Thermodynamic and kinetic modelling of the redox properties of tetrahaem cytochromes C3

Dissertação apresentada para obtenção do grau de Doutor em Bioquímica,especialidade Bioquímica-Física, pela Universidade Nova de Lisboa, Faculdade de Cincias e TecnologiaThe work presented in this thesis concerns the description and modelling of the thermodynamic and kinetic properties of tetrahaem cytochromes C3 isolated from different Desulfovibrio spp.. Sulfate-reducing bacteria produce tetrahaem cytochrome C3 in large quantities. This small (13 - 15 kD) protein is located in the periplasmic space of the cells,where it has been proposed to work as a cofactor of the enzyme hydrogenase. The four haems in cytochrome C3 are covalently bound to the protein through thioether linkages with cysteinyl residues and all display bis-histidinyl axial coordination. Although the degree of homology between the amino acid sequence of cytochromes C3 isolated from different organisms is low, the architecture of the haem core, is strictly conserved. The modelling of the thermodynamic properties of this protein has to take into account the fact that the four haems display different, interacting, and pH dependent redox potentials. Various approaches are described and discussed in this thesis, giving special emphasis to models which include both haem-haem and haem-proton interactions. To explain the pH dependence of the NMR resonances, the acid/base (NB) model was developed under the assumption that the protein could undergo a proton-linked conformational change, each conformation being characterised by a different set of microscopic redox potentials and haemhaem interacting potentials. The model of five interacting centres, developed later, demonstrated that it is not necessary to make any structural assumptions and that the experimental data can be simulated using fewer parameters, which are therefore better defined. According to this model, the thermodynamic properties of cytochrome C3 can be described by the intrinsic microscopic parameters of one acid/base and four redox centres plus the two-site interactions established between the five centres, namely, six haem-haem interactions plus four haem-proton interactions. Application of this model to NMR and visible redox titrations enabled the accurate determination of the complete set of microscopic parameters that characterise the thermodynamic behaviour of cytochromes C3 isolated from D. gigas and D. vulgaris. It is apparent from the values of the thermodynamic parameters that these cytochromes are able to perform a concerted two-electron step, which is coupled to the simultaneous uptake or release of protons, depending on the direction of the electron flow. These properties allow cytochrome C3 to work as an energy transducing system. However, since kinetic control of the electron and proton transfer steps is essential to achieve energy transduction, the kinetic properties of cytochrome C3 isolated from D. gigas are described and analysed in the second half of this thesis, making use of a specially developed kinetic model

Sacrococcygeal teratoma with malignant transformation in an adult female: CT and MRI findings

This report describes a case of sacrococcygeal teratoma with adenocarcinomatous transformation in a 45-year-old woman. This is an infrequent location for teratoma in adults and malignant transformation has rarely been described. Prognosis depends on complete excision. Clinical manifestations, imaging aspects and histological findings of this case are presented. CT and MRI adequately document the mixed cystic and solid nature of the tumour, its extension and relations with adjacent structures, allowing accurate pre-operative planning

