de l’élastoplasticité.Le travail de cette thèse s’inscrit dans la continuité des travaux de Maireet Nkonga [JCP, 2009] pour la modélisation de l’hydrodynamique et des travauxde Kluth et Després [JCP, 2010] pour l’hyperelasticité. Plus précisément, cettethèse propose le développement de méthodes robustes et précises pour l’extension3D du schéma EUCCLHYD avec une extension d’ordre deux basée sur les méthodesMUSCL (Monotonic Upstream-centered Scheme for Conservation Laws) et GRP(Generalized Riemann Problem). Une attention particulière est portée sur la préservationdes symétries et la monotonie des solutions. La robustesse et la précision duschéma seront validées sur de nombreux cas tests Lagrangiens dont l’extension 3Dest particulièrement difficile. / High Energy Density Physics (HEDP) flows are multi-material flows characterizedby strong shock waves and large changes in the domain shape due to rarefactionwaves. Numerical schemes based on the Lagrangian formalism are good candidatesto model this kind of flows since the computational grid follows the fluid motion.This provides accurate results around the shocks as well as a natural tracking ofmulti-material interfaces and free-surfaces. In particular, cell-centered Finite VolumeLagrangian schemes such as GLACE (Godunov-type LAgrangian scheme Conservativefor total Energy) and EUCCLHYD (Explicit Unstructured Cell-CenteredLagrangian HYDrodynamics) provide good results on both the modeling of gas dynamicsand elastic-plastic equations. The work produced during this PhD thesisis in continuity with the work of Maire and Nkonga [JCP, 2009] for the hydrodynamicpart and the work of Kluth and Després [JCP, 2010] for the hyperelasticitypart. More precisely, the aim of this thesis is to develop robust and accurate methodsfor the 3D extension of the EUCCLHYD scheme with a second-order extensionbased on MUSCL (Monotonic Upstream-centered Scheme for Conservation Laws)and GRP (Generalized Riemann Problem) procedures. A particular care is taken onthe preservation of symmetries and the monotonicity of the solutions. The schemerobustness and accuracy are assessed on numerous Lagrangian test cases for whichthe 3D extensions are very challenging.

Extracting useful knowledge from data sets is a key concept in modern information systems. Consequently, the need of efficient techniques to extract the desired knowledge has been growing over time. Machine learning is a research field dedicated to the development of techniques capable of enabling a machine to \"learn\" from data. Many techniques have been proposed so far, but there are still issues to be unveiled specially in interdisciplinary research. In this thesis, we explore the advantages of network data representation to develop machine learning techniques based on dynamical processes on networks. The network representation unifies the structure, dynamics and functions of the system it represents, and thus is capable of capturing the spatial, topological and functional relations of the data sets under analysis. We develop network-based techniques for the three machine learning paradigms: supervised, semi-supervised and unsupervised. The random walk dynamical process is used to characterize the access of unlabeled data to data classes, configuring a new heuristic we call ease of access in the supervised paradigm. We also propose a classification technique which combines the high-level view of the data, via network topological characterization, and the low-level relations, via similarity measures, in a general framework. Still in the supervised setting, the modularity and Katz centrality network measures are applied to classify multiple observation sets, and an evolving network construction method is applied to the dimensionality reduction problem. The semi-supervised paradigm is covered by extending the ease of access heuristic to the cases in which just a few labeled data samples and many unlabeled samples are available. A semi-supervised technique based on interacting forces is also proposed, for which we provide parameter heuristics and stability analysis via a Lyapunov function. Finally, an unsupervised network-based technique uses the concepts of pinning control and consensus time from dynamical processes to derive a similarity measure used to cluster data. The data is represented by a connected and sparse network in which nodes are dynamical elements. Simulations on benchmark data sets and comparisons to well-known machine learning techniques are provided for all proposed techniques. Advantages of network data representation and dynamical processes for machine learning are highlighted in all cases / A extração de conhecimento útil a partir de conjuntos de dados é um conceito chave em sistemas de informação modernos. Por conseguinte, a necessidade de técnicas eficientes para extrair o conhecimento desejado vem crescendo ao longo do tempo. Aprendizado de máquina é uma área de pesquisa dedicada ao desenvolvimento de técnicas capazes de permitir que uma máquina \"aprenda\" a partir de conjuntos de dados. Muitas técnicas já foram propostas, mas ainda há questões a serem reveladas especialmente em pesquisas interdisciplinares. Nesta tese, exploramos as vantagens da representação de dados em rede para desenvolver técnicas de aprendizado de máquina baseadas em processos dinâmicos em redes. A representação em rede unifica a estrutura, a dinâmica e as funções do sistema representado e, portanto, é capaz de capturar as relações espaciais, topológicas e funcionais dos