Aumento de energia renovável na Ilha da Madeira: proposta integrada para o setor dos transportes e da geração de energia elétrica

Dissertação para obtenção do grau de Mestre em Engenharia Electrotécnica Ramo de Energia

Development of biocompatible and “smart” porous structures using CO2-assisted processes

Dissertação apresentada para a obtenção do grau de Doutor em Engenharia Química, especialidade Engenharia da Reacção Química, pela Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia

Chemical composition and antioxidante activity of Tunisian Origanum glandulosum Desf. essential oil and volatile oil obtain by supercritical CO2 extraction

Dried flowers and leaves of Origanum glandulosum Desf. were submitted to hydrodistillation (HD) and supercritical fluid extraction with CO2 (SFE). The essential oils isolated by HD and volatile oils obtained by SFE were analysed by GC and GC/MS. Total phenolics content and antioxidant effectiveness were performed. The main components of the essential oils from Bargou and Nefza were: p-cymene (40.4% and 39%), thymol (38.7% and 34.4%) and γ- terpinene (12.3% and 19.2%), respectively. The major components obtain by SFE in the volatile oil, from Bargou and Nefza, were: p-cymene (32.3% and 36.2%), thymol (41% and 40%) and γ-terpinene (20.3% and 13.3%). Total phenolic content, expressed in gallic acid equivalent (GAE) g kg-1 dry weight, varied from 12 to 27 g kg-1 dw, and the ability to scavenge the DPPH radicals, expressed by IC50 ranged from 44 to143 mg L-1.

Strategies for price reduction of HIV medicines under a monopoly situation in Brazil

ABSTRACT OBJECTIVE To analyze Government strategies for reducing prices of antiretroviral medicines for HIV in Brazil. METHODS Analysis of Ministry of Health purchases of antiretroviral medicines, from 2005 to 2013. Expenditures and costs of the treatment per year were analyzed and compared to international prices of atazanavir. Price reductions were estimated based on the terms of a voluntary license of patent rights and technology transfer in the Partnership for Productive Development Agreement for atazanavir. RESULTS Atazanavir, a patented medicine, represented a significant share of the expenditures on antiretrovirals purchased from the private sector. Prices in Brazil were higher than international references, and no evidence was found of a relationship between purchase volume and price paid by the Ministry of Health. Concerning the latest strategy to reduce prices, involving local production of the 200 mg capsule, the price reduction was greater than the estimated reduction. As for the 300 mg capsule, the amounts paid in the first two years after the Partnership for Productive Development Agreement were close to the estimated values. Prices in nominal values for both dosage forms remained virtually constant between 2011 (the signature of the Partnership for Productive Development Agreement), 2012 and 2013 (after the establishment of the Partnership). CONCLUSIONS Price reduction of medicines is complex in limited-competition environments. The use of a Partnership for Productive Development Agreement as a strategy to increase the capacity of local production and to reduce prices raises issues regarding its effectiveness in reducing prices and to overcome patent barriers. Investments in research and development that can stimulate technological accumulation should be considered by the Government to strengthen its bargaining power to negotiate medicines prices under a monopoly situation.

A comparison of Sinogram Affirmed Iterative Reconstruction and filtered back projection on image quality and dose reduction in paediatric head CT: a phantom study

