The role of electron transfer in DNA building blocks: evaluation of strand breaks and their implications

Dissertação para obtenção do Grau de Doutor em Engenharia Física

Avaliação da tolerância e nefrotoxicidade do antimonial pentavalente administrado na dose de 40mg Sb v/kg/dia, de 12/12h, por 30 dias na forma cutaneo-mucosa de leishmaniose

Foi avaliada a função renal de 11 pacientes com leishmaniose cutâneo-mucosa tratados com antimonial pentavalente na dose de 40mg SbV/kg/dia aplicada de 12/12 horas, em esquema contínuo, durante trinta dias. No estudo, um paciente apresentou insuficiência renal reversível e dois desenvolveram alterações enzimáticas hepáticas e eletrocardiográficas sendo o esquema terapêutico interrompido. Nos demais pacientes observou-se efeitos nefrotóxicos tais como diminuição da taxa de filtração glomerular, diminuição da capacidade de concentração urinária, avaliada por um jejum hídrico de 16 horas e aumento na fração de excreção de sódio. No exame do sedimento urinário observou-se um aumento no número de leucócitos e cilindros. Os resultados encontrados neste estudo sugerem que o tratamento com antimonial pentavalente na dose de 40mg SbV/kg/dia foi menos tolerado em virtude de seus efeitos tóxicos, não parecendo apresentar índice de cura superior ao esquema atualmente preconizado de 20mg SbV/kg/dia.

Argamassas de cal aérea e metacaulino: a influência do traço e da cura

Dissertação para obtenção do Grau Mestre em Engenharia Civil – Perfil de Construção

Um modelo de avaliação da eficiência de gestão de projectos: caso de estudo EDP Distribuição

No mercado energético, o tema eficiência tem-se tornado um pilar fundamental na obtenção de valor estratégico para as organizações deste negócio. Este foco tem muito que ver com as alterações que este mercado tem vindo a sofrer nos últimos anos com a mudança de mercado regulado para um mercado liberalizado. Permitir que novos players entrem no mercado e com eles novas formas de executar o negócio, tem aumentado a competividade entre as várias or-ganizações no ramo da electricidade. Consequentemente, essas organizações focam-se cada vez mais na eficiência, produzindo o mesmo mas utilizando menos recursos, promovendo, em simultâneo, uma maior satisfação dos seus clientes. Paralelamente, as organizações na última década têm-se virado cada vez mais para a gestão de projectos, percebendo que através dela podem concretizar valor estratégico mais facilmente, com menor redundância. Assim, muitas organizações vivem actualmente em ambientes de multi-projecto, em que as iniciativas dos diferentes projectos são inúmeras e na maioria das vezes não existe capital suficiente para as satisfazer na totalidade. Perceber quais os projectos que acrescentam maior valor à organização torna-se fundamental. Neste contexto, a presente dissertação visa avaliar a eficiência na gestão de um tipo de projec-tos da EDP Distribuição, utilizando o método matemático Data Envelopment Analysis (DEA). Com este método avaliou-se a capacidade que a organização tem em converter inputs em out-puts nos projectos de telecomando da rede de distribuição que levou a cabo durante o ano de 2013. Após um estudo sobre gestão de projectos e da análise DEA, analisou-se a melhor forma de aplicar o método DEA em empresas de electricidade, especificando-se as variáveis do modelo que traduzem melhor o processo a avaliar. Pretende-se fornecer resultados específicos sobre como a organização pode melhorar os seus processos na gestão de projectos de telecomando indicando onde, como e em quanto a empresa é ineficiente, identificando adicionalmente ac-ções de melhoria.