Collective expression and local identity: the case-study of philharmonic bands

O primeiro aparecimento das Bandas Filarmónicas em Portugal remete-nos para o século XIX, sendo um tipo de organização que se mantém até aos dias de hoje. De origem popular, as bandas eram uma forma de entretenimento e fonte de oportunidades para as comunidades, tornando-se assim um pilar central da sociedade e da cultura. Esta dissertação tem dois objetivos distintos que estão ligados à cultura, à sociedade e à interculturalidade. Assim, a primeira parte deste estudo centra-se no impacto sociocultural das Bandas Filarmónicas nas comunidades, i.e., procura-se saber de que forma a sua organização e as atividades que promovem podem afetar positivamente a sociedade. Para atingir este objetivo, realizaram-se entrevistas a vários membros da Banda Musical de Arouca, procurando as motivações que os levaram a querer fazer parte de uma Banda Musical e as experiências obtidas nesse contexto. Relativamente à segunda parte, o objetivo foi compreender se, numa experiência internacional, os músicos passam por alguns encontros interculturais. Para tal realizou-se uma revisão bibliográfica da literatura e entrevistas indagando as experiências, aquando da recente participação da banda no World Music Contest em Kerkrade (Holanda), um dos concursos internacionais de bandas mais conceituado a nível mundial. Os resultados obtidos demonstram a importância das Bandas Filarmónicas nas comunidades locais e o valor que as suas atividades têm para quem nelas participa, relativamente à luta contra os problemas da sociedade contemporânea e à defesa dos valores culturais e tradicionais portugueses. A experiência relativa à saída internacional foi limitada devido à falta de recursos da Banda Musical de Arouca, sendo que o elemento de interculturalidade foi limitado a pequenos episódios de necessidade. Contudo, foi possível aferir, neste caso de estudo, uma significativa amostragem de valor imaterial e de troca intercultural que demonstra ser autossustentável.The first appearance of the Philharmonic Bands in Portugal takes us back to the 19th century, being a type of organization that remains to this day. Of popular origin, bands were a form of entertainment and source of opportunities for communities, thus becoming a central pillar of society and culture. This dissertation has two distinct objectives that are linked to culture, society and interculturality. Thus, the first part of this study focuses on the sociocultural impact of Philharmonic Bands on communities, i.e., it seeks to know how their organization and the activities they promote can positively affect society. To achieve this objective, interviews were conducted with several members of the Arouca Musical band, namely about the motivations that led them to want to be part of a musical band and the experiences obtained in this context. In the second part, the objective is to understand if, in an international experience, musicians go through some intercultural encounters. As such, in addition to carrying out a literature review, the interviewees were asked about their experience during the band's recent participation in World Music Contest in Kerkrade (Netherlands), one of the most prestigious international band competitions worldwide. The presented results demonstrate the importance of Philharmonic Bands in local communities and the value their activities have for those who participate in them, particularly regarding the fight against the problems of contemporary society and safeguarding Portuguese cultural and traditional values. Regarding the international outing, the experience was limited due to the lack of resources of the Arouca Musical Band, from which it was concluded that the element of interculturality was limited to small episodes of need. Even though, it has been possible to attain a significant sampling rate of immaterial value, namely of intercultural transfer in this case-study, which, in fact, is self-sustainable

Simulation-based methods for time series diagnostics.

We present sampling-based methodologies for the estimation of structural time series in the presence of outliers and structural shifts. We start by considering a simple structural model: a local level model, in the presence of outliers and level shifts. The existence of shocks is accounted for by including a product of intervention variables in the measurement and transition equations. These factors are composed of the product of an indicator variable and a parameter for the magnitude of the intervention variable, defining the size of the shocks. The Gibbs sampler is the Markov chain Monte Carlo method used for estimating the intervention model. Our contribution is in the use of a uniform prior distribution for the size of intervention variables. We show that this choice provides advantages over the usual multinomial and normal prior assumptions. The methodology is extended to a basic structural model. Using this model formulation, we consider 4 types of shocks: outliers, level, slope and seasonal shifts. The use of simulation based methods for this range of different breaks in structural models is not dealt with in the existing literature. By using the Gibbs sampler, we simultaneously estimate all the hyperparameters, detect the position of the shocks and estimate their size. Finally, we consider the local level model in the presence of outliers and level shifts for the case where one of the hyperparameters is equal to zero. In this situation, simulation based methods usually assume a multinomial prior distribution for the size of the intervention variables. We use a uniform prior, and present a two stages sampling scheme. In this two stage process the Gibbs sampler is first run on an auxiliary data set which has the same shocks as the original data set. For all the methods presented, performance is assessed by Monte Carlo studies and empirical applications to real data sets

Genograma orientado para a justiça íntima : uma abordagem colaborativa de terapia familiar em contextos de violência íntima

Tese de mestrado integrado em Psicologia (Psicologia Clínica da Saúde - Núcleo de Psicologia Clínica Sistémica), apresentada à Universidade de Lisboa através da Faculdade de Psicologia e de Ciências da Educação, 200

