Yes / Provision of care and support for people with dementia and family carers is complex, given variation in how dementia manifests, progresses and affects people, co-morbidities associated with ageing, as well as individual preferences, needs, and circumstances. The traditional service-led approach, where individual needs are assessed against current service provision, has been recognised as unfit to meet such complexity. As a result, people with dementia and family members often fail to receive adequate support, with needs remaining unmet. Current research lacks a conceptual framework for explaining variation in satisfaction of care needs. This work develops a conceptual framework mapped onto the care delivery process to explain variations in whether, when and why care needs of people with dementia are met and to expose individual-, service-, system-level factors that enable or hinder needs satisfaction. METHODS: Data collected through 24 in-depth interviews and two focus groups (10 participants) with people with dementia and family carers living in the North East of England (UK) were analysed thematically to develop a typology of care needs. The need most frequently reported for people with dementia (i.e. for support to go out and about) was analysed using themes stemming from the conceptual framework which combined candidacy and discrepancy theories. RESULTS: The operationalisation of the framework showed that satisfaction of the need to go out was first determined at the point of service access, affected by issues about navigation, adjudication, permeability, users' resistance to offers, users' appearance, and systems-level operating conditions, and, subsequently, at the point of service use, when factors related to service structure and care process determined (dis)satisfaction with service and, hence, further contributed to met or unmet need. CONCLUSION: The conceptual framework pinpoints causes of variations in satisfaction of care needs which can be addressed when designing interventions and service improvements. / We gratefully acknowledge financial support from the Health Foundation (grant number 1274233).

In dieser Arbeit ein neues bioanalytisches Konzept untersucht, das nanoskalige Zeolith-Imidazolat-Frameworks (ZIFs) als Marker für antikörperbasierte Analysemethoden einsetzt, einschließlich Enzyme-Linked-Immunosorbent-Assay (ELISA) und Lateral Flow Immunoassay (LFIA). Der Vorteil von ZIFs als Marker gegenüber etablierten Materialien ist ihre vielseitige, einfache und kostengünstige Synthese. Dazu gehört die Möglichkeit, niedermolekulare Substanzen für zusätzliche Sensorzwecke zu verkapseln und für eine hohe Selektivität stabil an Biomakromoleküle zu konjugieren. Als modellhafter Zielanalyt von Relevanz wurden Phthalat-Acylester (PAEs) ausgewählt. Die Relevanz des Nachweises von PAEs ergibt sich aus ihren Eigenschaften als endokrin wirksame Chemikalien (EDCs) und krebserregend. In Kombination mit der Tatsache, dass PAEs aufgrund ihrer Verwendung als Weichmacher in Kindergeschirr, Spielzeug, Trinkflaschen und anderen Produkten auf Polyvinylchlorid-Basis in der Umwelt reichlich vorhanden sind, zeigt, wie wichtig der routinemäßige Nachweis von PAEs in Trinkwasser oder Lebensmitteln ist. / This work explores a new bioanalytical concept that employs nanosized Zeolite Imidazolate Frameworks (ZIFs) particles as labels for antibody-based analytical methods, including enzyme-linked immunosorbent assay (ELISA) and lateral flow immunoassay (LFIA). The advantage of ZIFs as labels over established materials is their versatile, facile, and cheap synthesis. This includes the ability to encapsulate low molecular weight substances for additional sensing purposes and for stable conjugation to biomacromolecules for high selectivity. As a model target analyte of relevance Phthalate acyl esters (PAEs) have been selected. The relevance of the detection of PAEs is due to their properties as endocrine disrupting chemicals (EDCs) and carcinogenic. Combined with PAEs being abundant on the environment because of their use as plasticizers in plastic-made tableware for children, toys, drinking bottles and other polyvinylchloride-based products, shows the importance or their routine detection of drinking water or foods being so critical.