Shiva's dance: Crisis, local institutions and private firms

The uneven spatial distribution of start-ups and their respective survival may reflect comparative advantages resulting from the local institutional background. For the first time, we explore this idea using Data Envelopment Analysis (DEA) to assess the relative efficiency of Portuguese municipalities in this specific context. We depart from the related literature where expenditure is perceived as a desirable input by choosing a measure of fiscal responsibility and infrastructural variables in the first stage. Comparing results for 2006 and 2010, we find that mean performance decreased substantially 1) with the effects of the Global Financial Crisis, 2) as municipal population increases and 3) as financial independence decreases. A second stage is then performed employing a double-bootstrap procedure to evaluate how the regional context outside the control of local authorities (e.g. demographic characteristics and political preferences) impacts on efficiency.

Reactive electron scattering from biomolecules and technologically relevant molecules

The role of a set of gases relevant within the context of biomolecules and technologically relevant molecules under the interaction of low-energy electrons was studied in an effort to contribute to the understanding of the underlying processes yielding negative ion formation. The results are relevant within the context of damage to living material exposed to energetic radiation, to the role of dopants in the ion-molecule chemistry processes, to Electron Beam Induced Deposition (EBID) and Ion Beam Induced Deposition (IBID) techniques. The research described in this thesis addresses dissociative electron attachment (DEA) and electron transfer studies involving experimental setups from the University of Innsbruck, Austria and Universidade Nova de Lisboa, Portugal, respectively. This thesis presents DEA studies, obtained by a double focusing mass spectrometer, of dimethyl disulphide (C2H6S2), two isomers, enflurane and isoflurane (C3F5Cl5) and two chlorinated ethanes, pentachloroethane (C2HCl5) and hexachloroethane (C2Cl6), along with quantum chemical calculations providing information on the molecular orbitals as well as thermochemical thresholds of anion formation for enflurane, isoflurane, pentachloroethane and hexachloroethane. The experiments represent the most accurate DEA studies to these molecules, with significant differences from previous work reported in the literature. As far as electron transfer studies are concerned, negative ion formation in collisions of neutral potassium atoms with N1 and N3 methylated pyrimidine molecules were obtained by time-of-flight mass spectrometry (TOF). The results obtained allowed to propose concerted mechanisms for site and bond selective excision of bonds.

Electron driven reactions in sulphur containing biological prototypes

The interaction of ionising radiation with living tissues may direct or indirectly generate several secondary species with relevant genotoxic potential. Due to recent findings that electrons with energies below the ionisation threshold can effectively damage DNA, radiation-induced damage to biological systems has increasingly come under scrutiny. The exact physico-chemical processes that occur in the first stages of electron induced damage remain to be explained. However, it is also known that free electrons have a short lifetime in the physiological medium. Hence, electron transfer processes studies represent an alternative approach through which the role of "bound" electrons as a source of damage to biological tissues can be further explored. The thesis work consists of studying dissociative electron attachment (DEA) and electron transfer to taurine and thiaproline. DEA measurements were executed in Siedlce University with Prof. Janina Kopyra under COST action MP1002 (Nanoscale insights in ion beam cancer therapy). The electron transfer experiments were conducted in a crossed atom(potassium)-molecule beam arrangement. In these studies the anionic fragmentation patterns were obtained. The results of both mechanisms are shown to be significantly different, unveiling that the damaging potential of secondary electrons can be underestimated. In addition, sulphur atoms appear to strongly influence the dissociation process, demonstrating that certain reactions can be controlled by substitution of sulphur at specific molecular sites.

Análise da eficiência na gestão do risco de fornecedores: aplicação de um modelo Data Envelopment Analysis

