Application of NMR RDC’s, relaxation and self-diffusion for the study of dynamic processes of small molecules in solution

Spin-lattice Relaxation, self-Diffusion coefficients and Residual Dipolar Couplings (RDC’s) are the basis of well established Nuclear Magnetic Resonance techniques for the physicochemical study of small molecules (typically organic compounds and natural products with MW < 1000 Da), as they proved to be a powerful and complementary source of information about structural dynamic processes in solution. The work developed in this thesis consists in the application of the earlier-mentioned NMR techniques to explore, analyze and systematize patterns of the molecular dynamic behavior of selected small molecules in particular experimental conditions. Two systems were chosen to investigate molecular dynamic behavior by these techniques: the dynamics of ion-pair formation and ion interaction in ionic liquids (IL) and the dynamics of molecular reorientation when molecules are placed in oriented phases (alignment media). The application of NMR spin-lattice relaxation and self-diffusion measurements was applied to study the rotational and translational molecular dynamics of the IL: 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF4]. The study of the cation-anion dynamics in neat and IL-water mixtures was systematically investigated by a combination of multinuclear NMR relaxation techniques with diffusion data (using by H1, C13 and F19 NMR spectroscopy). Spin-lattice relaxation time (T1), self-diffusion coefficients and nuclear Overhauser effect experiments were combined to determine the conditions that favor the formation of long lived [BMIM][BF4] ion-pairs in water. For this purpose and using the self-diffusion coefficients of cation and anion as a probe, different IL-water compositions were screened (from neat IL to infinite dilution) to find the conditions where both cation and anion present equal diffusion coefficients (8% water fraction at 25 ºC). This condition as well as the neat IL and the infinite dilution were then further studied by 13C NMR relaxation in order to determine correlation times (c) for the molecular reorientational motion using a mathematical iterative procedure and experimental data obtained in a temperature range between 273 and 353 K. The behavior of self-diffusion and relaxation data obtained in our experiments point at the combining parameters of molar fraction 8 % and temperature 298 K as the most favorable condition for the formation of long lived ion-pairs. When molecules are subjected to soft anisotropic motion by being placed in some special media, Residual Dipolar Couplings (RDCs), can be measured, because of the partial alignment induced by this media. RDCs are emerging as a powerful routine tool employed in conformational analysis, as it complements and even outperforms the approaches based on the classical NMR NOE or J3 couplings. In this work, three different alignment media have been characterized and evaluated in terms of integrity using 2H and 1H 1D-NMR spectroscopy, namely the stretched and compressed gel PMMA, and the lyotropic liquid crystals CpCl/n-hexanol/brine and cromolyn/water. The influence that different media and degrees of alignment have on the dynamic properties of several molecules was explored. Different sized sugars were used and their self-diffusion was determined as well as conformation features using RDCs. The results obtained indicate that no influence is felt by the small molecules diffusion and conformational features studied within the alignment degree range studied, which was the 3, 5 and 6 % CpCl/n-hexanol/brine for diffusion, and 5 and 7.5 % CpCl/n-hexanol/brine for conformation. It was also possible to determine that the small molecules diffusion verified in the alignment media presented close values to the ones observed in water, reinforcing the idea of no conditioning of molecular properties in such media.

Evaporation from porous building materials and its cooling potential

Evaporative cooling is a traditional strategy to improve summer comfort, which has gained renewed relevance in the context of the transition to a greener economy. Here, the potential for evaporative cooling of two common porous building materials, natural stone and ceramic brick, was evaluated. The work has relevance also to the protection of built heritage becauseevaporation underlies the problems of dampness and salt crystallization, which are so harmful and frequent in this heritage. It was observed that the drying rate of the materials is, in some cases, higher than the evaporation rate of a free water surface. Surface area measurements by a three-dimensional optical technique suggested, as probable cause of this behavior, that surface irregularity gives rise to a large effective surface of evaporation in the material. Surface temperature measurements by infrared were performed afterward during evaporation experiments outside during a hot summer day in Lisbon. Their results indicate that ordinary building materials can be very efficient evaporative media and, thus, may help in achieving higher energy efficiency while maintaining a simultaneous constructive or architectural function.

