Synthesis and structural characterization of new Piano-stool Ruthenium(II) complexes bearing 1-Butylimidazole heteroaromatic ligand

New cationic ruthenium(II) complexes with the formula [Ru(eta(5)-C5H5)(LL)(1-BuIm)] [Z], with (LL) = 2PPh(3) or DPPE, and Z = CF3SO3-, PF6-, BPh4-, have been synthesized and fully characterized. Spectroscopic and electrochemical studies revealed that the electronic properties of the coordinated 1-butylimidazole were clearly influenced by the nature of the phosphane coligands (LL) and also by the different counter ions. The solid state structures of the six complexes determined by X-ray crystallographic studies, confirmed the expected distorted three-legged piano stool structure. However the geometry of the 1-butylimidazole ligand was found considerably different in all six compounds, being governed by the stereochemistry of the mono and bidentate coligands (PPh3 or DPPE).

Plataforma de negociação de componentes multimédia

O objectivo da tese é demonstrar a adequação do paradigma dos mercados electrónicos baseados em agentes para transaccionar objectos multimédia em função do perfil dos espectadores. Esta dissertação descreve o projecto realizado no âmbito da plataforma de personalização de conteúdos em construção. O domínio de aplicação adoptado foi a personalização dos intervalos publicitários difundidos pelos distribuidores de conteúdos multimédia, i.e., pretende-se gerar em tempo útil o alinhamento de anúncios publicitários que melhor se adeqúe ao perfil de um espectador ou de um grupo de espectadores. O projecto focou-se no estudo e selecção das tecnologias de suporte, na concepção da arquitectura e no desenvolvimento de um protótipo que permitisse realizar diversas experiências nomeadamente com diferentes estratégias e tipos de mercado. A arquitectura proposta para a plataforma consiste num sistema multiagente organizado em três camadas que disponibiliza interfaces do tipo serviço Web com o exterior. A camada de topo é constituída por agentes de interface com o exterior. Na camada intermédia encontram-se os agentes autónomos que modelam as entidades produtoras e consumidoras de componentes multimédia assim como a entidade reguladora do mercado. Estes agentes registam-se num serviço de registo próprio onde especificam os componentes multimédia que pretendem negociar. Na camada inferior realiza-se o mercado que é constituído por agentes delegados dos agentes da camada superior. O lançamento do mercado é efectuado através de uma interface e consiste na escolha do tipo de mercado e no tipo de itens a negociar. Este projecto centrou-se na realização da camada do mercado e da parte da camada intermédia de apoio às actividades de negociação no mercado. A negociação é efectuada em relação ao preço da transmissão do anúncio no intervalo em preenchimento. Foram implementados diferentes perfis de negociação com tácticas, incrementos e limites de variação de preço distintos. Em termos de protocolos de negociação, adoptou-se uma variante do Iterated Contract Net – o Fixed Iterated Contract Net. O protótipo resultante foi testado e depurado com sucesso.