Atualmente a tendência dos negócios leva a cadeias de abastecimento complexas e dinâmicas, que consequentemente levanta questões relativas ao aumento do risco de fornecimento em torno dessas mesmas cadeias; pelo que existe cada vez mais uma necessidade dos gestores identificarem e gerirem o risco de um modo mais diversificado. Associado às cadeias de abastecimento estão os fornecedores. A maioria dos riscos relativos a estes, está incluída no contexto de risco de fornecimento, resultando assim numa problemática de seleção e avaliação de fornecedores. Riscos como baixa qualidade, atrasos na entrega, falha ou interrupção de fornecimento, são exemplos de fatores de risco associados. Neste contexto, um dos maiores desafios para as organizações atualmente é trabalharem com os melhores fornecedores do mercado, procurando garantir a estabilidade em termos de fornecimento, com as melhores condições possíveis, quer a nível de preço, qualidade, entre outros, exigindo cada vez mais relações comerciais eficientes com os fornecedores. Assim, este trabalho tem como objetivo o desenvolvimento de um modelo baseado no método Data Envelopment Analysis (DEA), que permite às organizações avaliar e melhorar a eficiência das suas relações comerciais na gestão de risco de fornecimento nas suas cadeias de abastecimento. Como tal, o modelo proposto é divido em dois casos, que diferem pela origem da obtenção dos seus valores. Ou seja, num dos casos é aplicada uma avaliação externa à organização, e no outro é utilizada uma avaliação interna, o que permitirá discutir a sua utilização. Segundo o modelo proposto verificou-se que a eficiência média foi de 93% no caso I e 94% no caso II. Concluindo-se ainda ambos os casos necessitam de melhorias nos fornecimentos ao nível de: Qualidade, Logística e Tecnologia, ou seja, melhorar a qualidade dos serviços prestados, diminuir os seus prazos de execução dos serviços/fornecimento de material e aumento do conhecimento tecnológico.

Um modelo Data Envelopment Analysis para avaliação da eficiência dos terminais de contentores do grupo TERTIR

O transporte marítimo tem vindo a adquirir uma considerável importância na economia mundial desde o século XV. O transporte marítimo é visto como um dos meios de transporte mais viáveis, que engloba um largo número de destinos no mundo e representa, para uma determinada distância a percorrer, o menor custo por tonelada. É, também, comparativamente com o transporte aéreo e rodoviário, o meio de transporte menos poluente, tornando-o, assim, uma alternativa “amiga do ambiente”. Em particular, o transporte via contentores tem vindo a ser cada vez mais utilizado devido às suas inúmeras vantagens. O contentor permite o transporte de qualquer tipo de mercadoria em boas condições de acondicionamento e permitiu otimizar as operações efetuadas através da redução de tempo de trabalho, custos e espaço. Ademais, com a globalização, a evolução do mercado, a construção de navios de maiores dimensões e a maior tecnologia investida no setor, a competição entre os portos alcançou níveis que exigem uma maior eficiência de toda a estrutura portuária. Neste contexto, a presente dissertação visa avaliar a eficiência dos terminais de contentores do grupo TERTIR, nomeadamente os de Lisboa, Leixões e Setúbal, utilizando o método Data Envelopment Analaysis (DEA). De um modo geral, o método DEA avalia a capacidade dos terminais em converter inputs em outputs. Mais especificamente os inputs selecionados nesta dissertação dizem respeito às infraestruturas e equipamentos dos terminais em estudo, e o output considera a carga movimentada por cada terminal, sendo neste caso representada pelo número de TEUs movimentados. O modelo proposto é aplicado a um conjunto de 30 terminais de contentores Europeus de 6 países diferentes, nomeadamente, Alemanha, Bélgica, Espanha, França, Holanda e Portugal. De um modo geral, os terminais TERTIR apresentam níveis de eficiência baixos quando comparados com outros terminais Europeus. Os resultados contribuem, também, para auxiliar o grupo TERTIR no debate de algumas questões atuais com as autoridades portuárias, nomeadamente no que se refere à descida dos tarifários praticados aos seus clientes e à enunciada construção do terminal de contentores do Barreiro.

The reasons behind the progression in PISA scores: An education production function approach using semi-parametric techniques

Research Masters

Discussing Chevalier’s data on the efficiency of tariffs for american and french canals in the 1830s

This article revisits Michel Chevalier’s work and discussions of tariffs. Chevalier shifted from Saint-Simonism to economic liberalism during his life in the 19th century. His influence was soon perceived in the political world and economic debates, mainly because of his discussion of tariffs as instruments of efficient transport policies. This work discusses Chevalier’s thoughts on tariffs by revisiting his masterpiece, Le Cours d’Économie Politique. Data Envelopment Analysis (DEA) was conducted to test Chevalier’s hypothesis on the inefficiency of French tariffs. This work showed that Chevalier’s claims on French tariffs are not validated by DEA.