Liderança Feminina no Poder Político Local em Portugal: Representações, Media e Visibilidade

A comunidade científica avalia a diferença de proporção entre mulheres e homens nos parlamentos nacionais como reveladora do índice democrático dos países, com esta dissertação sublinhamos a relevância de aprofundar o conhecimento sobre o poder local para compreender a realidade da sub-representação política feminina em Portugal. A recolha e análise de dados do último ato eleitoral autárquico de setembro de 2013, permitiu-nos ilustrar o problema de discriminação revelado pela sub-representação política feminina. Entre as causas para a sub-representação política feminina identificadas na literatura, destacamos a invisibilidade das mulheres políticas, considerada superior à sua sub-representação real. Por outro lado, uma das soluções prosseguidas por vários países para combater o problema da sub-representação política feminina é a introdução de um sistema de quotas no processo eleitoral.Com este trabalho, em que revelamos que a introdução de quotas em Portugal não influenciou os resultados eleitorais locais, consideramos poder relacionar a exígua presença das mulheres na liderança dos executivos municipais com a sua invisibilidade mediática. O presente trabalho contribui para esclarecer as seguintes questões: (i) como evoluiu a liderança feminina no poder local; (ii) qual a medida atual desta representação; (iii) qual o impacto das quotas legislativas no número de mulheres presidentes de Câmara eleitas; (iv) quais os obstáculos específicos que afastam as mulheres da liderança do poder local, (v) como contribuem os media para a invisibilidade das autarcas junto do eleitorado. Em Portugal, a taxa de feminização parlamentar conheceu uma evolução sempre crescente desde as primeiras eleições democráticas em 1976, até ao valor atual de 31,30%. Este trabalho demonstra que a presença feminina na liderança do órgão executivo municipal, tem sido sempre residual. Uma representação atual de 7,5%, configura não só a situação mais acentuada de sub-representação política feminina como, em contracorrente com a realidade da Assembleia da República e do Parlamento Europeu, a inexpressiva evolução estagnou. Para aprofundar o conhecimento sobre o poder local e testar as hipóteses colocadas, realizámos um questionário junto das 23 autarcas eleitas em 2013 com o qual foi possível fazer a sua caracterização sociodemográfica, além de avaliar o seu percurso político-partidário e conhecer a relação estabelecida com os media nacionais e locais/regionais durante a sua candidatura e após a eleição. Para complementar esta informação e aprofundar o tema da eficácia das quotas, realizámos entrevistas em profundidade com nove mulheres eleitas presidentes de Câmara antes e depois de 2009 (primeiro ato eleitoral autárquico após a implementação da Lei da Paridade). Neste contexto, seguimos as orientações metodológicas sobre análise de conteúdo de entrevistas de Laurence Bardin. O trabalho de campo foi efetuado entre julho e setembro de 2014 em quatro distritos que se encontram entre os que mais mulheres elegeram na história política autárquica: Santarém, Portalegre, Lisboa e Setúbal. Com este trabalho pretendemos demonstrar que é ao nível da liderança política feminina que as resistências são mais profundas, tal como revela a realidade local, colocando em questão a pertinência dos mecanismos de ação positiva que atuam sobre os efeitos mas não sobre a causa do problema da sub-representação política feminina.