Modelização da volatilidade do índice BVL-30

Mestrado em Matemática Aplicada à Economia e à GestãoOs estudos efectuados para séries financeiras, permitiram estabelecer algumas regularidades empíricas. Entre essas regularidades destacam-se a não-lineariedade e a existência de volatilidade, características relacionadas entre si. Com o objectivo de modelizar a volatilidade, têm sido desenvolvidos diversos modelos teóricos, que podem ser classificados em dois grandes grupos: modelos de heterocedasticidade condicionada e modelos de volatilidade estocástica. Estes modelos distinguem-se entre si pela caracterização que é feita da volatilidade. Os modelos de heterocedasticidade condicionada, definem a volatilidade como função de variáveis observáveis. Nos modelos de volatilidade estocástica a volatilidade é uma variável latente. Adicionalmente, para modelizar a persistência da volatilidade, surgiram, nos últimos anos, modelos de heterocedasticidade condicionada e de volatilidade estocástica de "memória longa". Pretende-se com este trabalho modelizar a volatilidade do índice BVL-30. Para tal, são apresentados os resultados mais importantes e os principais modelos para a volatilidade que aparecem na literatura, é feita a sua aplicação ao estudo do índice BVL-30 e são comparados e discutidos os resultados obtidos.The studies published about financial time series have established some empirical regularities. Among these properties are non-linearity and volatility, which are related between them. With the purpose of modelling volatility, many theoretical models have been developed, and most of them can be classified in one of two classes: conditional heteroscedasticity models and stochastic volatility models. The major difference between these two models is that, while the first one defines volatility as a function of past observations, the last one takes volatility as a latent variabl e. To model persistence in volatility, long memory conditional heteroscedasticity models and long memory stochastic volatility models have been purposed. The purpose of this study is to model the volatility of the BVL-30 index. To do so, the most important results and models, which appear in literature, are presented. Its application is made to the BVL-30 index and the obtained results are compared and discussed.info:eu-repo/semantics/publishedVersio

Comunicação 360º : estudo de caso da Ogilvy Portugal

O presente trabalho de investigação tem por base o estágio realizado na agência de comunicação Ogilvy Portugal, em particular no departamento de relações públicas, onde adquirimos um conhecimento prático das funções que se prendem com o desenvolvimento das marcas e sua projeção, nomeadamente assessoria de imprensa e ativação da marca. Este período de estágio proporcionou, entre outros, o contacto com o tema Comunicação 360º, um tema que, até à data, desconhecíamos. Assim sendo, em razão do interesse e curiosidade que nos suscitou, optámos por explorar a aplicação deste novo conceito no mercado das agências e marcas. Contudo, observámos que sendo um conceito inovador e, por conseguinte, implementado em poucas agências e empresas, são poucos os estudos que versam sobre esta matéria. Pretendemos por este meio dar um contributo para o aprofundamento deste novo conceito. A opção de trabalhar este tema abriu-nos a possibilidade de abordar a totalidade das áreas trabalhadas na agência multinacional Ogilvy, e de aprofundar a comunicação interdepartamental, o que nos deu um entendimento prático das funções e responsabilidades inerentes a cada área individualmente, bem como do que subjaz às reuniões interdepartamentais, a saber, o processo de discussão de diferentes ideias entre elementos que têm um objetivo comum e abrangente, dando assim lugar à comunicação 360º. A comunicação 360º tem-se destacado como uma boa ferramenta comunicacional onde todas áreas que constituem as agências de comunicação interagem para trabalhar a melhor projeção das marcas. Atualmente, as empresas (marcas) e agências tomam cada vez mais consciência de que uma comunicação 360º é tão ou mais importante do que os restantes processos comunicacionais individuais que se estabelecem externamente com os mais variados stakeholders. O presente relatório visa principalmente esclarecer e aprofundar o conceito de comunicação 360º e a sua importância para o sucesso das marcas. Mais especificamente, a forma como se articula e se coordena esta estratégia que integra diversas áreas exigindo, ao mesmo tempo, uma coerência comunicacional e, também, uma forte abrangência. Nesse sentido, e de forma a dar seguimento aos objetivos a que nos propomos, recorremos a um conjunto de autores e às suas respetivas abordagens teóricas relativamente ao tema. Elaboramos igualmente um estudo de caso prático sobre a Ogilvy - agência de comunicação onde realizámos o estágio curricular - com recurso a inquéritos validados e analisados, e ainda um estudo complementar sobre outras agências de grande prestígio e renome no mercado de forma a tornar mais abrangente a conclusão final sobre a mais-valia desta estratégia 360º.This research work is based on the curricular placement that took place in Ogilvy Portugal, an advertising agency, namely in the public relations department. This placement enabled us to acquire a practical knowledge of the duties pertaining to the development of a brand and its projection, including press relations and activation of the brand. Additionally, this period gave us, among others things, the chance to contact with 360º Communication, a topic that, to date, was unknown for us. Thus, on account of the interest and curiosity that prompted us, our option was to explore the application of this new concept in the market for agencies and brands. However, we could observe that the fact of being an innovative concept and therefore implemented in a few agencies and companies, reduces the number of studies dealing with this matter. We hereby intend to contribute to the deepening of this new concept. To work out this topic allowed us to address all the areas that are part of the Ogilvy multinational agency, and to deepen the interdepartmental communication. We could get a practical understanding of the tasks and activities related to each area, and of what it takes to carry out interdepartmental meetings, namely, the debate of different ideas among different elements that have a common overarching goal, leading this way to a 360º communication. The 360 degree branding (360 degree Communication) is standing out as a good communication tool, which allows an interaction between the whole set of areas within an advertising agency in order to assure the best brand projection. Currently, enterprises (brands) and agencies are increasingly aware that a 360 degree branding is so or more important than all the other individual communication processes that are established externally with several stakeholders. Most importantly, this report seeks to shed light on, as well as explore the 360 degree branding concept and its weight for the success of brands. More specifically, the way this strategy - which incorporates several areas and requires at the same time a communication consistency and comprehensiveness - is articulated and coordinated. To that end, and in order to meet the abovementioned set goals, we draw on a number of authors and their theoretical approaches on the subject. We also develop a practical case study on Ogilvy, the advertising agency where we did our curricular placement, using validated and reviewed surveys, as well as an additional study on other prestigious and renowned agencies in the market to make the final conclusion about the added value of this 360º strategy more reliable and comprehensive