Criação de um sistema de apoio para o suporte avançado de vida

Dissertação de mestrado integrado em Engenharia Biomédica (área de especialização em Eletrónica Médica)

How does banking industry influence economic growth in Latin American countries?

Mestrado em Finanças

Transfer of radionuclides from soil to vegetation in selected Irish ecosystems

This thesis details the findings of a study relating the transfer of 238U, 228Ra (232Th), 226Ra, and 137Cs from soil to vegetation in an Atlantic blanket bog, upland blanket bog and semi-natural grassland situated along the north-west coast of Ireland. The results of this study provide information on the uptake of these radionuclides by the indigenous vegetation found present in these ecosystems. The ecosystems chosen are internationally recognizable ecosystems and provide a wide variety of vegetation species and contrasting soil physiochemical properties which allow the influence of these parameters on radionuclide uptake to be assessed. The levels of radionuclides in the soil and vegetation were measured using gamma spectrometry, alpha spectrometry and ICP-MS. The nutrient status of the vegetation and soil physiochemical properties were measured using atomic absorption, flame photometry and other analytical techniques. The results of the study indicate that the uptake of 238U and 228Ra (232Th) by vegetation from all three ecosystems was negligible as the levels in all vegetation was below the limits of detection for the methods used in this study. These results appear to indicate that the vegetation studied do not possess the ability to accumulate significant levels of these radionuclides however this assumption cannot be upheld in the case of the Atlantic blanket bog as the levels in the soil of this ecosystem were too low for detection. Similar results were obtained for 226Ra uptake in both the Atlantic blanket bog and grassland for all vegetation with the exception of H. lanatus from the grassland ecosystem. Radium-226 uptake in upland blanket bog was higher and was detectable in the majority of vegetation indigenous to this ecosystem. Transfer factor values ranged from 0.07 to 2.35 and the TF values for E. tetralix were significantly higher than all other vegetation studied. This species of heather demonstrated the ability to accumulate 226Ra to a greater extent than all other vegetation. The uptake of 226Ra by upland blanket bog vegetation appears to be significantly influenced by a range of soil physiochemical properties. The nutrient status of the vegetation, in particular the calcium content in the vegetation appears to have a negative impact on the uptake of this radionuclide. Potassium-40 was detectable in all vegetation present in the three ecosystems and the levels in the grassland soil were significantly higher than the levels in both bogland soils. Transfer factor values for Atlantic blanket bog vegetation ranged from 0.9 to 13 .8 and were significantly higher in E. vaginatum in comparison to C. vulgaris. Potassium-40 TF values for upland blanket bog vegetation on average ranged from 1.4 for C. vulgaris (stems) to 5.2 for E. vaginatum and were statistically similar for all species of vegetation. Transfer factor values for grassland vegetation ranged from 0.7 to 3.8 and were also statistically similar for all species of vegetation indicating that the transfer of 40K to vegetation within the upland bog and grassland ecosystem is not dependent on plant species. Comparisons of 40K TF values for all three ecosystems indicate that the uptake in E. vaginatum from the Atlantic blanket bog was statistically higher than all other vegetation studied. This appears to indicate that E. vaginatum has the ability to accumulate 40K, however, this species of vegetation was also present in the upland blanket and did not demonstrate the same behaviour. The uptake of 40K by vegetation from all three ecosystems was significantly affected by a range of soil physiochemical properties and in some cases the results were contradictory in nature possibly indicating that the affect of these parameters on 40K uptake is species dependent. The most obvious trend in the data was the influence of soil CEC and magnesium levels in vegetation on 40K TF values. A positive correlation was apparent between the CEC of the soil and 40K uptake in vegetation from both the Atlantic blanket bog and grassland ecosystem. A similar trend was apparent between magnesium levels in vegetation and 40K TF values for the upland blanket bog and grassland vegetation. Caesium-13 7 levels were found to be significantly higher in the two bogland soils in comparison to the grassland soil and levels of 137Cs decreased with increasing soil depth. Transfer factor values for Atlantic blanket bog vegetation ranged from 1.9 to 9.6 and TF values were significantly higher in the leaves o f C. vulgaris in comparison to all other vegetation from this ecosystem. Caesium-13 7 TF values for the upland blanket bog vegetation on average ranged from 0.29 for E. tetralix to 1.6 for C. vulgaris. Uptake by the leaves of C. vulgaris was significantly higher than all other vegetation present thereby supporting the trend found within the Atlantic blanket bog vegetation. These results appear to indicate that the leaves of C. vulgaris have the ability to accumulate significant quantities of 137Cs and also that the uptake of 137Cs by this vegetation is dependent on plant compartment as the stems of this vegetation contained significantly lower levels than the leaves in both ecosystems. The uptake of 137Cs by grassland vegetation was very low and was only detectable in a fraction of the vegetation sampled. Caesium-137 TF values for grassland vegetation were in general lower than 0.02. The impact of soil physiochemical properties and nutrient status of vegetation on 137Cs uptake by vegetation appears to be complex and in some cases contradictory. The most apparent trend in the data was the positive influence of vegetation nutrients on 137Cs uptake in particular the magnesium levels present in the vegetation and to a lesser extent the calcium levels present. The results in general indicate that the uptake of 226Ra, 40K and 137Cs by the chosen vegetation is varied and complex and is significantly dependent on the species of vegetation, soil radionuclide concentration, soil physiochemical properties and the nutrient status of the vegetation.