In den letzten Jahren konzentriert sich die Entwicklung in der kommerziellen Informatik zunehmend auf den Einsatz von Standardsoftware, vorgefertigten Komponenten und Frameworks. Gleichzeitig stehen bei steigenden funktionalen Anforderungen regelmäßig geringere personelle und monetäre Ressourcen für die Anwendungsentwicklung zur Verfügung. Andererseits ist immer mehr Rechenleistung zu sinkenden Preisen verfügbar. Vorhandene, individuell entwickelte und an die Prozesse im Unternehmen angepasste Software muss häufig für den Einsatz im Intranet und Internet erweitert werden. Die technologischen Veränderungen und der Zwang zur Konsolidierung erfordern und erzwingen ein anderes Management von IT-Projekten. Die Diskussionen der letzten Jahre über leichtgewichtige Verfahren geben den Praktikern das theoretische Rüstzeug für die Umsetzung dieser Vorgehensweisen in die Hand [COC 03]. Nachfolgend werden die Aspekte dieser Veränderungen für das Projektmanagement diskutiert. In einem Großprojekt einer deutschen Versicherung wurden einige der betrachteten Verfahren und Methoden durch den Autor im praktischen Einsatz angewandt.

Les MOFs résultent de l’organisation de polyèdres métalliques reliés par des molécules organiques chélatantes pour former un réseau poreux. La construction de solides hybrides organiques/inorganiques permet d’imaginer un très grand nombre de matériaux aux propriétés structurales et physico-chimiques variées. Le confinement du substrat dans une structure rigide, associé à des propriétés particulières des clusters métalliques ainsi qu’à des parois pouvant être fonctionnalisées, fournissent un environnement catalytique unique, plaçant les MOF à la frontière entre les espèces types zéolites et les enzymes. Cependant, il existe aujourd’hui très peu de MOFs possédant plus d’une fonction catalytique. Néanmoins, les propriétés catalytiques des MOFs peuvent être améliorées de façons non négligeables grâce aux méthodes de post-fonctionalisation. Dans ce travail, nous reportons le développement d’une méthode de post-fonctionnalisation originale des amino-MOFs. La première étape consiste à convertir la fonction amine en fonction azoture. Puis, sans isolation ni purification, le MOF fonctionnalisé est obtenu par « Click Chemistry » en ajoutant l’alcyne correspondant. Cette méthode peut être appliquée à tous les types d’amino-MOFs et à quasi toutes les fonctions chimiques que l’on souhaite greffer. Une large librairie de nouveaux matériaux a ainsi été obtenue et complètement caractérisée. Cette méthode a aussi été utilisée pour créer des MOFs catalytiques à façon pour une réaction de transesterification, ainsi que pour l’investigation de nouvelles applications plus fines (niches industrielle) / MOFs result from the association of metallic clusters connected by organic linkers to form a net. It is acknowledged that ultimately MOFs could mimic “enzymes” using “molecular recognition” concept to allow high chemio-, regio-, enantio-selectivity. We could indeed anticipate MOFs as potential “artificial enzymes” that can combine several properties at the nanometer scale in a concerted fashion. However to date, the number of MOFs with more than one reactive “catalytic” function is rather scarce. A key to address advanced MOF materials suitable for more sophisticated applications is to add functionalities of greater complexity in a controlled manner. The ability to modify the chemical environment of the cavities within MOFs would allow tuning of the interactions with guest species, and serve as a route to tailor the chemical reactivity of the framework. However, the introduction of reactive chemical functions by self-assembly methods is not a trivial task. In this work, we report an original PSM method starting from amino derived MOFs. The first step consists in converting the amino group into azide (N3). Without isolation nor purification, the desired functionalized material is obtained by grafting the corresponding alkyne using “Clik Chemistry”. This method can be applied to all kind of amino-MOFs and to all kind of grafted chemical functions. A diverse library of original MOFs was synthesized and characterized. Finally, this method was used to engineer catalytic MOFs for the transesterification of ethyldecanoate with methanol or to investigate applications in specialized industrial niches

[pt] Com o crescimento dos sistemas de informação baseados na internet, empresas que mantém seus negócios eletrônicos através de sistemas web necessitam monitorar o andamento das atividades dos seus negócios. Várias técnicas para monitoramento e análise da execução de processos de negócio podem ser empregadas, dentre elas: (i) mineração de arquivos de log de servidores web, tais como o Apache; e (ii) inserção explícita de código de monitoramento diretamente no código da aplicação. Tais técnicas possuem várias limitações, entre elas, a dificuldade e falta de flexibilidade para corelacionar informação ocorrendo em diferentes requisições web, e/ou necessidade de várias modificações invasivas transversais diretamente no código de componentes/classes do sistema. Esse