Com o crescimento da indústria dos jogos eletrônicos, surgem novos mercados e tecnologias. Os jogos eletrônicos da última geração exigem cada vez mais processamento e placas de vídeo mais poderosas. Uma solução que vem ganhando cada vez mais destaque é o Cloud Gaming, no qual o jogador realiza um comando e a informação é enviada e processada remotamente em uma nuvem, localizada na Internet, e que retorna com as imagens como uma sequência de vídeo para o jogador. Para melhorar a qualidade de experiência (QoE) é proposto um modelo que diminui o tempo de resposta entre o jogador e a nuvem, através de um arcabouço chamado Cloud Manager que utiliza a técnica de implementação de camadas, na camada do plano de fundo e predição de movimentos, utilizando uma matriz de predição, na camada do personagem. Para validar os resultados é utilizado um jogo de ação com ponto de vista onipresente dentro do sistema de Cloud Gaming Uniquitous. / With the growing video games industry, new markets and technologies are emerging. Electronic games of the new generation are increasingly requiring more processing and powerful video cards. The solution that is gaining more prominence is Cloud Gaming, which the player performs a command, the information is sent and processed remotely on a cloud, then the images return as a video stream back to the player using the Internet. To improve the Quality of Experience (QoE), it is proposed a model that reduces the response time between the player command and the stream of the resulting game scenes through a framework called Cloud Manager that use layer caching techniques, in the background, and future state prediction using a prediction matrix, in the character layer. To validate the results, a action game with god-view as point of view is used in a Cloud Gaming system called Uniquitous.

In recent decades, the concept of ecosystem services has deepened our appreciation of the myriad benefits provided by ecosystems, and the risks to human societies posed by ecosystem degradation. There is a growing realisation that problems traditionally considered to be outside the environmental policy arena are in truth strongly connected to the environment: ecosystems underlie issues spanning climate, energy, food, water, urban planning, human health, economic development, social justice, and national security. Payments for ecosystem services (PES) create positive financial incentives for the protection and restoration of ecosystems, and represent one way to better represent the value of ecosystem services across a range of sectors. PES schemes are gaining traction in climate mitigation and biodiversity protection strategies, and most of all in the water sector. PES is complementing traditional approaches to water management and helping to address deteriorating water quality, declining water flows, and flooding. This thesis takes a legal perspective, examining the role of legal frameworks in the design and administration of PES. It focuses on PES aimed at protecting freshwater ecosystem services, and considers how legal frameworks can incorporate PES into strategies for drinking water provision. It examines an emerging body of law relating directly to PES, and provides an opportunity to consider some of the leading examples of the ES concept being reflected in law. It distinguishes three broad categories of legal frameworks that establish, regulate or enable PES. A comparative methodology is applied to an analysis of case studies of legal frameworks for PES from: Costa Rica, Ecuador, Peru, Colombia, New York, England and Ontario. This analysis draws out conclusions about how the law relates to key policy issues around ES and PES, and different approaches to developing legal frameworks to guide PES, depending on different contexts and policy objectives.

A análise e construção de um sistema computacional utilizando conceitos de frameworks, para simulação do fluxo de peças em Sistemas Flexíveis de Fabricação são apresentados. A criação da estrutura de dados para descrição completa do Sistema Flexível de Fabricação e a simulação da etapa de torneamento, durante o fluxo da peça são implementados. O método de simulação no framework é baseado na modelagem geométrica e funcional da placa de fixação durante a operação de torneamento. Para a escolha da melhor fixação durante o torneamento, é utilizado um índice calculado pelo sistema computacional, de acordo com a qualidade da fixação. No processo de desenvolvimento do framework são utilizados conceitos de Reuso de Software, associações entre Frameworks e uma estrutura de persistência de dados utilizando um banco de dados relacional, com um modelo de armazenamento desvinculado dos tipos de dados e tabelas especificas, permitindo assim implementações de novos métodos para simulação de outros meios produtivos. / Analysis and construction of a computer system using concepts of frameworks, for simulation of the workflow pieces in flexible manufacturing systems are presented. The creation of a database to fully describe the flexible manufacturing system and the simulation of the turning stage, during the workflow pieces are implemented. The method of simulation in the framework is based on geometric modeling and functional of the mounting plate during the turning operation. To choose the best mounting during the turning operation, its assigned an index calculated by the computer system, according to the quality of mounting. In the process of development of the framework were used concepts of software reuse, frameworks and associations between a structure of data persistence using relational database, with a detached storage model data types and specific tables, allowing implementation of new methods to simulate other productive means.