Avaliação do desempenho energético de um grande edifício de serviços existente

Nesta dissertação pretende-se caracterizar o desempenho energético de um grande edifício de serviços existente, da tipologia ensino, avaliar e identificar potenciais medidas que melhorem aquele desempenho, permitindo, em complemento, determinar a sua classificação energética no âmbito da legislação vigente. A pertinência do estudo prende-se com a avaliação do desempenho energético dos edifícios e com o estudo de medidas de melhoria que permitam incrementar a eficiência energética, por recurso a um programa de simulação energética dinâmica certificado – DesignBuilder e tendo em conta a regulamentação portuguesa em vigor. Inicialmente procedeu-se à modelação do edifício com recurso ao programa DesignBuilder, e, simultaneamente, realizou-se um levantamento de todas as suas características ao nível de geometria, pormenores construtivos, sistemas AVAC e de iluminação e fontes de energia utilizadas. Com vista à caracterização do modo de operação do edifício, foi realizado um levantamento dos perfis reais de utilização em termos de ocupação, iluminação e equipamentos para os vários espaços. Foram realizadas medições de caudais de ar novo e da temperatura do ar, em alguns equipamentos e alguns espaços específicos. Foram realizadas medições em tempo real e leituras de contagens da energia eléctrica utilizada, quer em período de aulas quer em período de férias, que permitiram a desagregação das facturas da energia eléctrica que se apresentam globais para o campus do ISEP. Foram realizadas leituras de contagens de gás natural. Em sequência, foi realizada a simulação energética dinâmica com o intuito de ajustar o modelo criado aos consumos reais e de analisar medidas de melhoria que lhe conferissem um melhor desempenho energético. Essas medidas são agrupadas em quatro tipos: - Medidas de natureza comportamental; - Medidas de melhoria da eficiência energética nos sistemas de iluminação; - Medidas de melhoria de eficiência energética nos sistemas AVAC;- Medidas que visam a introdução de energias de fonte renovável; Em sequência, foi elaborada a simulação nominal e calculados os indicadores de eficiência energética com vista à respectiva classificação energética do edifício, tendo o edifício apresentado uma Classe Energética D de acordo com a escala do SCE. Finalmente, foi avaliado o impacto das diferentes medidas de melhoria identificadas e com potencial de aplicação, isto é, que apresentaram um retorno simples do investimento inferior a oito anos, tanto ao nível do desempenho energético real do edifício, como ao nível da sua classificação energética. De onde se concluiu que existe um potencial de 7% de redução nos consumos energéticos actuais do edifício e de 18% se o funcionamento do edifício for em pleno, ou seja, se todos os seus sistemas estiverem efectivamente em funcionamento, e que terá impacto na classificação energética alcançado uma Classe Energética C.

Age constraints on the late cretaceous alkaline magmatism on the West Iberian margin

Cretaceous Research 30 (2009) 575–586

Project, modelling and simulation of air stripping columns for the treatment of groundwater contaminated with volatile organic compounds

Volatile organic compounds are a common source of groundwater contamination that can be easily removed by air stripping in columns with random packing and using a counter-current flow between the phases. This work proposes a new methodology for the column design for any particular type of packing and contaminant avoiding the necessity of a pre-defined diameter used in the classical approach. It also renders unnecessary the employment of the graphical Eckert generalized correlation for pressure drop estimates. The hydraulic features are previously chosen as a project criterion and only afterwards the mass transfer phenomena are incorporated, in opposition to conventional approach. The design procedure was translated into a convenient algorithm using C++ as programming language. A column was built in order to test the models used either in the design or in the simulation of the column performance. The experiments were fulfilled using a solution of chloroform in distilled water. Another model was built to simulate the operational performance of the column, both in steady state and in transient conditions. It consists in a system of two partial non linear differential equations (distributed parameters). Nevertheless, when flows are steady, the system became linear, although there is not an evident solution in analytical terms. In steady state the resulting system of ODE can be solved, allowing for the calculation of the concentration profile in both phases inside the column. In transient state the system of PDE was numerically solved by finite differences, after a previous linearization.

Radiological impact associated to Technologically Enhanced Naturally Occurring Radioactive Materials (TENORM) from coal-fired power plants emissions

Certain materials used and produced in a wide range of non-nuclear industries contain enhanced activity concentrations of natural radionuclides. In particular, electricity production from coal is one of the major sources of increased human exposure to naturally occurring radioactive materials. A methodology was developed to assess the radiological impact due to natural radiation background. The developed research was applied to a specific case study, the Sines coal-fired power plant, located in the southwest coastline of Portugal. Gamma radiation measurements were carried out with two different instruments: a sodium iodide scintillation detector counter (SPP2 NF, Saphymo) and a gamma ray spectrometer with energy discrimination (Falcon 5000, Canberra). Two circular survey areas were defined within 20 km of the power plant. Forty relevant measurements points were established within the sampling area: 15 urban and 25 suburban locations. Additionally, ten more measurements points were defined, mostly at the 20-km area. The registered gamma radiation varies from 20 to 98.33 counts per seconds (c.p.s.) corresponding to an external gamma exposure rate variable between 87.70 and 431.19 nGy/h. The highest values were measured at locations near the power plant and those located in an area within the 6 and 20 km from the stacks. In situ gamma radiation measurements with energy discrimination identified natural emitting nuclides as well as their decay products (Pb-212, Pb-2142, Ra-226, Th-232, Ac-228, Th-234, Pa-234, U- 235, etc.). According to the results, an influence from the stacks emissions has been identified both qualitatively and quantitatively. The developed methodology accomplished the lack of data in what concerns to radiation rate in the vicinity of Sines coal-fired power plant and consequently the resulting exposure to the nearby population.