conjuntos de dados sob análise. Desenvolvemos técnicas baseadas em rede para os três paradigmas de aprendizado de máquina: supervisionado, semissupervisionado e não supervisionado. O processo dinâmico de passeio aleatório é utilizado para caracterizar o acesso de dados não rotulados às classes de dados configurando uma nova heurística no paradigma supervisionado, a qual chamamos de facilidade de acesso. Também propomos uma técnica de classificação de dados que combina a visão de alto nível dos dados, por meio da caracterização topológica de rede, com relações de baixo nível, por meio de medidas de similaridade, em uma estrutura geral. Ainda no aprendizado supervisionado, as medidas de rede modularidade e centralidade Katz são aplicadas para classificar conjuntos de múltiplas observações, e um método de construção evolutiva de rede é aplicado ao problema de redução de dimensionalidade. O paradigma semissupervisionado é abordado por meio da extensão da heurística de facilidade de acesso para os casos em que apenas algumas amostras de dados rotuladas e muitas amostras não rotuladas estão disponíveis. É também proposta uma técnica semissupervisionada baseada em forças de interação, para a qual fornecemos heurísticas para selecionar parâmetros e uma análise de estabilidade mediante uma função de Lyapunov. Finalmente, uma técnica não supervisionada baseada em rede utiliza os conceitos de controle pontual e tempo de consenso de processos dinâmicos para derivar uma medida de similaridade usada para agrupar dados. Os dados são representados por uma rede conectada e esparsa na qual os vértices são elementos dinâmicos. Simulações com dados de referência e comparações com técnicas de aprendizado de máquina conhecidas são fornecidos para todas as técnicas propostas. As vantagens da representação de dados em rede e de processos dinâmicos para o aprendizado de máquina são evidenciadas em todos os casos

The purpose of this study was to determine the limiting nutrient in a set of coastal areas and estuaries in the Baltic Sea. Although the subject as been studied for several decades, no clear consensus has been reached in the scientific community as to whether primary production is limited by phosphorus or nitrogen. A total of five coastal areas, all located on the east coast of Sweden, were assessed regarding their limiting nutrient by using three methods. The first method was applying linear regression analysis on measured TP and TN concentration together with chlorophyll-a and Secchi depth. The data was collected from sampling programs stretching back to the 1970s and 80s, studying the summer period May to September for all sites but one, were the period April to October was studied. The second method calculated the TN/TP ratio during the summer period and compared it to the Redfield ratio. Thirdly, basic mass-balance calculations were carried out, with empirical data on the external loads and calibrated with the yearly average concentration in the surface water (0–10 m). From the calculations, both the annual external and internal load of TP and TN was obtained. The different TP and TN loads were likewise tested for a correlation with the measured summer chlorophyll-a concentration and Secchi depth. The results of using linear regression analysis on measured concentrations were mostly inconclusive, as the TP and TN concentrations for all sites and most years were related to each other. Consequently both nutrients often gave equal correlation coefficients. Similarly the TP and TN loads also matched each other for most sites and years, inherently obtaining the same inconclusive, but also contradictory results, as when using the measured concentrations. The TN/TP ratio indicated, for one site that it was limited by phosphorus and another site possibly nitrogen limitation. The ratio in the other sites periodically dropped between nitrogen and phosphorus limitation over the years. Thus it was difficult to draw an overall conclusion as to what nutrient was the limiting one for all the sites. However analysing the results from the individual sites showed that three of the five sites had signs of phosphorus limitation. Two factors were deemed as being the main reasons as to why the methods did not achieve more conclusive results. The first factor was the empirical data, which varied in frequency and extent over the studied time periods and between sites, making representative concentrations difficult to calculate and evaluate. The second was the matching trends between both the concentrations and the loads of TP and TN. To achieve a better result one nutrient could be increased or decreased while one remains relatively constant. The problem with such an experiment would be controlling the inflow of nutrients from the adjacent sea. / Syftet med detta projekt var att bestämma det begränsande näringsämnet för ett antal kustområden i Östersjön. Frågan huruvida fosfor eller kväve är det begränsande näringsämnet i kustområden runt Östersjön har varit omdiskuterad under flera år och undersökts vid ett flertal tillfällen. I denna studie testades tre metoder, i fem olika kustområden, med syftet att fastställa det begränsande näringsämnet. Först användes linjär regressionsanalys med uppmätta värden på TP och TN koncentrationer tillsammans med klorofyll-a och Secchidjup. Empirisk data insamlades från övervakningsprogram där prover tagits sedan 1970- och 80-talet. Medelvärden beräknades för perioden maj till september för alla områden förutom ett, där undersöktes