abstract: Among the alternative processes for the traditional distillation, adsorption and membrane separations are the two most promising candidates and metal-organic frameworks (MOFs) are the new material candidate as adsorbent or membrane due to their high surface area, various pore sizes, and highly tunable framework functionality. This dissertation presents an investigation of the formation process of MOF membrane, framework defects, and two-dimensional (2D) MOFs, aiming to explore the answers for three critical questions: (1) how to obtain a continuous MOF membrane, (2) how defects form in MOF framework, and (3) how to obtain isolated 2D MOFs. To solve the first problem, the accumulated protons in the MOF synthesis solution is proposed to be the key factor preventing the continuous growth among Universitetet I Oslo-(UiO)-66 crystals. The hypothesis is verified by the growth reactivation under the addition of deprotonating agent. As long as the protons were sufficiently coordinated by the deprotonating agent, the continuous growth of UiO-66 is guaranteed. Moreover, the modulation effect can impact the coordination equilibrium so that an oriented growth of UiO-66 film was achieved in membrane structures. To find the answer for the second problem, the defect formation mechanism in UiO-66 was investigated and the formation of missing-cluster (MC) defects is attributed to the partially-deprotonated ligands. Experimental results show the number of MC defects is sensitive to the addition of deprotonating agent, synthesis temperature, and reactant concentration. Pore size distribution allows an accurate and convenient characterization of the defects. Results show that these defects can cause significant deviations of its pore size distribution from the perfect crystal. The study of the third questions is based on the established bi-phase synthesis method, a facile synthesis method is adopted for the production of high quality 2D MOFs in large scale. Here, pyridine is used as capping reagent to prevent the interplanar hydrogen bond formation. Meanwhile, formic acid and triethylamine as modulator and deprotonating agent to balance the anisotropic growth, crystallinity, and yield in the 2D MOF synthesis. As a result, high quality 2D zinc-terephthalic acid (ZnBDC) and copper-terephthalic acid (CuBDC) with extraordinary aspect ratio samples were successfully synthesized. / Dissertation/Thesis / Doctoral Dissertation Chemical Engineering 2019

abstract: The large-scale anthropogenic emission of carbon dioxide into the atmosphere leads to many unintended consequences, from rising sea levels to ocean acidification. While a clean energy infrastructure is growing, mid-term strategies that are compatible with the current infrastructure should be developed. Carbon capture and storage in fossil-fuel power plants is one way to avoid our current gigaton-scale emission of carbon dioxide into the atmosphere. However, for this to be possible, separation techniques are necessary to remove the nitrogen from air before combustion or from the flue gas after combustion. Metal-organic frameworks (MOFs) are a relatively new class of porous material that show great promise for adsorptive separation processes. Here, potential mechanisms of O2/N2 separation and CO2/N2 separation are explored. First, a logical categorization of potential adsorptive separation mechanisms in MOFs is outlined by comparing existing data with previously studied materials. Size-selective adsorptive separation is investigated for both gas systems using molecular simulations. A correlation between size-selective equilibrium adsorptive separation capabilities and pore diameter is established in materials with complex pore distributions. A method of generating mobile extra-framework cations which drastically increase adsorptive selectivity toward nitrogen over oxygen via electrostatic interactions is explored through experiments and simulations. Finally, deposition of redox-active ferrocene molecules into systematically generated defects is shown to be an effective method of increasing selectivity towards oxygen. / Dissertation/Thesis / Masters Thesis Chemical Engineering 2019

Dissertação apresentada para obtenção do grau de Doutor em Engenharia Electrotécnica e de Computadores, sob a orientação do Doutor Gabriel David