trabalho apresenta o projeto e implementação de um framework orientado a aspectos para monitoramento e análise de processos de negócio que ocorrem em sistemas web. Aspectos foram usados para implementar as variabilidades orientadas a aspectos de monitoramento de processos de negócio ocorrendo em sistemas web. O framework foi implementado usando as linguagens Java e AspectJ e foi validado por meio da sua instanciação para duas diferentes aplicações web. / [en] Over the last years, many mechanisms and techniques to monitor web applications have been proposed, such as, mining of log files from web servers and insertion of monitoring code directly in web applications. The adoption of these techniques presents several limitations such as: obstacles to correlate information from different web requests and/or requires several intrusive changes in the code of existing web applications. This dissertation presents an aspect-oriented framework to monitoring and analysing business processes. Aspect-oriented technologies are used to implement crosscutting variabilities of monitoring of web business processes. The framework has been developed using Java and AspectJ programming languages. It was instantiated and validated through the development of two different web applications.

Polímeros de coordenação têm atraído a atenção de pesquisadores na última década por conta de sua incrível versatilidade e virtualmente infinito número de possibilidades de combinação de ligantes orgânicos e centros metálicos. Estes compostos normalmente herdam as características magnéticas, eletrônicas e espectroscópicas de seus componentes base. Entretanto, apesar do crescente número de trabalhos na área, ainda são raros os polímeros de coordenação que apresentem condutividade elétrica. Para este fim, utilizou-se a N,N\'-bis(4-piridil)-1,4,5,8-naftaleno diimida, ou NDI-py, que pertence a uma classe de compostos rígidos, planares, quimicamente e termicamente estáveis e que já foram extensamente estudados por suas propriedades fotoeletroquímicas e semicondução do tipo n. O primeiro polímero de coordenação sintetizado, MOF-CoNDI-py-1, indicou ser um polímero linear, de estrutura 1D. O segundo, MOF-CoNDI-py-2, que conta com ácido tereftálico como ligante suporte, é um sólido cristalino com cela unitária monoclínica pertencente ao grupo espacial C2/c, determinado por difração de raios-X de monocristal. A rede apresenta um arranjo trinuclear de íons Co(II) alto spin com coordenados em uma geometria de octaedro distorcido, enquanto os ligantes NDI-py se encontram em um arranjo paralelo na estrutura, em distâncias apropriadas para transferência eletrônica. Com o auxílio de cálculo teóricos a nível de DFT, foi realizado um estudo aprofundado dos espectros eletrônicos e vibracionais, com atribuição das transições observadas, tanto para o MOF-CoNDI-py-2 quanto para o ligante NDI-py livre. A rede de coordenação absorve em toda a região do espectro eletrônico analisada, de 200 nm a 2500 nm, além de apresentar luminescência com característica do ligante. Dispositivos eletrônicos fabricados com um cristal do MOF-CoNDI-py-2 revelaram condutividades da ordem de 7,9 10-3 S cm -1, a maior já observada para um MOF. Além de elevada, a condutividade elétrica dos cristais demonstrou-se altamente anisotrópica, sendo significativamente menos condutor em algumas direções. Os perfis de corrente versus voltagem foram analisados em termos de mecanismos de condutividade, sendo melhores descritos por um mecanismo limitado pelo eletrodo to tipo Space-Charge Limited Current, concordando com a proposta de condutividade através dos planos de NDI-py na rede. A condutividade dos cristais também é fortemente dependente de luz, apresentando fotocondução quando irradiado por um laser vermelho, de 632 nm, enquanto apresenta um comportamento fotorresistivo frente a uma fonte de luz branca. Estes resultados, combinados, trazem um MOF em uma estrutura incomum e com elevada condutividade elétrica, modulada por luz, em medidas diretas de corrente. Não existem exemplos conhecidos de MOFs na literatura com estas características. / Coordination polymers have been a major topic in materials science during the past decade, thanks to their versatility and virtually infinite possible combinations between metal centers and organic ligands. These coordination polymers usually inherit the properties of their components, such as magnetic, spectroscopic and electronic characteristics. However, despite the increasing number of research papers in this topic, it is still hard to find coordination polymers featuring electronic conductivity. To achieve that, we used a naphthalene diimide derivative, N,N\'-bis(4-pyridyl)-1,4,5,8- naphthalene diimide or NDI-py, which belongs to a class of rigid, planar, thermally and chemically stable compounds, extensively studied due to their photoelectrochemical properties and their n-type semiconductivity. The first coordination polymer synthesised, MOF-CoNDI-py-1, was an amorphous linear polymer, with a 1D structure. Based on these observations, MOF-CoNDI-py-2 was synthesised by using terephthalic acid