perioden april till oktober. Sommarmedelvärdena för TN/TP kvoten analyserades också för alla områden med avseende på Redfield kvoten. Slutligen genomfördes massbalansberäkningar med data för de externa belastningarna av TP och TN, dessa beräkningar kalibrerades sedan med uppmätta värden på koncentrationen i ytvattnet (0–10 m). Utifrån beräkningarna erhölls värden på den externa och den interna belastningen. Dessa belastningar testades med linjär regression för ett samband med de uppmätta värdena på Secchidjup och klorofyll-a. Metoden att använda linjär regressionsanalys med empiriskt uppmätta koncentrationer och djup, gav generellt ett oklart resultat. Detta var en följd av att halterna av både TP och TN i regel följdes åt, vilket fick konsekvensen att korrelationskoefficienterna för TP och TN ofta var lika stora. Samma problem uppstod för regressionsanalysen med belastningarna, då även dessa ofta följde varandra, men även motsade resultatet med koncentrationerna. Analysen av TN/TP kvoten tydde på att ett område var fosforbegränsat och ett område möjligen var kvävebegränsat. För de övriga tre områdena skiftade TN/TP kvoten under åren mellan kväve- och fosforbegränsning. De oklara resultaten gjorde det svårt att dra en övergripande slutsats. Däremot vid analysen av de enskilda områdena uppvisade tre av de fem områdena tecken på fosforbegränsning, även om detta inte kunde med säkerhet fastställas. Det var huvudsakligen två faktorer vars inverkan anses ha haft stor betydelse för det oklara resultatet. Den första faktorn var uppmätt data, vars frekvens och omfattning skiljde sig avsevärt mellan år och platser. Följaktligen försvårades beräkningarna av koncentrationerna och tillförlitligheten i hur representativa värdena var. Den andra och avgörande faktorn var de matchande trenderna hos både koncentrationerna och belastningarna. För att förbättra resultatet kan ett näringsämne ändras, medan det andra näringsämnet hålls relativt konstant. Problemet med att genomföra ett sådant experiment skulle vara att kontrollera inflödet av näringsämnen från närliggande hav.

L’objectif de cette thèse consistait à développer des colorants de la famille des polyméthines absorbant dans le proche infrarouge et présentant des propriétés d’optique non-linéaire (ONL) prononcées. De nouveaux chromophores ont été préparés et leurs propriétés spectroscopiques ont été systématiquement étudiées afin d’établir des relations structures-propriétés. Cette stratégie a permis l’identification des facteurs permettant d’exalter la réponse ONL des polyméthines et de prédire leur comportement face à de subtiles modifications structurales. Trois familles de colorants ont été préparées : des monométhines aza-dipyrrométhènes de bore, des heptaméthines symétriques ainsi que des heptaméthines dissymétriques.Dans un premier temps, des aza-bodipys possédant des groupements donneurs périphériques sont synthétisés. Une étude spectroscopique approfondie permet d’identifier les structures présentant une absorption à deux photons importante en vue d’applications en limitation optique aux longueurs d’onde des télécommunications (1500 nm). Le chapitre suivant a pour but de rationaliser les équilibres de la limite cyanine. L’étude de la substitution centrale de nombreux dérivés heptaméthines a permis de moduler leurs propriétés optiques sur une large gamme spectrale et de mettre en évidence une nouvelle structure électronique limite de type bis-dipôle. Parmi cette famille de colorants, des dérivés keto-heptaméthines ont été utilisées en imagerie biologique (cellules et cerveau) par microscopie non-linéaire. Enfin, l’élaboration de structures heptaméthines dissymétriques originales est détaillée dans le dernier chapitre. Ces chromophores ont révélé des propriétés ONL du second ordre idéales pour des applications en modulation électro-optique. / The aim of this thesis consisted in developing dyes from the polymethine family absorbing in the near-infrared (NIR) region and featuring pronounced nonlinear optical (NLO) properties. Several new chromophores have been prepared and their spectroscopic properties have been systematically investigated in order to establish structure-properties relationships. This strategy has permitted the identification of the factors that enhance the NLO response of polymethines and allowed the prediction of their optical behaviour depending on subtle structural modifications. Three families of dyes have been prepared and investigated: boron aza-dipyrro-monomethines (aza-bodipys), symmetrical heptamethines and unsymmetrical heptamethines.In a first time, aza-bodipys possessing electro-donating peripherical substituants has been synthesized. A detailed spectroscopic study allow the identification of structures that present a high two-photon absorption (TPA), towards optical limiting applications at telecommunication wavelengths (1500 nm). The next chapter rationalizes the equilibrium surrounding the cyanine limit. The study of the central substitution of several heptamethines derivatives permitted the fine tuning of their optical properties upon a large spectral region and evidenced a new bis-dipolar electronic structure. Within this dye family, keto heptamethine derivatives has been tested in bio-imaging experiments (living cells and brain) using non-linear microscopy. Finally, the elaboration of original unsymmetrical heptamethines is detailed in the last chapter. These chromophores revealed ideal second order NLO properties for applications in electro-optic modulation.