Background: Computed tomography (CT) is one of the most used modalities for diagnostics in paediatric populations, which is a concern as it also delivers a high patient dose. Research has focused on developing computer algorithms that provide better image quality at lower dose. The iterative reconstruction algorithm Sinogram-Affirmed Iterative Reconstruction (SAFIRE) was introduced as a new technique that reduces noise to increase image quality. Purpose: The aim of this study is to compare SAFIRE with the current gold standard, Filtered Back Projection (FBP), and assess whether SAFIRE alone permits a reduction in dose while maintaining image quality in paediatric head CT. Methods: Images were collected using a paediatric head phantom using a SIEMENS SOMATOM PERSPECTIVE 128 modulated acquisition. 54 images were reconstructed using FBP and 5 different strengths of SAFIRE. Objective measures of image quality were determined by measuring SNR and CNR. Visual measures of image quality were determined by 17 observers with different radiographic experiences. Images were randomized and displayed using 2AFC; observers scored the images answering 5 questions using a Likert scale. Results: At different dose levels, SAFIRE significantly increased SNR (up to 54%) in the acquired images compared to FBP at 80kVp (5.2-8.4), 110kVp (8.2-12.3), 130kVp (8.8-13.1). Visual image quality was higher with increasing SAFIRE strength. The highest image quality was scored with SAFIRE level 3 and higher. Conclusion: The SAFIRE algorithm is suitable for image noise reduction in paediatric head CT. Our data demonstrates that SAFIRE enhances SNR while reducing noise with a possible reduction of dose of 68%.

A narrative review on the reduction of effective dose to a paediatric patient by using different combinations of kVp, mAs and additional filtration whilst maintaining image quality

This paper reviews the literature for lowering of dose to paediatric patients through use of exposure factors and additional filtration. Dose reference levels set by The International Commission on Radiological Protection (ICRP) will be considered. Guidance was put in place in 1996 requires updating to come into line with modern imaging equipment. There is a wide range of literature that specifies that grids should not be used on paediatric patients. Although much of the literature advocates additional filtration, contrasting views on the relative benefits of using aluminium or copper filtration, and their effects on dose reduction and image quality can vary. Changing kVp and mAs has an effect on the dose to the patient and image quality. Collimation protects adjacent structures whilst reducing scattered radiation.

An SEM investigation of the pozzolanic activity of a waste catalyst oil refinery

The most active phase of the fluid catalytic cracking (FCC) catalyst, used in oil refinery, is zeolite-Y which is an aluminosilicate with a high internal and external surface area responsible for its high reactivity. Waste FCC catalyst is potentially able to be reused in cement-based materials - as an additive - undergoing a pozzolanic reaction with calcium hydroxide (Ca(OH)2) formed during cement hydration [1-3]. This reaction produces additional strength-providing reaction products i.e., calcium silicate hydrate (C-S-H) and hydrous calcium aluminates (C-A-H) which exact chemical formula and structure are still unknown. Partial replacement of cement by waste FCC catalyst has two key advantages: (1) lowering of cement production with the associated pollution reduction as this industry represents one of the largest sources of man-made CO2 emissions, and (2) improving the mechanical properties and durability of cement-based materials. Despite these advantages, there is a lack of fundamental knowledge on pozzolanic reaction mechanisms as well as spatial distribution of porosity and solid phases interactions at the microstructural level and consequently their relationship with macroscopical engineering properties of catalyst/cement blends. Within this scope, backscattered electron (BSE) images acquired in a scanning electron microscope (SEM) equipped with Energy-Dispersive Spectroscopy (EDS) and by X-ray diffraction were used to investigate chemical composition of hydration products and to analyse spatial information of the microstructure of waste FCC catalyst blended cement mortars. For this purpose mortars with different levels of cement substitution by waste catalyst as well as with different hydration ages, were prepared. The waste FCC catalyst used is produced by the Portuguese refinery company Petrogal S.A.

Redox-active cytotoxic diorganotin(IV) cycloalkylhydroxamate complexes with different ring sizes: Reduction behaviour and theoretical interpretation