A New Approach in the Design of Air Stripping Columns for the Treatment of Groundwater Contaminated With Volatile Organic Compounds

Volatile organic compounds are a common source of groundwater contamination that can be easily removed by air stripping in columns with random packing and using a counter-current flow between the phases. This work proposes a new methodology for column design for any type of packing and contaminant which avoids the necessity of an arbitrary chosen diameter. It also avoids the employment of the usual graphical Eckert correlations for pressure drop. The hydraulic features are previously chosen as a project criterion. The design procedure was translated into a convenient algorithm in C++ language. A column was built in order to test the design, the theoretical steady-state and dynamic behaviour. The experiments were conducted using a solution of chloroform in distilled water. The results allowed for a correction in the theoretical global mass transfer coefficient previously estimated by the Onda correlations, which depend on several parameters that are not easy to control in experiments. For best describe the column behaviour in stationary and dynamic conditions, an original mathematical model was developed. It consists in a system of two partial non linear differential equations (distributed parameters). Nevertheless, when flows are steady, the system became linear, although there is not an evident solution in analytical terms. In steady state the resulting ODE can be solved by analytical methods, and in dynamic state the discretization of the PDE by finite differences allows for the overcoming of this difficulty. To estimate the contaminant concentrations in both phases in the column, a numerical algorithm was used. The high number of resulting algebraic equations and the impossibility of generating a recursive procedure did not allow the construction of a generalized programme. But an iterative procedure developed in an electronic worksheet allowed for the simulation. The solution is stable only for similar discretizations values. If different values for time/space discretization parameters are used, the solution easily becomes unstable. The system dynamic behaviour was simulated for the common liquid phase perturbations: step, impulse, rectangular pulse and sinusoidal. The final results do not configure strange or non-predictable behaviours.

Projecto de parceria entre a ONGD Estímulo e a Rede de Farmácias Portuguesas: a união de esforços entre sectores para a resolução de problemas contemporâneos

Trabalho de projeto apresentado à Escola Superior de Comunicação Social como parte dos requisitos para obtenção de grau de mestre em Gestão Estratégica das Relações Públicas.

Transient Spaces: unsettling boundaries and norms at the cultural event Noc Noc, Guimarães, Portugal

Cities are increasingly expected to be creative, inventive and to exhibit intense expressivity. In the past decades many cities have experienced growing pressure to produce and stage cultural events of different sorts and to develop new strategies that optimize competitive advantages, in order to promote themselves and to boost and sell their image. Often these actions have relied on heavy public investment and major private corporation sponsoring, but it is not always clear or measured how successful and reproductive these investments have been. In the context of strained public finances and profound economic crisis of European peripheral countries, events that emerge from local communities and have low budgets, which manage to create significant fluxes of visitors and visibility, assume an increased interest. In order to reflect and sketch possible answers, we look to an emerging body of literature concerning creative cities, and we focus on the organisation of a particular cultural event and its impact and assimilation into a medium size Portuguese city. This paper looks at the two editions (2011 and 2012) of one of such events – Noc Noc – organized by a local association in the city of Guimarães, Portugal. Inspired by similar events, Noc Noc is based on creating transient spaces of culture which are explored by artists and audiences, by transforming numerous homes into ephemeral convivial and playful social ‘public’ environments. The event is based on a number of cultural venues/homes scattered around the old and newer city, which allows for an informal urban exploration and an autonomous rambling and getting lost along streets. This strategy not only disrupts the cleavages between public and private space permitting for various transgressions, but it also disorders normative urban experiences and unsettles the dominant role of the city council as the culture patron of the large majority of events. Guimarães, an UNESCO World Heritage City was the European Capital of Culture in 2012, with a public investment of roughly 73 million euro. By interviewing a sample of people who have hosted these transitory art performances and exhibitions, sometimes doubling as artists, the events’ organizers and by experience both editions of the event, this paper illustrates how urban citizens’ engagement and motivations in a low budget cultural event can strengthen community ties. Furthermore, it also questions the advantages of large scale high budget events, and how this event may be seen as unconscious counter movement against a commodification of cultural events and everyday urban experience at large, engaging with the concepts of staging and authenticity.

