A demanda de eficiência no gerenciamento das redes aumenta atualmente devido ao rápido desenvolvimento da computação em nuvem e a implantação em grande escala de centros de dados. O controle da infraestrutura deve ser capaz de classificar os diversos tipos de tráfego para aplicações diferentes, e prover o atendimento adequado no menor tempo possível. Porém, devido ao dinamismo da rede, nem sempre podem ser garantidos os requisitos mínimos necessários na Internet. Os mecanismos propostos para a engenharia de tráfego até hoje, são baseados em arquiteturas inflexíveis com a camada de controle e dados fortemente integrados. Isto dificulta um atendimento diferenciado adaptável aos diversos padrões de tráfego das aplicações modernas. Para enfrentar os problemas de flexibilidade das redes tradicionais, as Redes Definidas por Software, apresentam um paradigma inovador que separa as camadas de controle e encaminhamento de pacotes de forma a garantir a utilização eficiente dos recursos disponíveis, e ao mesmo tempo maior flexibilidade de implementação. Este paradigma permite conhecer o estado da rede e a sua topologia em tempo real, o que faz possível a reconfiguração de rotas e alocação de recursos de forma dinâmica. Esta dissertação apresenta um framework para engenharia de tráfego em SDN que utiliza a teoria matemática Network Calculus como ferramenta para subsidiar a caracterização e o policiamento de fluxos de pacotes. Através desta teoria, as decisões de encaminhamento e a distribuição do tráfego são baseadas não só por valores obtidos monitorando a rede, como também por projeções determinísticas que descrevem o comportamento do tráfego. Os resultados obtidos nos experimentos, comprovaram a eficiência no balanceamento de carga da rede em termos de atraso, demonstrando ganhos em termos de vazão do sistema e possibilitando a diminuição da porcentagem de perda de pacotes dos fluxos trafegados. O framework proposto visa contribuir na solução dos desafios relacionados a se estabelecer Engenharia de Tráfego para SDN com a especificação de mecanismos de gerenciamento adaptáveis as mudanças topológicas da rede, as diferentes características dos fluxos e que sejam capazes de distribuir de forma equilibrada o tráfego na rede. / The demand for network management efficiency is currently boosted by the rapid development of cloud computing and the large-scale deployment of data centers. Infrastructure control should be able to classify the various types of traffic for different applications, and provide adequate service in the shortest time possible. However, due to the dynamism of the network, the necessary minimum requirements on the Internet can not always be guaranteed. The proposed mechanisms for traffic engineering to date are based on inflexible architectures with the control and data layer strongly integrated. This hinders a differentiated service adaptable to the different traffic patterns of modern applications. To address the flexibility problems of traditional networks, Software Defined Networks presents an innovative paradigm that separates packet control and datapath layers to ensure the ecient use of available resources while providing greater deployment flexibility. This paradigm allows to know the state of the network and its topology in real time, which makes it possible to reconfigure routes and allocate resources dynamically. This work presents a framework for SDN traffic engineering that uses the mathematical theory Network Calculus as a tool to subsidize the characterization and policing of packet flows. Through this theory, routing decisions and traffic distribution are based not only on values obtained by monitoring the network, but also on deterministic projections of traffic behavior. The results obtained in the experiments, proved the efficiency in the load balancing of the network based on flow delay, demonstrating gains in terms of total system throughput and enabling the reduction of the percentage of packet loss of the traffic flows. The framework proposed aims to contribute to the solution of the challenges related to establishing Traffic Engineering for SDN with specification of management mechanisms, adaptables to the topological changes of the network, the different characteristics of the flows and capable of distribute in a balanced way the traffic in the network.