Two series of new diorganotin(IV) cycloalkylhydroxamate complexes with different ring sizes (cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl), formulated as the mononuclear [R2Sn(HL)(2)] (1:2) (a, R=Bu-n and Ph) and the polymeric [R2SnL](n) (1:1) (b, R=Bu-n) compounds, were prepared and fully characterized. Single crystal X-ray diffraction for [(Bu2Sn)-Bu-n{C5H9C(O)NHO}(2)] (3a) discloses the cis geometry and strong intermolecular NH center dot center dot center dot O interactions. The in vitro cytotoxic activities of the complexes were evaluated against HL-60, Bel-7402, BGC-823 and KB human tumour cell lines, the greater activity concerning [(Bu2Sn)-Bu-n(HL)(2)] [HL=C3H5C(O)NHO (1a), C6H11C(O)NHO (4a)] towards BGC-823. The complexes undergo, by cyclic voltammetry and controlled-potential electrolysis, one irreversible overall two-electron cathodic process at a reduction potential that does not appear to correlate with the antitumour activity. The electrochemical behaviour of [R2Sn(C5H9C(O)NHO)(2)] [R=Bu-n (3a), Ph (7a)] was also investigated using density functional theory (DFT) methods, showing that the ultimate complex structure and the mechanism of its formation are R dependent: for the aromatic (R = Ph) complex, the initial reduction step is centred on the phenyl ligands and at the metal, being followed by a second reduction with Sn-O and Sn-C ruptures, whereas for the alkyl (R=Bu-n) complex the first reduction step is centred on one of the hydroxamate ligands and is followed by a second reduction with Sn-O bond cleavages and preservation of the alkyl ligands. In both cases, the final complexes are highly coordinative unsaturated Sn-II species with the cis geometry, features that can be of biological significance.

Electric vehicles as a mean to reduce, energy, emissions and electricity costs

Electric vehicles (EVs) and plug-in hybrid electric vehicles (PHEVs), which obtain their fuel from the grid by charging a battery, are set to be introduced into the mass market and expected to contribute to oil consumption reduction. This research is concerned with studying the potential impacts on the electric utilities of large-scale adoption of plug-in electric vehicles from the perspective of electricity demand, fossil fuels use, CO2 emissions and energy costs. Simulations were applied to the Portuguese case study in order to analyze what would be the optimal recharge profile and EV penetration in an energy-oriented, an emissions-oriented and a cost-oriented objective. The objectives considered were: The leveling of load profiles, minimization of daily emissions and minimization of daily wholesale costs. Almost all solutions point to an off-peak recharge and a 50% reduction in daily wholesale costs can be verified from a peak recharge scenario to an off-peak recharge for a 2 million EVs in 2020. A 15% improvement in the daily total wholesale costs can be verified in the costs minimization objective when compared with the off-peak scenario result.

The electric vehicles as a mean to reduce Co2 emissions and energy costs in isolated regions: the São Miguel (Azores) case study

Most of small islands around the world today, are dependent on imported fossil fuels for the majority of their energy needs especially for transport activities and electricity production. The use of locally renewable energy resources and the implementation of energy efficiency measures could make a significant contribution to their economic development by reducing fossil fuel imports. An electrification of vehicles has been suggested as a way to both reduce pollutant emissions and increase security of supply of the transportation sector by reducing the dependence on oil products imports and facilitate the accommodation of renewable electricity generation, such as wind and, in the case of volcanic islands like Sao Miguel (Azores) of the geothermal energy whose penetration has been limited by the valley electricity consumption level. In this research, three scenarios of EV penetration were studied and it was verified that, for a 15% LD fleet replacement by EVs with 90% of all energy needs occurring during the night, the accommodation of 10 MW of new geothermal capacity becomes viable. Under this scenario, reductions of 8% in electricity costs, 14% in energy, 23% in fossil fuels use and CO2 emissions for the transportation and electricity production sectors could be expected.