as a supporting ligand, and it is a crystalline solid which its monoclinic unit cell belongs to a C2/c space group, as determined by single crystal X-ray diffraction. This network features a trinuclear high-spin Co(II) unit, and each metal ion sits on a distorted octahedra coordination geometry, while the NDI-py ligands sit in a parallel arrangement, with distances suitable for electronic transfers. A detailed study of their vibrational and electronic spectra, supported by DFT calculations, was performed, as well as a full description and assignment of the observed bands. MOF-CoNDI-py-2 absorbs in the whole studied spectral region, from 200 nm to 2500 nm, while it also features a ligand-centered emission spectrum. Electronic devices built around its crystals revealed electric conductivities of 7.9 10 -3 S cm -1, which is, to the best of our knowledge, the highest for a MOF to this date. This conductivity is also highly anisotropic, being significantly less conductive in certain directions. The current versus voltage profiles were analysed in terms of known conduction mechanisms, with best fits when using an electrode-limited Space-Charge Limited Current mechanism, in agreement with the proposition that this conductivity happens through the NDI-py stacking planes. Additionally, this mechanism is influenced by an external light source, being a photoconductor with a red laser, 632 nm, and a photoresistor with a white light. Combined, these results bring a light-modulated, highly conductive MOF material with an unusual structure. As far as we know, there are no similar MOFs in the literature, which makes MOF-CoNDI-py-2 one of a kind.

[pt] Dispositivos portáteis dotados de computador são cada vez mais utilizados em diversos domínios de aplicações. Juntamente com as redes de telecomunicações provêem a base tecnológica para a computação móvel. Neste ambiente, os Sistemas de Gerência de Bancos de Dados (SGBDs) podem fornecer todos os mecanismos para confiança, segurança, disponibilidade, integridade e acesso eficiente a dados persistentes. Estes SGBDs podem estar localizados na rede com fio (fixa), desempenhando seu papel convencional de servidor de banco de dados, ou podem prover dados para computadores móveis e tecnologias relacionadas. Vários modelos para transações em banco de dados para o ambiente de computação móvel têm sido propostos. No entanto, não satisfazem plenamente as características únicas deste tipo de ambiente, tais como desconexões freqüentes, fraca conectividade na rede sem fio e a movimentação dos clientes. Esta tese tem por objetivo propor um modelo de computação que permita a integração de um SGBD a um ambiente de computação móvel. É apresentado um novo modelo de transações de banco de dados em múltiplos níveis no sentido de garantir o atendimento dos requisitos da computação móvel e as propriedades ACID de transações, onde há participação efetiva do SGBD. O modelo é definido em lógica de primeira ordem seguindo o formalismo ACTA. A implementação desse modelo de transações é apresentada em uma arquitetura que faz uso das abordagens de frameworks orientados a objetos e agentes de software, de forma a tratar com maior eficiência as especificidades do ambiente de computação móvel. Finalmente, é feita uma comparação entre alguns dos modelos mais relevantes de transações para bancos de dados no ambiente de computação móvel e o modelo proposto nesta tese, ressaltando o tratamento dado às propriedades ACID das transações de banco de dados. / [en] Portable computerized devices have become widely used in many different application domains and are, together with telecommunication networks, the underlying technology for mobile computing. In this environment Data- base Management Systems (DBMS) may provide reliability, security and availability, besides data integrity and efficiency persistent data access. These DBMS might be located either in conventional (fixed) networks, with the conventional data server role, or might serve global and local data for mobile computers and related technology. There are many transaction models for mobile database management. However, the particular characteristics of this mobile environment, such as frequent disconnections, weak and intermittent connectivity of wireless networks and clients movement, are not always well addressed. The goal of this thesis is to propose a computational model that enables the integration of a DBMS to a mobile environment. Indeed, we present a new multi-level database transactional model in order to handle mobile requirements and ACID transaction properties, where a DBMS is present. Our model is defined using the ACTA formalism based in first-order logic. The implementation of proposed transaction model becomes feasible through the use of object-oriented frameworks and software agents, with gave support to deal with the particularities of the mobile computing environment. Finally, we give a comparison between the most relevant transaction models for the mobile computing environment and our proposed model, emphasizing the treatment given to the ACID transactions properties.