The primary aim of this thesis is to detail and evaluate the appraisal frameworks and techniques employed on river restoration projects in the UK. This research evaluates the extent to which restoration projects have implemented the appraisal frameworks and techniques proposed in the practical restoration literature, and examines barriers to the incorporation of appraisal into river restoration projects. An ideal type appraisal framework is developed in this thesis and is used as a tool against which to evaluate the nature and extent of UK river restoration project appraisal. This research was undertaken through a national and a regional investigation of appraisal procedures. The national investigation is designed to be extensive and aims to draw out the basic dimensions of river restoration projects and appraisal. The regional investigation, in contrast, intensive adopting a case study approach which examines in detail how appraisal has and has not been implemented. The national investigation involved a questionnaire survey, sent to 161 people involved in 440 river restoration projects (80% response rate achieved). The regional investigation of the Thames region of the Environment Agency (EA) focused in detail on three case study sites (River Ravensbourne, River Cole and Upper River Kennet) undertaking twenty-five in-depth interviews with restoration practitioners. This enabled the appraisal and decision-making structures of these three projects to be evaluated. This thesis argues that it is not only the structure of a project's appraisal which influences a project's trajectory but also the nature and composition of the decision-making structure. The influence of scientific and lay knowledge in decision making is also explored. This thesis concludes by drawing together key empirical, theoretical and practical findings from these investigations. The results of this research are discussed and evaluated against how effectively UK river restoration projects incorporate the ideal type appraisal framework proposed in Chapter 2. The results of this research are further evaluated in the light of a workshop on river restoration appraisal (undertaken in November 2002) where appraisal frameworks are discussed and ways of including appraisals in river restoration projects are put forward.

This thesis is built upon two areas of research concerning metal-organic frameworks (MOFs). The first focuses on the functionalisation of MOFs via post-synthetic modification (PSM). The second involves the investigation on the potential of MOFs as hosts for insect pheromones. Chapter 1 introduces the field of MOF chemistry, and covers their properties along with a brief description of their applications. The concept of PSM is introduced and a review of recent literature given. The aims of the thesis are also detailed at the end of this chapter. Chapter 2 describes the PSM of [Zr6O4(OH)4(BDC-NH2)6], UiO-66-NH2, via Aza-Michael reactions. Different functionalities were successfully introduced into its pores and the degrees of conversion were determined via 1H NMR spectroscopy. Gas sorption measurements (CO2 and N2) of the PSM products were carried out and compared. In particular, two PSM products were shown to exhibit higher CO2 over N2 selectivity than that for the starting MOF, UiO-66-NH2. Chapter 3 describes a new PSM route in obtaining azole-functionalised MOFs via Mannich reactions. The amino groups in three different MOFs were converted into a range of azole-functionalised MOFs with conversions up to 100%. In particular, one of the PSM reactions afforded a new material, formulated as [Zn3(BDC-NH2)1.32(BDC-NHCH2N2C3H3)1.68(C6H12N2)], based on single crystal X-ray crystallography, 1H NMR and TGA analyses. Gas sorption studies demonstrate increased selectivity for CO2 over N2 for the PSM products. One of the modified MOFs was shown to exhibit a high Hg(II) uptake from aqueous solutions. Chapter 4 introduces the concept of using MOFs as hosts for ant pheromones. The factors which influenced the pheromone loading in zinc and zirconium based MOFs were investigated. The MOFs containing the linker BDC-NHPr (2-(propylamino)benzene-1,4-dicarboxylate) were found to be effective at hosting two types of ant pheromones, 3-octanone and (S)-4-methyl-3-heptanone.