Análise do balanço entre sequestro e emissão de CO2 resultante do circuito de produção e consumo de biomassa florestal numa central de co-geração

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Bioenergia

Eficiência energética em edifícios residenciais da cidade do Porto

O consumo de energia a nível mundial tem atingido valores históricos, devido ao crescimento da população mundial e ao aumento do consumo per capita. Nesta medida é extremamente importante existirem alternativas para que a redução do consumo de energia de todos os países seja uma realidade, evitando também as consequências ambientais, em particular as alterações climáticas, resultantes da utilização intensiva de combustíveis fósseis. Portugal, tal como outros países da União Europeia, tem que cumprir metas, pelo que é urgente encontrarem-se soluções de forma a diminuir o consumo de energia sem interferir com o nosso dia-a-dia. A cidade do Porto, tal como qualquer cidade, precisa de imensa energia desde os transportes até à indústria, passando pelos edifícios. Os edifícios, residenciais e de serviços, são responsáveis por mais de 50% de energia primária consumida no concelho do Porto, sendo que aos edifícios residenciais corresponde um consumo de 1.473 GWh/ano de energia primária, o que é um valor elevado. Numa primeira parte deste trabalho foi efetuado um levantamento de informação caracterizando a cidade do Porto relativamente ao seu edificado e consumos energéticos. Numa segunda parte propuseram-se medidas para reduzir o consumo para cada tipo de utilização de energia, nomeadamente preparação de refeições, AQS (água quente sanitária), aquecimento ambiente, frio (frigorífico, arcas, etc.), outros e iluminação. Para cada um destes tipos de utilização estudou-se, sempre que possível, a evolução do longo do tempo (2004 a 2012) e possíveis cenários de evolução para o futuro. Para além disso, também se estudou a evolução do mix de produção de energia elétrica de 2004 até 2012 e previsões da evolução do mix para o futuro. Nesta análise foi tido em conta o aspeto ambiental contabilizando-se, sempre que possível, as emissões de poluentes resultantes do consumo de energia. Por fim, efetuou-se uma avaliação técnica, ambiental e económica das medidas propostas. Pode dizer-se que a maioria das medidas propostas a serem implementadas conduziria a uma redução do consumo de energia e consequentemente a uma diminuição das emissões de poluentes, em particular dos gases com efeito de estufa (CO2). Em termos técnicos a maioria das medidas pode ser aplicada embora algumas delas envolvam custos de investimento significativos. Dada a conjuntura atual, seria importante obter o financiamento necessário para a implementação das medidas propostas e a divulgação de medidas já existentes, tais como os programas para AQS e janelas eficientes.

Gestão de instalações eléctricas para optimização do desempenho, eficiência e qualidade de energia em grandes edifícios com integração de Miniprodução

As alterações climáticas e as emissões de CO2 são questões que suscitam a nível internacional e nacional o desenvolvimento de estratégias que atenuem os seus impactes. A Eficiência Energética (EE) é essencial para que num futuro próximo não haja impactes significativos no meio ambiente devido a elevado e ineficiente consumo energético. A União Europeia (UE) e Portugal têm desenvolvido políticas e programas que estimulam a eficiência energética, bem como a diminuição de gases com efeito de estufa (GEE) e a promoção da utilização de fontes de energia renovável. Por outro lado vivemos numa sociedade que passa cerca de 80% do seu tempo em edifícios e, nestes, é consumida 40% da energia mundial. Com uma dependência energética superior a 80%, Portugal tem vindo a apostar, nos últimos anos, em fontes de energia renovável. Esta aposta serve como substituição de fontes, mas não leva directamente à redução de consumos. A redução da factura de energia só pode ser atingida com uma maior eficiência energética e melhores práticas de gestão de energia em edifícios, transportes e industria. Esta dissertação centra-se especificamente num conjunto de edifícios públicos, património municipal da autarquia de Matosinhos, cujo modelo de fornecimento da energia eléctrica é passível de análise crítica no sentido de uma optimização radical ao nível da concepção da rede e exploração, com consequente redução de custos ao nível da facturação. Esta nova metodologia de exploração e gestão de sistemas eléctricos incidirá na criação de um “campus” energético autárquico resultante do novo layout da rede e respectivo fornecimento de energia a partir da rede de distribuição pública. O estudo permitirá fornecer ferramentas fundamentais para a gestão municipal e empresarial ao nível da sustentabilidade energética nos edifícios públicos com abrangência aos serviços empresariais. De referir que a gestão das instalações eléctricas para optimização do desempenho, eficiência e qualidade de energia é aplicável aos 308 municípios nacionais com relevância para as empresas que apresentam consumos significativos nos seus edifícios. Enquanto funcionário da Câmara Municipal de Matosinhos, este município foi uma escolha natural como referência, na análise da relação existente entre a administração local e a gestão da energia. Para ajudar à análise foi efectuado um benchmarketing a cinco edifícios municipais: Edifício dos Paços do Concelho, Biblioteca Municipal Florbela Espanca, Palacete Visconde Trevões, ex-Edifício dos SMAS e Edifício do ex-Tribunal, visando potenciar a correcta gestão de energia destes edifícios por parte das entidades que os gerem, perante novas oportunidades de melhoria e soluções encontradas. Como contributo às metas impostas pela Directiva 2009/28/CE para 2020, a qual prevê uma redução de 20% no consumo final de energia através da eficiência energética, a incorporação de 20% de energia renovável no consumo energético global e a consequente redução em 20% da emissão de GEE, é apresentado um estudo ao nível de um parque fotovoltaico com a componente técnica e económica.