The antimicrobial properties of Moringa oleifera Lam. for water treatment: a systematic review

Plant extracts have been used as alternatives to the conventional chemical water treatment. Moringa oleifera Lam. is one of the plants used for this purpose due to its antimicrobial and coagulant properties. However, there is no systematization of Moringa’s application methodology. Different parts of the plant, extraction methods and concentrations can be applied to remove several pathogens present in contaminated drinking water. In the present work, reported Moringa applications with antimicrobial effect were systematically reviewed, in order to identify effective methodology(ies) for water treatment. Forty-nine articles were screened for: (1) part of the plant used, (2) extraction method, (3) extract concentration, (4) targeted pathogens, and (5) inhibition zone obtained. Nine articles complied with these criteria and were carefully analyzed; eight of them reported on leaf extracts and only one on seed extracts. Two approaches were used: analysis by pathogen and overall analysis. A total of eight different extraction methods were reported. Extract concentrations used ranged from 0.02 to 800 mg mL−1 and were tested on twenty pathogens. Our analysis revealed that none of such methods is effective against all the tested pathogens. However, leaf extracts obtained with distilled water or with 95% ethanol were the most effective ones for a higher number of pathogens such as Escherichia coli and, possibly, Vibrio cholerae. Moreover, Moringa’s extract concentration of 30 mg mL−1 obtained by the 95% ethanol extraction method was the most efficient. Findings suggest an effective procedure to use Moringa, reinforcing its importance as an environmentally friendly alternative for water treatment in areas lacking a water supply system.info:eu-repo/semantics/publishedVersio

Moringa as a household water purification method – community perception and pilot study in Guinea-Bissau

Background: Public perceptions of water-related issues are still under-researched topics. The current paper intends to explore a local community’s perceptions regarding household water purification (HWP) strategies, namely before and after trying a new method: moringa seeds powder (moringa-teabag). Methods: In September 2020, six focus group discussions (N = 65) assessing perceptions about the usefulness of Moringa oleifera Lam (Moringaceae) as a HWP method (before moringa-based HWP trials), and questionnaires (N = 104) evaluating successes and identifying difficulties (after one week of moringa-based HWP trials). Participants were all women aged over 18 years, living in Ondame, Biombo region, Guinea-Bissau. Data were analyzed using qualitative and quantitative approaches. Results: The focus group discussions revealed that people are aware of the fact that water can transmit diseases. Although certain persons showed concern about shallow well water safety, people generally underestimate the risk, as they trust tubewell water. Not everyone had an understanding of what water contamination is, or the concept of medical importance. Some respondents declared they use traditional methods such as boiling and bleach to treat water before drinking. However, those who reported no kind of treatment indicated reasons such as lack of time, cost, and bleach’s taste and smell. In the questionnaire, more than half of the participants (68%) reported treating water before consumption. Nevertheless, these results are not consistent with our field notes. Participants demonstrated a strong belief in the capacity of moringa-teabags to purify water and even consider them better or much better (81%) than other methods. Participants asked for more information on moringa-teabag for household water purification. Conclusion: More information on water treatment and water safety would help to raise public awareness about waterborne diseases. These findings could be used to promote greater adherence to moringa-based HWP as an alternative to household water treatment.info:eu-repo/semantics/publishedVersio

Cooperação empresarial em I&=eD : a percepção das empresas portuguesas sobre o papel das instituições de apoio

O título no SIFEUP é: Cooperação empresarial em ID+I. O papel das instituições de apoio ao ID+I em PortugalTese de mestrado. Inovação e Empreendedorismo Tecnológico. Faculdade de Engenharia. Universidade do Porto. 200