A demanda de eficiência no gerenciamento das redes aumenta atualmente devido ao rápido desenvolvimento da computação em nuvem e a implantação em grande escala de centros de dados. O controle da infraestrutura deve ser capaz de classificar os diversos tipos de tráfego para aplicações diferentes, e prover o atendimento adequado no menor tempo possível. Porém, devido ao dinamismo da rede, nem sempre podem ser garantidos os requisitos mínimos necessários na Internet. Os mecanismos propostos para a engenharia de tráfego até hoje, são baseados em arquiteturas inflexíveis com a camada de controle e dados fortemente integrados. Isto dificulta um atendimento diferenciado adaptável aos diversos padrões de tráfego das aplicações modernas. Para enfrentar os problemas de flexibilidade das redes tradicionais, as Redes Definidas por Software, apresentam um paradigma inovador que separa as camadas de controle e encaminhamento de pacotes de forma a garantir a utilização eficiente dos recursos disponíveis, e ao mesmo tempo maior flexibilidade de implementação. Este paradigma permite conhecer o estado da rede e a sua topologia em tempo real, o que faz possível a reconfiguração de rotas e alocação de recursos de forma dinâmica. Esta dissertação apresenta um framework para engenharia de tráfego em SDN que utiliza a teoria matemática Network Calculus como ferramenta para subsidiar a caracterização e o policiamento de fluxos de pacotes. Através desta teoria, as decisões de encaminhamento e a distribuição do tráfego são baseadas não só por valores obtidos monitorando a rede, como também por projeções determinísticas que descrevem o comportamento do tráfego. Os resultados obtidos nos experimentos, comprovaram a eficiência no balanceamento de carga da rede em termos de atraso, demonstrando ganhos em termos de vazão do sistema e possibilitando a diminuição da porcentagem de perda de pacotes dos fluxos trafegados. O framework proposto visa contribuir na solução dos desafios relacionados a se estabelecer Engenharia de Tráfego para SDN com a especificação de mecanismos de gerenciamento adaptáveis as mudanças topológicas da rede, as diferentes características dos fluxos e que sejam capazes de distribuir de forma equilibrada o tráfego na rede. / The demand for network management efficiency is currently boosted by the rapid development of cloud computing and the large-scale deployment of data centers. Infrastructure control should be able to classify the various types of traffic for different applications, and provide adequate service in the shortest time possible. However, due to the dynamism of the network, the necessary minimum requirements on the Internet can not always be guaranteed. The proposed mechanisms for traffic engineering to date are based on inflexible architectures with the control and data layer strongly integrated. This hinders a differentiated service adaptable to the different traffic patterns of modern applications. To address the flexibility problems of traditional networks, Software Defined Networks presents an innovative paradigm that separates packet control and datapath layers to ensure the ecient use of available resources while providing greater deployment flexibility. This paradigm allows to know the state of the network and its topology in real time, which makes it possible to reconfigure routes and allocate resources dynamically. This work presents a framework for SDN traffic engineering that uses the mathematical theory Network Calculus as a tool to subsidize the characterization and policing of packet flows. Through this theory, routing decisions and traffic distribution are based not only on values obtained by monitoring the network, but also on deterministic projections of traffic behavior. The results obtained in the experiments, proved the efficiency in the load balancing of the network based on flow delay, demonstrating gains in terms of total system throughput and enabling the reduction of the percentage of packet loss of the traffic flows. The framework proposed aims to contribute to the solution of the challenges related to establishing Traffic Engineering for SDN with specification of management mechanisms, adaptables to the topological changes of the network, the different characteristics of the flows and capable of distribute in a balanced way the traffic in the network.