On and off air: an ethnographic exploration of minority radio in Portugal

Taking a Media Anthropology’s approach to dynamics of mediated selfrepresentation in migratory contexts, this thesis starts by mapping radio initiatives produced by, for and/or with migrants in Portugal. To further explore dynamics of support of initial settlement in the country, community-making, cultural reproduction, and transnational connectivity - found both in the mapping stage and the minority media literature (e.g. Kosnick, 2007; Rigoni & Saitta, 2012; Silverstone & Georgiou, 2005) - a case study was selected: the station awarded with the first bilingual license in Portugal. The station in question caters largely to the British population presenting themselves as “expats” and residing in the Algarve. The ethnographic strategy to research it consisted of “following the radio” (Marcus, 1995) beyond the station and into the events and establishments it announces on air, so as to relate production and consumption realms. The leading research question asks how does locally produced radio play into “expats” processes of management of cultural identity – and what are the specificities of its role? Drawing on conceptualizations of lifestyle migration (Benson & O’Reilly, 2009), production of locality (Appadurai 1996) and the public sphere (Butsch, 2007; Calhoun & et al, 1992; Dahlgren, 2006), this thesis contributes to valuing radio as a productive gateway to research migrants’ construction of belonging, to inscribe a counterpoint in the field of minority media, and to debate conceptualizations of migratory categories and flows. Specifically, this thesis argues that the station fulfills similar roles to other minority radio initiatives but in ways that are specific to the population being catered to. Namely, unlike other minority stations, radio facilitates the process of transitioning between categories along on a continuum linking tourists and migrants. It also reflects and participates in strategies of reterritorialization that rest on functional and partial modes of incorporation. While contributing to sustain a translocality (Appadurai, 1996) it indexes and fosters a stance of connection that is symbolically and materially connected to the UK and other “neighborhoods” but is, simultaneously, oriented to engaging with the Algarve as “home”. Yet, besides reifying a British cultural identity, radio’s oral, repetitive and ephemeral discourse particularly trivializes the reproduction of an ambivalent stance of connection with place that is shared by other “expats”. This dynamic is related to migratory projects driven by social imaginaries fostered by international media that stimulate the search for idealized ways of living, which the radio associates with the Algarve. While recurrently localizing and validating the narrative projecting an idealized “good life”, radio amplifies dynamics among migrants that seem to reaffirm the migratory move as a good choice.

Management consulting labs- Galp social media

The purpose of this project was to study a possible presence of Galp at Social Media. The importance of this study appears as a consequence of the company’s need to adapt to a new mean of communication that is changing our society and the companies way of doing business. In the consulting labs, the analysis was done taking into account the best practices for business at Social Media and the singularities of the company. The output of this study was a collection of specific guidelines concerning several fields to develop a strategic presence at Social Media.

How to engage low category users through social media- The case of the make-up sector in Portugal

Purpose: This work project should be inevitably deemed as a practical approach to a marketing problem; “How to engage low category users through the social media – the case of the make-up sector in Portugal”. Design/methodology/approach: Online structured questionnaires and in-depth interviews were used. The questionnaire was answered by 110 women aged from 15 to 45 years old and the interviews were conducted with 14 women of the same age. The interviews provided key insights for the questionnaire formulation. Findings: Women are poorly informed on make-up properties and characteristics, feeling a genuine concern in regard to this subject. Lack of time, occasional usage and skin damage are the main barriers for make-up usage by low category users. Overcoming these aspects pass by demystifying the association of make-up with skin damage and emphasise the functional and emotional benefits of make-up. Further, brands need to create contents more consumer-oriented and ask directly to fans/followers suggestions and other insights. Resort to Portuguese “common” women for greater empathy in campaigns, promote online meetings between followers and make-up professionals on social media; and finally take advantage of the hybrid condition of Facebook, which incorporates multiple forms of content presentation, including videos, the most appealing format of make-up presentation for women. Research limitations/implications: Further studies addressing this topic, by using larger samples and study of specific make-up brands and campaign programs, over social media to reach a solid growth potential of make-up market evidences in Portugal. Originality/ value: Make-up brands are emphasising their interest in linking social media and marketing their promotional mix around social marketing.

Comedy shows: humour, crisis and the resilience of radio

Being a part of many radio stations' progra

A radiodifusão no Brasil e em Portugal e a invasão dos brasucas: uma nova linguagem

Tese de Doutoramento em Ciências da Comunicação (área de especialização em Sociologia da Comunicação e da Informação).