The spatial analysis and speciation of uranium and thorium series radionuclides in the soil of the Cronamuck Valley, County Donegal, Ireland

This thesis details the findings of a study into the spatial distribution and speciation of 238U, 226Ra and 228Ra in the soils of the Cronamuck valley, County Donegal . The region lies on the north-eastern edge of the Barnesmore granite and has been the subject of uranium prospecting efforts in the past. The results of the project provide information on the practicability of geostatistical techniques as a means of estimating the spatial distribution of natural radionuclides and provide insight into the behaviour of these nuclides and their modes of occurrence and enrichment in an upland bog environment. The results of the geostatistical survey conducted on the area indicate that the primary control over the levels of the studied nuclides in the soil of the valley is the underlying geology. Isopleth maps of nuclide levels in the valley indicate a predominance of elevated nuclide levels in the samples drawn from the granite region, statistical analysis of the data indicating that levels of the nuclides in samples drawn from the granite are greater than levels drawn from the non-granite region by up to a factor of 4.6 for 238U and 4.9 for 226Ra. Redistribution of the nuclides occurs via drainage systems within the valley, this process being responsible for transport of nuclides away from the granite region resulting in enrichment of nuclides in soils not underlain by the granite. Distribution of the nuclides within the valley is erratic, the effect of drainage f lows on the nuclides resulting in localized enriched areas within the valley. Speciation of the nuclides within one of the enriched areas encountered in the study indicates that enrichment is as a result of saturation of the soil with drainage water containing trace amounts of radionuclides. 238U is primarily held within the labile fractions (exchangeable cat ions + easily oxidisable organics + amorphous iron oxides ) of the soil , 226Ra being associated with the non- labile fractions, most probably the resistant organic material. 228Ra displays a significant occurrence in both the labile and non- labile fractions. The ability of the soil to retain uranium appears to be affected largely by the redox status of the soil, samples drawn from oxidizing environments tending to have little or no uranium in the easily oxidisable and amorphous iron oxide fractions. This loss of uranium from oxidised soil samples is responsible for the elevated 226Ra /238U disequilibrium encountered in the enriched areas of the valley. Analysis of the data indicates that samples displaying elevated 226Ra/238U ratios also exhibit elevated 228Ra/238U ratios indicating a loss of uranium from the samples as opposed to an enrichment of 226Ra.