Estágio realizado na ALERT Life Sciences Computing, S. A / Tese de mestrado integrado. Engenharia Informática e Computação. Faculdade de Engenharia. Universidade do Porto. 2009

Tese de mestrado. Engenharia Informática. Faculdade de Engenharia. Universidade do Porto, Universidad de Castilla-La Mancha. 2009

Au cours de la dernière décennie, une nouvelle classe de composés de coordination, à base de métaux et de ligands organiques de pontage, connus sous le nom de «Metal Organiques Frameworks (MOFs)» a été largement étudiée. Ces composés ont été popularisés par Yaghi et ses collaborateurs en 1995 et ont attiré l'attention considérablement en raison de leur structure hautement modulable, leur large gamme de tailles de pores avec une grande surface et leurs fonctionnalités facilement adaptables. Ces matériaux offrent un grand potentiel pour diverses applications, en particulier dans le domaine de la catalyse, du stockage et de séparation des gaz.Malgré leurs applications diverses, en particulier dans la séparation de gaz, il y a très peu de rapports concernant la croissance des MOFs sous forme des films minces ou de membranes synthétiques. Dans ce travail, nous décrivons l'utilisation de l'électrofilage pour construire des structures hiérarchiques et des membranes autosupportées de MOF. En fait, l'électrofilage est une technique simple et polyvalente pour produire des libres continues avec des diamètres moyens allant de quelques nanomètres à quelques micromètres.Deux stratégies, basées sur l'utilisation des nanofibres de différents polymères, ont été adoptées : pour produire des membranes auto­ supportées, différents composites polymère/MOF ont été d'abord électrofilés, puis les nanofibres obtenues ont été exposées à des différentes solutions contenant un mélange cation/linker. En conséquence, après la croissance des MOFs, des membranes auto­supportées ont été obtenues avec les nanofibres servant de matrice.D'autre part, pour construire des structures hiérarchiques, des mélanges polymère/cation ont été électrofilés et les nanofibres obtenues ont été immergées dans des solutions de linkers pour la croissance de différents MOFs sur les fibres. Les méthodes décrites ont été testées avec succès en utilisant deux polymères différents (PVA, PAN) et quelques MOFs (MOF-5, HKUST-1, ZIF-8). En effet, ces structures font partie des structures les plus représentatives de celle classe de composés hybrides. Enfin, les différents matériaux obtenus ont été caractérisés par la microscopie électronique à balayage (MEB), la spectroscopie infrarouge à transformée de Fourier, la diffraction des rayons X sur poudre et l'analyse thermogravimétrique / Ln the last decade, a novel class of coordination compounds comprising metal-based nodes and bridging organic linkers known as «Metal Organic Frameworks (MOFs) » has been extensively studied. These compounds were popularized by Yaghi et al. around 1995 and have attracted enormous attention due to their highly designable structure, their wide range of pore sizes with a large surface area and their easily tailorable functionalities. These materials offer a great potential for various applications especially in the field of catalysis, gas storage and gas separation. Despite the huge potential especially in the gas separation, there are few reports about the growth of MOFs as thin films or synthetic membranes.In this work, we describe the use of electrospinning for building hierarchical structures and auto-supported membranes of MOFs. ln fact, the electrospinning is a simple and versatile technique to produce continuous fibers with average diameters in the range of nanometers to a few micrometers.Two strategies were adopted: for producing auto-supported membranes, different polymer/MOF composites were firstly electrospun, then, the obtained nanofibers were exposed to solutions containing different cation/linker mixtures. Accordingly, after the MOFs' growth, auto-supported membranes were obtained with the nanofibers serving as backbone. ln another hand, for building hierarchical structures, polymer/cation mixtures were electrospun and the obtained nanofibers were immersed in linkers' solutions for growing different MOFs on the fibers. The described methods were successfully tested using 1\\0 polymers (PVA,P/\N) and different metal organic frameworks (MOF-5. I IKUST- 1 and ZIF-8). Indeed, these MOFs are among the most representative metal organic frameworks. Finally, the different obtained materials were characterized using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy, powder X-ray diffraction and thermogravimetric analysis.