Silent citizens: on silence and silencing in journalism

Constructivist approaches to journalism, which have dominated the field for most of the second half of the 20th century, underline how selection and ranking processes produce representations and interpretations of social reality. Theoretical perspectives such as agenda-setting or framing have been pointing to the ways production of news messages are shaped and issues are defined. Research inspired by these contributions does however seem to keep in an area of relative shade not so much what is said and published but what is not selected: the unsaid, the withheld, the untold of journalism. The reality that remains in silence, for not being noticed or for being silenced, is the reverse of the coin of what is made visible. In this paper, it is suggested that this situation opens up the debate to a relatively unknown continent, which could contribute to the larger discussion on the current crisis in journalism. It is our contention that ‘the untold’ might be at the confluence of different levels: the journalistic agenda-setting by news sources; the deterioration of working conditions of journalists, compromising the investigation; and the social capital asymmetries from important segments of the population, hampering the public word (speech?) and the right to communicate. In order to build a comprehensive picture of the potentialities and contradictions of journalism from the unsaid side, we would put forward the outline of a typology of journalism's silences, with particular emphasis on some aspects of "discursive discrimination" (Boréus, 2006), on the one hand, and on citizen silence in the process of journalistic production, on the other hand.

Os social media como parte integrante da comunicação empresarial

Relatório de estágio de mestrado em Ciências da Comunicação (área de especialização Publicidade e Relações Públicas)

A imprensa desportiva do papel ao online: o exemplo do jornal Record

Dissertação de mestrado em Ciências da Comunicação (área de especialização em Informação e Jornalismo)

Characterization of microbial populations in a wastewater treatment plant focusing on Staphylococcus aureus and Pseudomonas aeruginosa

Dissertação de mestrado em Bioengenharia

Nous perfils professionals de l'actual panorama informatiu audiovisual i multimèdia de Catalunya

Aquest treball forma part de una recerca –finançada pel Consell de l’Audiovisual de Catalunya- dedicada a l’anàlisi de les conseqüències dels processos de digitalització en els mitjans de comunicació de Catalunya (Espanya). El document presenta les transformacions que han afectat al periodista, especialment les noves tasques i funcions. Després d’una introducció dedicada al marc teòric i a la metodologia de la recerca, el document explica les tendències principals observades en les ràdios, emissores de televisió, agències de noticies i mitjans en línia de Catalunya. El document també presenta una sèrie de reflexions sobre la polivalència, la re-qualificació i altres processos que afecten als professionals de la informació. Finalment, es proposa una classificació de les formes que assumeix la polivalència en els mitjans.

The Cultural Olympiad: objectives, programme and development

Working paper analysing the Cultural Olympiad of Barcelona in 1992. This was published as a chapter of the book entitled "Olympic Games, media and cultural exchanges: the experience of the last four summer Olympic Games" and edited by M. Ladrón de Guevara and M. Bardají.

Delayed otogenic hydrocephalus after acute otitis media in pediatric patients: the changing presentation of a serious otologic complication.

CONCLUSIONS: The clinical presentation of otogenic dural sinus thrombosis (DST) as a complication of acute otitis media (AOM) can be masked by antibiotic treatment. Morning episodes of vomiting and/or headache, visual impairment and a history of AOM seem to be indicative of otogenic hydrocephalus. We therefore advocate that the MRI scans of patients with similar symptoms should be carefully studied to facilitate the early diagnosis of a potentially life-threatening complication. OBJECTIVE: To describe the frequency, pathognomonic signs, clinical course and outcome of otogenic hydrocephalus and DST as complications of AOM in pediatric patients. MATERIAL AND METHODS: We undertook a retrospective chart review of all pediatric patients (age 1-14 years) treated for otitis media and its complications at an academic medical center between 1999 and 2003. The main outcome measures were otologic and ophthalmologic findings and CT and MRI scans at the beginning of treatment and 3 months later. RESULTS: We report on five cases with otogenic DST following AOM. All but one of them presented initially with diplopia caused by otogenic hydrocephalus. In four cases the otologic complaints had already disappeared by the time of MRI confirmation of the diagnosis. Only one child was referred with severe otologic symptoms. Management included systemic antibiotics, short-term heparin anticoagulation and surgical decompression. In our cases, even after intensive i.v. antibiotic treatment, only surgery led to a significant improvement in the clinical condition.