Role of SPARC in Bone Remodeling and Cancer‐Related Bone Metastasis

There is a growing socioeconomic recognition that clinical bone diseases such as bone infections, bone tumors and osteoporotic bone loss mainly associated with ageing, are major issues in today0s society. SPARC (secreted protein, acidic and rich in cysteine), a matricellular glycoprotein, may be a promising therapeutic target for preventing or treating bone‐related diseases. In fact, SPARC is associated with tissue remodeling, repair, development, cell turnover, bone mineralization and may also participate in growth and progression of tumors, namely cancer‐related bone metastasis. Yet, the function of SPARC in such biological processes is poorly understood and controversial. The main objective of this work is to review the current knowledge related to the activity of SPARC in bone remodeling, tumorigenesis, and bone metastasis. Progress in understanding SPARC biology may provide novel strategies for bone regeneration and the development of anti‐angiogenic, anti‐proliferative, or counter‐adhesive treatments specifically against bone metastasis.

How Complex, Probable, and Predictable is Genetically Driven Red Queen Chaos?

Coevolution between two antagonistic species has been widely studied theoretically for both ecologically- and genetically-driven Red Queen dynamics. A typical outcome of these systems is an oscillatory behavior causing an endless series of one species adaptation and others counter-adaptation. More recently, a mathematical model combining a three-species food chain system with an adaptive dynamics approach revealed genetically driven chaotic Red Queen coevolution. In the present article, we analyze this mathematical model mainly focusing on the impact of species rates of evolution (mutation rates) in the dynamics. Firstly, we analytically proof the boundedness of the trajectories of the chaotic attractor. The complexity of the coupling between the dynamical variables is quantified using observability indices. By using symbolic dynamics theory, we quantify the complexity of genetically driven Red Queen chaos computing the topological entropy of existing one-dimensional iterated maps using Markov partitions. Co-dimensional two bifurcation diagrams are also built from the period ordering of the orbits of the maps. Then, we study the predictability of the Red Queen chaos, found in narrow regions of mutation rates. To extend the previous analyses, we also computed the likeliness of finding chaos in a given region of the parameter space varying other model parameters simultaneously. Such analyses allowed us to compute a mean predictability measure for the system in the explored region of the parameter space. We found that genetically driven Red Queen chaos, although being restricted to small regions of the analyzed parameter space, might be highly unpredictable.

Planning smart cities using wireless low energy monitoring systems

Thesis to obtain the Master Degree in Electronics and Telecommunications Engineering

Using dynamic reconfiguration to reduce the area of a JPEG decoder on FPGA

Partial dynamic reconfiguration of FPGAs can be used to implement complex applications using the concept of virtual hardware. In this work we have used partial dynamic reconfiguration to implement a JPEG decoder with reduced area. The image decoding process was adapted to be implemented on the FPGA fabric using this technique. The architecture was tested in a low cost ZYNQ-7020 FPGA that supports dynamic reconfiguration. The results show that the proposed solution needs only 40% of the resources utilized by a static implementation. The performance of the dynamic solution is about 9X slower than the static solution by trading-off internal resources of the FPGA. A throughput of 7 images per second is achievable with the proposed partial dynamic reconfiguration solution.

A comunicação empresarial nos mercados internacionais através de feiras exposições

Dissertação de Mestrado Apresentada ao Instituto de Contabilidade e Administração do Porto para a obtenção do grau de Mestre em Empreendedorismo e Internacionalização, sob orientação do Mestre Adalmiro Álvaro Malheiro de Castro Andrade Pereira

Multi-agent Simulation of Bilateral Contracting in Competitive Electricity Markets

Traditional vertically integrated power utilities around the world have evolved from monopoly structures to open markets that promote competition among suppliers and provide consumers with a choice of services. Market forces drive the price of electricity and reduce the net cost through increased competition. Electricity can be traded in both organized markets or using forward bilateral contracts. This article focuses on bilateral contracts and describes some important features of an agent-based system for bilateral trading in competitive markets. Special attention is devoted to the negotiation process, demand response in bilateral contracting, and risk management. The article also presents a case study on forward bilateral contracting: a retailer agent and a customer agent negotiate a 24h-rate tariff.