Glucose-6-phosphate dehydrogenase and glutathione reductase activity in methemoglobin reduction by methylene blue and cyst amine: study on glucose-6-phosphate dehydrogenase-deficient individuals, on normal subjects and on riboflavin-treated subjects

The authors have standardized methods for evaluation of the activity of the glucose-6-phosphate dehydrogenase and of glutathione reductase. The general principle of the first method was based on methemoglobin formation by sodium nitrite followed by stimulation of the glucose-6-phosphate dehydrogenase with methylene blue. Forty six adults (23 males and 23 females) were studied. Subjects were not G6PD deficient and were aged 20 to 30 years. The results showed that methemoglobin reduction by methylene blue was 154.40 and 139.90 mg/min (p<0.05) for males and females, respectively, in whole blood, and 221.10 and 207.85 mg/min (n.s.), respectively, in washed red cells. These data showed that using washed red cells and 0.7g% sodium nitrite concentration produced no differences between sexes and also shortened reading time for the residual amount of methemoglobin to 90 minutes. Glutathione reductase activity was evaluated on the basis of the fact that cystamine (a thiol agent) binds to the SH groups of hemoglobin, forming complexes. These complexes are reversed by the action of glutathione reductase, with methemoglobin reduction occurring simultaneously with this reaction. Thirty two adults (16 males and 16 females) were studied. Subjects were not G6PD deficient and were aged 20 to 30 years. Methemoglobin reduction by cystamine was 81.27 and 91.13 mg/min (p<0.01) for males and females, respectively. These data showed that using washed red cells and 0.1 M cystamine concentration permits a reading of the residual amount of methemoglobin at 180 minutes of incubation. Glutathione reductase activity was evaluated by methemoglobin reduction by cystamine in 14 females before and after treatment with 10 mg riboflavin per day for 8 days. The results were 73.69 and 94.26 jug/min (p<0.01) before and after treatment, showing that riboflavin treatment increase glutathione reductase activity even in normal individuals. Three Black G6PD-deficient individuals (2 males and 1 female) were also studied. The G6PD and glutathione reductase were partially activated, the change being more intense in males. On the basis of race and of the laboratory characteristics observed, it is possible to suggest that the G6PD deficiency of these individuals is of the African type and that the female is heterozygous for this deficiency. Analysis of the results as a whole permitted us to conclude that the methods proposed here were efficient for evaluating the activity of the glucose-6-phosphate dehydrogenase and of glutathione reductase. The latter is dependent on the pentose pathway, which generates NADPH, and on riboflavin, a FAD precursor vitamin.