Metal-organic materials (MOMs) represent a unique class of porous materials that captured a great scientific interest in various fields such as chemical engineering, physics and materials science. They are typically assembled from metal ions or metal clusters connected by multifunctional organic ligands. They represent a wide range of families of materials that varied from 0D to 3D networks: the discrete (0D) structures exemplified by metal-organic polyhedra (MOPs), cubes and nanoballs while the polymeric 1D, 2D and 3D structures exemplified by coordination polymers (CPs). Indeed, the porous 3D structures include metal-organic frameworks (MOFs), porous coordination polymers (PCPs) and porous coordination networks (PCNs). Nevertheless, MOMs are long and well-known from more than 50 years ago as exemplified by CPs that were firstly introduced in early 1960s and reviewed in 1964. However, the scientific interest toward MOMs has been enormously grown only since late 1990s, with the discovery of MOMs with novel properties, especially the high permanent porosity as exemplified by MOF-5 and HKUST-1. The inherent tunability of MOMs from the de novo design to the post-synthetic modification along with their robustness, afford numerous important families of nets "platforms" such as pcu, dia, tbo, mtn and rht topology networks. There are more than 20,000 crystal structures of MOMs in the Cambridge Structure Database (CSD). However, only a few of the networks can be regarded as families or platforms where the structure is robust, fine-tunable and inherently modular. Such robustness and inherent modularity of the platforms allow the bottom-up control over the structure "form comes before function" which subsequently facilitates the systematic study of structure/function in hitherto unprecedented way compared with the traditional screening approaches that are commonly used in materials science. In this context, we present the crystal engineering of two MOM platforms; dia and novel fsc platforms as well we introduce the novel two-step synthetic approach using trigonal prismatic clusters to build multinodal 2D and 3D MOM platforms. For the dia platform, we introduce a novel strategy to control over the level of the interpenetration of dia topology nets via solvent-template control and study the impact of the resulting different pore sizes on the squeezing of CH4, CO2 and H2 gases. New benchmark material for methane isosteric heat of adsorption was produced from this novel work. Indeed we introduce the crystal engineering of a novel versatile 4,6-c fsc platform that is formed from linking two of the longest known and most widely studied MBBs: the square planar MBB [Cu(AN)4]2+( AN = aromatic nitrogen donor) and square paddlewheel MBB [Cu2(CO2R)4] that are connected by five different linkers with different length, L1-L5. The resulting square grid nets formed from alternating [Cu(AN)4]2+ and [Cu2(CO2R)4] moieties are pillared at the axial sites of the [Cu(AN)4]2+ MBBs with dianionic pillars to form neutral 3D 4,6-connected fsc (four, six type c) nets. Pore size control in this family of fsc nets was exerted by varying the length of the linker ligand whereas pore chemistry was implemented by unsaturated metal centers (UMCs) and the use of either inorganic or organic pillars. 1,5-naphthalenedisulfonate (NDS) anions pillar in an angular fashion to afford fsc-1-NDS, fsc-2-NDS, fsc-3-NDS, fsc-4-NDS and fsc-5-NDS from L1-L5, respectively. Experimental CO2 sorption studies revealed higher isosteric heat of adsorption (Qst) for the compound with the smaller pore size (fsc-1-NDS). Computational studies revealed that there is higher CO2 occupancy about the UMCs in fsc-1-NDS compared to other extended variants that were synthesized with NDS. SiF62- (SIFSIX) anions in fsc-2-SIFSIX form linear pillars that result in eclipse [Cu2(CO2R)4] moieties at a distance of just 5.86 Å. The space between the [Cu2(CO2R)4] moieties is a strong CO2 binding site that can be regarded as being an example of a single-molecule trap; this finding has been supported by modeling studies. Furthermore, we present herein the implementation of the two-step synthetic approach for the construction of novel multinodal MOM platforms, using the trigonal prism cluster [M3(µ3-O)(RCO2)6] as a precursor to build novel stable multinodal 2D and 3D frameworks. In the first step, the bifunctional carboxylate ligands are reacted with Fe+3 or Cr+3 salts to isolate highly symmetrical decorated trigonal prismatic clusters with diverse decoration such as pyridine, amine and cyano coordinating functional groups using pyridine carboxylate, amino carboxylate, cyano carboxylate type ligands, respectively. Afterward, the isolated highly soluble trigonal prismatic salts were reacted in the second step with another metal that can act as node or linker to connect the discrete trigonal prismatic clusters to build 2D or 3D networks. Indeed, we were able to develop another novel high-symmetry Cu cluster [Cu3(µ3-Cl)(RNH2)6Cl6] by utilizing CuCl2 salt and amine decorated trigonal prismatic cluster. Two novel 3D water stable frameworks with acs and stp topologies have been afforded. Our work on the crystal engineering design and synthesis of new MOM platforms offer an exceptional level of control over the resulting structure including; the resulting topology, pore size, pore chemistry and thereby enable the control over the resulting physicochemical properties in a manner that facilitates the achieving of the desired properties.