Les Poly(HydroxyAlcanoates) (PHA) sont des polymères naturels, biodégradables et biocompatibles, synthétisés par de nombreux organismes, et plus particulièrement des procaryotes. Il existe à ce jour plus de 150 types de monomères de PHA différents, accumulés chez différents genres bactériens, en tant que source d’énergie et de carbone. En effet, les granules de PHA intracellulaires sont produites en réponse à un apport en excès de sources de carbone dans l’environnement (glucides, acides gras…), couplé à une carence en éléments azotés nécessaires à la division cellulaire. De par leur caractère biodégradable et biocompatible, les PHA sont employés depuis plus de 20 ans comme biomatériaux dans les domaines pharmaceutiques et biomédicaux, notamment comme micro/nanovecteurs à visée thérapeutique. Ce doctorat met en évidence des méthodes de criblage moléculaire par PCR pour la sélection de bactéries productrices de PHA, isolées de sites hydrothermaux des océans Atlantique et Pacifique au cours de campagnes océanographiques Ifremer. Selon des protocoles de fermentation standardisés et optimisés, des polymères de poly(3-hydroxybutyrate-4-hydroxybutyrate) P(3HB4HB) d’intérêt biomédical ont été produits, puis des études taxonomiques et phylogénétiques ont été menées pour explorer la biodiversité microbienne associée aux environnements marins profonds. Ensuite, des PHA ont été modifiés par réaction thiol-ène photoactivée afin d’obtenir des copolymères hydrosolubles, adaptés pour l’enrobage de nanoparticules poreuses de type Metal-Organic Frameworks (MOF). La caractérisation physicochimique a été réalisée par différentes techniques, et notamment par SEM et STEM-EDX. Les systèmes hybrides poreux MOF-PHA ont ensuite été évalués quant à leur biocompatibilité vis-à-vis de cellules immunitaires (macrophages), par des tests de cytotoxicité et de prolifération cellulaire. Cette étude met en lumière les potentialités de cette nouvelle génération de nanovecteurs, synthétisés pour augmenter le bénéfice thérapeutique tout en minimisant les effets secondaires sur l’organisme humain. / Poly(HydroxyAlkanoates) (PHA) are natural polymers, biodegradable and biocompatible, synthesized by many organisms, especially prokaryotes. There are over 150 kinds of these polyesters, accumulated in a wide variety of bacteria as carbon and energy storage material. PHA granules are deposited intracellularly when microorganisms are cultivated in the presence of an excess of carbon source (glucids, fatty acids...) together with a nitrogenous nutrient deficiency. Due to their biodegradability and biocompatibility, PHA can be used as biomaterials in medical or pharmaceutical fields, and numerous therapeutic micro/nanovectors have already been developed over the past two decades.The present PhD research project highlighted molecular screening methods by PCR for the PHA producing Bacteria selection, isolated during Ifremer cruises from hydrothermal vents in Atlantic and Pacific oceans.According to standardized and optimized fermentation protocols, poly(3-hydroxybutyrate-4-hydroxybutyrate) P(3HB4HB) polymers of biomedical interest were produced, then taxonomic and phylogenetic studies were performed to explore microbial biodiversity associated with deep-sea environments. Next, PHA were modified by ‘click chemistry’ to obtain hydrosoluble copolymers, suitable for coating high porous Metal-Organic Frameworks (MOF) therapeutic nanoparticles. Physico-chemical characterization was performed using different techniques, and more particularly by SEM and STEM-EDX. MOF-PHA hybrid porous systems were then evaluated for their biocompatibility against immune cells (macrophages), by cytotoxicity and cellular proliferation tests. This study highlights potentials of these new generations of nanovectors, synthesized to increase the therapeutic benefit while minimizing side effects on the human body.