År 1992 gick startskottet för att hållbarhet skulle bli företags skyldighet utifrån tidigare sattaglobala hållbarhetsmål. Detta medförde en diskussion om hur hållbarhet skulle rapporteras.Inte förrän 25 år senare anammas detta som ett lagkrav för större företag i Sverige. Problemetär sålunda, att trots lagkrav om hållbarhetsrapportering finns det inget lagstyrt ramverk somföretag måste använda. Målet med studien är därmed att studera vilka ramverk som användsav Sveriges börsbolag. Börsbolagen delas även upp i olika branscher för att synliggöraeventuella skillnader kring ramverkens användning i respektive bransch. I samband med dettahar vi studerat vilka företag som hållbarhetsredovisar under tre olika tidpunkter; 2014, 2016samt 2018. Med hjälp av en kvantitativ innehållsanalys har bland annat följande slutsatserpåträffats: Att fler företag och branscher hållbarhetsredovisar, vilket beror påÅrsredovisningslagens tvingande isomorfism, samt att hållbarhetsrapporterna frambringarlegitimitet. Ramverken Global Reporting Initiative (GRI) Sustainability Reporting Standards,International Organization for Standardization (ISO), UN Sustainable Development Goals(SDG) och UN Global Compact (UN GC) är de mest använda ramverken. / The importance of sustainable responsibility for enterprises was introduced in 1992 lead bythe global goals of sustainability at the time. This evoked a discussion involving methods forthe accounting of sustainability. After a period of approximately 25 years, the SwedishAnnual Accounts Act was reformed to include legislation meaning larger enterprises ought toaccount for their sustainability work. Beyond this legislation, however, there is no guidanceregarding which framework an enterprise should turn to for help. The goal of this study hastherefore been to examine the uses of specific frameworks in listed companies on TheNASDAQ Stockholm stock exchange. The companies’ choice of framework is also examinedin regards to their line of business. Three points for measurement have been distinguished asthe years of 2014, 2016 and 2018. A quantitative content analysis was conducted whichgenerated a few conclusions. The results pinpoint that most companies, as well as most of thelines of businesses, conduct a sustainability report. It was also shown that businesses conductthese reports in regards to the legitimacy it earns them, as well as the compelling isomorphismthrough the Swedish Annual Accounts Act. The most frequently used frameworks weredistinguished as the Global Reporting Initiative (GRI) Sustainability Reporting Standards,International Organization for Standardization (ISO), UN Sustainable Development Goals(SDG) and the UN Global Compact (UN GC).

Rapid industrial globalization and technological development and energy consumption across the globe has significantly increased in response to mounting energy needs. The necessity for alternative and sustainable energy conversion devices has become apparent with the growth of energy utilization. In recent years, many research efforts have been made in the development of low-cost, efficient, environmentally friendly energy conversion devices. One type of energy conversion device, polymer electrolyte membrane fuel cells (PEMFCs), uses hydrogen oxidation at the anode and oxygen reduction at the cathode, with a solid-state proton conducting membrane between to generate energy with water as a by-product. PEMFCs use Nafion®, a sulfonated fluoropolymer-copolymer for proton transport; however, temperature restraints and the need for hydration limits the efficacy of this polymer. Moreover, the kinetics of oxygen reduction (ORR) are significantly slower at the cathode than the anode. Platinum is currently the industry standard, but these materials have limited resources, are expensive, and can be sensitive to carbon monoxide poisoning. Platinum is also the preferred catalyst for hydrogen evolution reactions (HER)—critical electrochemical reactions at the cathode for water splitting applications for the generation of hydrogen. Metal-Organic Frameworks (MOFs) have been explored for proton conductivity and as electrode catalysts. The tunability of metal ions and organic linkers both in situ and post-synthesis allows for the targeted design of specific surface areas and topologies while fine tuning selective functionality. Furthermore, due to morphology retention upon pyrolysis, MOFs are good platforms for logical design both pre- and post- carbonization. Taking advantage of the amendable design, along with tunable porosity and growth in controlled dimensions, this work explores the modification of a zinc based MOF as a possible candidate for proton conduction, as well modification of zinc, cobalt, and iron based MOFs for ORR catalysis. Post-synthetic modification was employed as a technique to oxidize the imidazolate ligand to include carboxylic acid functionality of a zinc based MOF. Proton conductivity generally arises from the mobility of the charge carriers present (i.e. carboxylates and phosphates). The incorporation of Brønsted acidity by way of free carboxylates is often challenging, as these are generally sites of coordination in the framework. Herein, we report the successful augmentation of Brønsted acidity with retention of framework crystallinity in a robust MOF. Additionally, the effects of metal content and carbonization temperature of MOFs were explored for ORR and HER. Cobalt and iron were doped either pre- or post-synthesis and carbonized in an inert atmosphere at various temperatures to generate MOF-derived carbons with catalytically active centers without the need for additional support. Carbons with parent MOFs containing moderate amounts of cobalt doping in a bimetallic Co/Zn MOF, or carbons that contained no zinc in the parent material, showed excellent electrocatalytic performance for ORR when carbonized at temperatures just at or above the boiling point of zinc. Zinc based MOFs were doped with various amounts of iron post-synthesis and prior to carbonization in an inert atmosphere. The formation of iron nanoflakes and nanorods on the surface of these carbons generated from the pyrolysis of these iron doped MOFs yielded high surface areas and outstanding electrochemical performance for ORR in both acidic and alkaline media. Likewise, excellent HER catalysis was exhibited by the MOF-derived carbon matrix with the highest iron loading pre-carbonization and more disperse nanorods. Not only does the amenability of MOFs make them a good platform for the direct inclusion of essential electrochemically active moieties, but it also allows for more targeted, nuanced, and rational design of materials needed to enhance proton conduction and electrochemical performance, particularly in cases on non-precious metal electrocatalysts where mechanisms are often not well-understood.