Encapsulation of biomolecules is of great interest to research advances related to biology, physiology, immunology, and biochemistry, as well as industrial and biomedical applications such as drug delivery, biocatalysis, biofuel, food and cosmetics. Encapsulation provides functional characteristics that are not fulfilled by free biomolecules and stabilizes the fragile biomolecules. In terms of biocatalysis, solid support can often enhance the stability of enzymes, as well as facilitate separation and recovery for reuse while maintaining activity and selectivity. Various kinds of materials have been used for encapsulation of biomolecules, among which, porous materials are an important group. Metal-organic frameworks (MOFs) have attracted much attention and emerged as a new generation of highly porous functional materials with potential in a variety of fields such as gas separation and storage, catalysis, sensors and biomedical applications. Their structural versatility and amenability to be designed with specific functionality, together with their extra-large surface areas confer them a special place amongst traditional porous materials. In particular, because ligands can be designed with particular organic functional groups for specific interactions with biomolecules, they are attractive in the stabilization and retention of enzyme/proteins for biomedical or biocatalysis applications. With enlarged pore sizes, mesoporous (pore sizes in the range of 2 to 50 nm) MOFs are of great interest in the encapsulation of proteins. In this dissertation, I am focusing on the encapsulation of biomolecules into mesoporous MOFs (mesoMOFs) to estabilish the biomolecules@mesoMOF platform, including synthesis, characterization and mechanistic studies of a series of novel biomolecules@mesoMOF materials, and to develop the biomolecule@mesoMOFs platform for various applications.

Metal-organic materials (MOMs) represent an emerging class of materials comprised of molecular building blocks (MBBs) linked by organic linker ligands. MOMs recently attract great attention because of their ability to exhibit permanent porosity, thereby enabling study of properties in the context of gas storage, gas separation, solid supports for sensors, catalysis and so on. Although MOMs have been studied for over 60 years, the porous nature of MOMs was not systematically and widely explored until the early 1990's. This may be one of the reasons why template-directed synthesis of MOMs remains relatively underexplored, especially when compared to other classes of porous material (e.g. zeolite and mesoporous silicates). However, the study of template-directed synthesis exhibits great significance to the research field of MOMs as these considerations: (i) to access analogues of prototypal MOM platforms that cannot be prepared directly; (2) to create porous materials with new topologies; (3) to transfer the functionality of templates to MOMs; (4) to exert fine control over structural features. In this dissertation, I chose a functional organic material, porphyrin, as templates and succeeded to synthesize a series of porphyrin-encapsulating MOMs, (porph@MOMs), in which the porphyrins were encapsulated inside the cavities as guests. Porphyrins molecules can template the formation cavities with different shapes and sizes (e.g. triangle, square or hexagon) to accommodate the porphyrins molecules when organic ligands with different size and symmetry were utilized during the synthesis. On the other hand, the porphyrins molecules can also template the formation of octahemioctahedral cages or hexahedron cages with porphyrins trapped inside, which further built the tbo, pcu, rtl, zzz, mzz networks. By selecting templated porph@MOMs as platforms, post-synthetic modifications (PSMs) of porph@MOMs were further studied. A cadmium MOM, porph@MOM-10, can undergo PSM by Mn(II) or Cu(II) via single-crystal-to-single-crystal processes. The Mn- and Cu- exchanged PSM variants exhibit catalytic activity for epoxidation of trans-stilbene. Porph@MOM-11 can serve as a platform to undergo a new PSM process involving cooperative addition of metal salts via single-crystal-to-single-crystal processes. The incorporation of the salts leads to higher H2 and CO2 volumetric uptake and higher CO2 vs CH4 selectivity. Porph@MOM-11 was also found to be a versatile platform that can undergo metal ion exchange with Cu2+ in single-crystal-to-single-crystal fashion. The use of mixed metal salt solutions (Cu2+/Cd2+) with varying ratios of metal salts enabled systematic study of the metal exchange process in porph@MOM-11 in such a manner that, at one extreme, only the Cd porphyrin moieties undergo metal ion exchange, whereas at the other extreme both the framework and the porphyrin moiety are fully exchanged. It is also observed that a concerted PSMs approach of metal ion exchange and ligand addition towards a porphyrin-walled MOM, porphMOM-1 affords a porphyrin-encapsulating MOM, porph@MOM-14, in which porphyrin anions are encapsulated in the octahemioctahedral polyhedral cage via weak interactions. Beside of the template-directed synthesis and post-synthetic modification of porph@MOMs, pre-synthetic control of metal-organic materials' structures was also studied in this dissertation. Due to the partial flexibility of 1,3-benzenedicarboxylate linkers, kagom[eacute] lattice and NbO supramolecular isomers were observed from a complexation of bulky 1,3-benzenedicarboxylate ligand to Cu(II) paddlewheel moieties. In addition, a new family of hybrid nanoball vanadium MOM structures (Hyballs) was prepared by the self-assemble of trimesic acid with tetranuclear and pentanuclear vanadium polyoxometalates. These hyballs are robust, permanently porous and their exterior surfaces facilitate cross-linking via hydrogen bonds or coordination bonds to generate pcu networks.