O aumento no número de dispositivos móveis de alto desempenho e a disponibilidade de conexões sem fio permitiram o desenvolvimento de interfaces que são compartilhadas entre diversos dispositivos; tais interfaces são chamadas de Interfaces Distribuídas de Usuários. Esta pesquisa foca no desenvolvimento de um arcabouço que visa simplificar o desenvolvimento de jogos digitais que utilizem interfaces distribuídas, assim como analisar o atual estado da arte de outras tecnologias e arcabouços. É proposto um estudo de aceitação, utilizando parâmetros quantitativos e qualitativos, afim de comprovar as características necessárias para uma experiência fluída para o usuário. Tal tarefa é analisada através da criação de um jogo protótipo onde diversos jogadores podem jogar juntos e compartilhar informações entre diversos dispositivos. / The increasing number of high-end mobile devices and increased connection availability have allowed on the development of interfaces that can be shared between multiple devices; such interfaces are called Distributed User Interfaces. This research aims the development of a framework to simplify the development of games using distributed interfaces, as well as to assay the current state-of-art of technologies and frameworks. We propose a study of the acceptance, using both qualitative and quantitative parameters, in order to verify compliance with the necessary characteristics for a fluid user experience. This is accomplished through the creation of a prototype game in which several players can play together and share information through many devices.

Padrões, linguagens de padrões e frameworks são formas de reuso de software. A complexidade de frameworks, causada pela dificuldade tanto em construí-los quanto em utilizá-los, é um dos inibidores do uso dessa tecnologia. Um processo para facilitar a construção e instanciação de frameworks é apresentado. Uma linguagem de padrões é utilizada para apoiar todo o processo, desde a identificação da funcionalidade do framework, seu projeto, implementação, validação, até sua instanciação para sistemas específicos do domínio. O framework obtido é do tipo caixa-branca e sua instanciação é feita especializando-se suas classes para sistemas específicos. O processo inclui, também, a construção de uma ferramenta para automatizar a instanciação do framework, por meio da qual é possível obter um sistema específico fornecendo apenas informações sobre os padrões da linguagem utilizados na sua modelagem. O processo é ilustrado com a Linguagem de Padrões para Gestão de Recursos de Negócios (GRN), que serviu de base para construção do framework GREN. Apresenta-se também o GREN-Wizard, uma ferramenta para instanciação automática do GREN para sistemas no domínio da GRN. A avaliação do processo é feita por meio de alguns experimentos e vários relatos de uso dos diversos sub-processos que compõem o processo geral, usando o GREN, a GRN e o GREN-Wizard. / Patterns, pattern languages, and frameworks are ways of enhancing software reuse. The complexity of software frameworks, caused both by the difficulty to build and to use them, is one of the inhibitors of this technology. A process to ease the construction and instantiation of frameworks is presented, in which a pattern language is used to support the whole process, starting from the identification of the framework functionality, its design, implementation, validation, and its instantiation to domain-specific systems. The framework that results from applying the proposed process is white-box and its instantiation is done by specializing its abstract classes according to a specific system. The process includes the construction of a tool to automate the framework instantiation, through which it is possible to obtain a specific system only by supplying information about the language patterns used to model it. The proposed process is illustrated with the Pattern Language for Business Resource Management (GRN), which was used as the basis for the GREN framework construction. The GREN-Wizard is also presented, which is a tool to automatically instantiate the GREN framework to specific applications in the GRN domain. The proposed process is evaluated by a few experiments and several uses of the sub-processes that compose the general process, using GRN, GREN and the GREN-Wizard.