Les travaux décris dans cette thèse rapportent la conception de Metal-Organic Frameworks (MOFs) photoactifs et leur immobilisation sur surface dans le but d’obtenir et d’étudier des SurMOFs (Surface anchored Metal-Organic Frameworks) propices aux processus photoinduits dans le cadre de la photosynthèse artificielle. Pour accomplir cela, nous avons synthétisé différents ligands photoactifs et réalisé leur immobilisation sur surface à l’aide de la croissance épitaxiale en phase liquide. Ainsi, différents SurMOFs à base de zinc(II), présentant tous une structure de type SurMOF-2, ont été préparés avec succès. Les premiers matériaux obtenus à base de ligands rylènes (naphtalène dimide : NDI et pérylène diimide : PDI) ont mis en avant de fortes interactions  entre les chromophores au sein du SURMOF, causant une perte de la luminescence. Une deuxième génération de ligands plus encombrés a été synthétisée. Ils ont conduit à des SurMOFs luminescents et siège de transferts d’énergie interligands. Ces premiers travaux ont mis en avant l’impact de la disposition des ligands dans le matériau sur les propriétés photoniques. Par ailleurs, des SurMOFs constitués de ligands dicétopyrrolopyrrole (DPP) et d’anthracène (ADP) ont été synthétisés. L’étude de leurs propriétés photoniques alliée à des calculs théoriques ont montré que le transfert d’énergie au sein de ce SurMOF ne se fait pas de manière isotrope. Enfin, un SurMOF à partir de ligand DPP portant des fonctions réactives (azoture) a été synthétisé et nous avons pu greffer différentes molécules par réaction de cyclo-addition de type Huisgen, dont un accepteur d’électron, à sa périphérie par modification post-synthétique. / The aim of this thesis was the development of photoactive Metal-Organic Frameworks (MOFs) and their immobilizations on surface to obtain and study SurMOFs (Surface anchored Metal-Organic Frameworks) to investigate photoinduced processes in the context of the artificial photosynthesis. Towards this goal, we have synthesized photoactive ligands and immobilized them on surfaces using liquid phase epitaxy (LPE) in a layer-by-layer (LbL) fashion. Thus, different zinc (II) based SurMOFs, featuring a SurMOF-2 structure, were successfully prepared. The first rylene- (naphthalene diimide: NDI and perylene diimide: PDI) based SurMOFs described in this thesis showed strong  interactions between the chromophores within the MOF, causing the quenching of the luminescence. A second generation of ligands, sterically hindered, was then synthesized. They lead to luminescent SurMOFs showing efficient ligand-to-ligand energy transfer. These first results highlight the impact of linker arrangement within the material on its photonic properties. Furthermore, diketopyrrolopyrrole (DPP) and anthracene (DPA) based SurMOFs were prepared. The study of their photonic properties coupled with theoretical calculations showed that energy transfers, occurring within SurMOF-2 type materials, were not isotropic. Finally, a SurMOF, made out of a DPP ligand bearing reactive moieties (azide), was synthesized and was functionalized with different kinds of molecules, including an electron acceptor, at the periphery by post-synthetic modification using the Huisgen cycloaddtion reaction.