Metal-organic materials (MOMs) assembled from metal-based building blocks and organic linkers have attracted much interest due to their large pore dimensions and their enormous structural diversity. In comparison to their inorganic counterparts (zeolites), these crystalline materials can be easily modified to tailor pore dimensions and functionality for specifically targeted properties. The work presented herein encompasses the development of a synthetic 2-step process for the construction of novel families of MOMs or 'platforms' and allow us exquisite design and control over the resulting network topologies. Examples of cationic mesoporous structures were initially exploited, containing carboxylate based centers connected by metal-pyridine bonds. The inherently cationic nets allowed for subsequent anion exchange which can be regarded as an elegant and easy postsynthetic modification strategy. The incorporation of different functionalities inside the channels of the networks was then demonstrated as useful in terms of carbon dioxide capture. The scope of the 2-step process was then expanded to construction of the first trinodal MOM platform involving triangular, tetrahedral and trigonal prismatic building units: tp-PMBB-1-asc. Examples of reticular chemistry are shown which enable the formation of large and functionalized nanocages with retention of the underlying network topology. Gas adsorption studies indicate relatively high uptakes of carbon dioxide and hydrogen which, together with the use of inexpensive ligands, provide an excellent cost/performance ratio of these materials. Moreover, very high stability in organic solvents and especially in water are addressed which is a particularly challenging, but industrially relevant target in the field of Metal-Organic Materials. The 2-step approach was also used to synthesize a new and versatile class of metal-organic materials with augmented lonsdaleite-e (lon-e-a) topology. This family of lon-e nets is built by pillaring of hexagonal 2-dimensional kagomé (kag) lattices that are in turn pillared by a trigonal prismatic Primary Molecular Building Block (tp-PMBB-1). These MOMs represent the first examples of axial-to-axial-pillared undulating kag layers and they are readily fine-tuned because the bdc2- moieties can be varied at their 5-position without changing the overall structure. This lon-e platform possesses functionalized hexagonal channels since the kag lattices are necessarily eclipsed. The effect of the substituent at the 5-positions of the bdc2- linkers upon gas adsorption, particularly the heats of adsorption of carbon dioxide and methane, were studied. If linear dicarboxylates were instead utilized, we were able to synthesize a new and versatile class of metal-organic materials that exhibits 4,6-connected fsb topology. These networks are constructed from simple and inexpensive building units and since interpenetration is precluded, afford very high void volumes. They therefore represent ideal targets to generate a novel family of frameworks, because of the ready availability functionalized and expanded ligand derivatives. They also allow for systematic fine tuning and could ultimately provide a roadmap to ultra-high surface areas from simple building blocks.