Development of novel ionic liquids based on biological molecules

Ionic Liquids (ILs) belong to a class of compounds with unusual properties: very low vapour pressure; high chemical and thermal stability and the ability to dissolve a wide range of substances. A new field in research is evaluating the possibility to use natural chiral biomolecules for the preparation of chiral ionic liquids (CILs). This important challenge in synthetic chemistry can open new avenues of research in order to avoid some problems related with the intrinsic biodegradability and toxicity associated to conventional ILs. The research work developed aimed for the synthesis of CILs, their characterization and possible applications, based on biological moieties used either as chiral cations or anions, depending on the synthetic manipulation of the derivatives. Overall, a total of 28 organic salts, including CILs were synthesized: 9 based on L-cysteine derivatives, 12 based on L-proline, 3 based on nucleosides and 4 based on nucleotides. All these new CILs were completely characterized and their chemical and physical properties were evaluated. Some CILs based on L-cysteine have been applied for discrimination processes, including resolution of racemates and as a chiral catalyst for asymmetric Aldol condensation. L-proline derived CILs were also studied as chiral catalysts for Michael reaction. In parallel, the interactions of macrocyclic oligosugars called cyclodextrins (CDs) with several ILs were studied. It was possible to improve the solubility of CDs in water and serum. Additionally, fatty acids and steroids showed an increase in water solubility when ILs-CDs systems were used. The development of efficient and selective ILs-CDs systems is indispensable to expand the range of their applications in host-guest interactions, drug delivery systems or catalytic reactions. Novel salts derived from nucleobases were used in order to enhance the fluorescence in aqueous solution. Additionally, preliminary studies regarding ethyl lactate as an alternative solvent for asymmetric organocatalysis were performed.

Proteomics based approach to understand tissue regeneration

Dissertation presented to obtain the PhD degree in Biochemistry

Testes genéticos de venda direta ao consumidor : questões ético-legais no mercado português

RESUMO - As descobertas realizadas na área da genética levaram ao desenvolvimento de aplicações práticas, entre as quais se destacam os testes genéticos, cujas aplicações em saúde tiveram um impacto considerável na prática clínica. Uma das consequências deste desenvolvimento foi o nascimento de um novo mercado na área da saúde, o mercado dos Testes Genéticos de Venda Direta ao Consumidor (TGVDC). Este mercado está associado a questões do foro ético e legal muito específicas e importantes. Através da realização do presente trabalho de projeto pretende-se analisar e discutir as principais questões éticas e legais suscitadas pelos TGVDC, com maior enfoque no mercado português e na aplicação do enquadramento ético-legal em vigor em Portugal. No que toca à metodologia, no âmbito do presente trabalho de projeto, realizou-se uma análise da literatura científica e ético-legal do tema em estudo. Posteriormente realizou-se uma entrevista exploratória, a uma personalidade de reconhecido mérito na área da genética humana, a fim de compreender quais as principais questões suscitadas pelo mercado de TGVDC. Seguidamente realizou-se um mapeamento das entidades que operam no mercado de TGVDC, seguido de um inquérito a essas mesmas entidades, a fim de avaliar as características do serviço oferecido em Portugal e a aplicação do regime normativo ético-legal em vigor. Verificou-se, como era expectável, que o mercado português de TGVDC apresenta reduzida dimensão quando comparado com outros mercados a nível internacional, designadamente o mercado norte-americano que é, claramente, o mais desenvolvido nesta área. Os resultados obtidos apontaram ainda, no que toca à realidade portuguesa, para a pertinência de questões discutidas na literatura analisada. Em suma, apesar das limitações inerentes à realização de um projeto pioneiro e ambicioso num curto espaço de tempo, as conclusões deste trabalho permitem extrair conclusões importantes acerca do mercado português de TGVDC, sob a perspetiva ético-legal, bem como efetuar recomendações importantes para futuros estudos nesta área.

Satisfação profissional dos médicos dentistas na utilização do cheque-dentista : um estudo exploratório no concelho de Lisboa

RESUMO - A satisfação profissional é um fenómeno amplamente estudado e esse interesse decorre da influência que a mesma pode exercer sobre o trabalhador, afetando a sua saúde, atitudes, comportamento profissional e social, com repercussões tanto para a sua vida privada como para as organizações. Considerando a tendência mundial de se aproximarem os perfis da profissão para um perfil único e de que a investigação sobre a satisfação profissional dos médicos dentistas em vários países estar presentemente a ser divulgada, seria importante avaliar a situação em Portugal para fins comparativos. O presente estudo teve como objetivo investigar o grau de satisfação profissional dos médicos dentistas na utilização do cheque-dentista no concelho de Lisboa, procurando estabelecer relações entre as diferentes dimensões da satisfação profissional e variáveis socioprofissionais. Um questionário de autopreenchimento foi enviado por e-mail para as clínicas onde os médicos dentistas trabalham, num total de 99 obtendo-se uma taxa de resposta de 24,2%. Verificou-se que em relação à satisfação profissional em geral nas várias dimensões questionadas, é a relação profissional/paciente que os médicos dentistas consideram como mais importante logo seguida da realização pessoal e profissional. Como menos importante os médicos dentistas referiram o status/prestígio e a segurança profissional. Já no campo da satisfação profissional no âmbito do cheque-dentista concluiu-se que mais próximo do grau de satisfeito se encontra a relação estabelecida com o paciente assim como a relação de trabalho com a equipa. No grau de satisfação mais baixo, de total insatisfação encontra-se o número de tratamentos que são permitidos efetuar em cada cheque-dentista e um último lugar encontrase o valor remuneratório do cheque-dentista. Comparando a satisfação profissional com o cheque-dentista entre géneros, verificou-se que apenas na dimensão do valor remuneratório do cheque-dentista existem diferenças estatisticamente significativas (p=0,026), sendo que o género feminino demonstra maior satisfação que o género masculino. O número de participantes não foi suficiente para que se possa generalizar os resultados para a população. É necessária a realização de mais estudos neste âmbito com um maior número de profissionais de forma a que os resultados sejam estatisticamente significativos.

Tempos de espera cirúrgicos: situação em Portugal e determinantes

RESUMO - Objectivos Um dos problemas mais comuns nos sistemas de saúde e particularmente naqueles que têm uma estrutura predominantemente pública são os elevados Tempos Espera (TE) para cirurgia. Este projecto tem como principal objectivo identificar a importância relativa em Portugal das determinantes do TE cirúrgico. Metodologia Para clarificar essa importância, aplicou-se um questionário desenvolvido pelo Fraser Institute, utilizado para a análise anual dos TE no Canadá, recorrendo a um painel de peritos e através da realização da técnica Delphi, procurou-se consensualizar quais as determinantes das Listas Espera (LE), mais importantes. Para ilustrar a diversidade de perspectivas, recorreu-se também à análise de trabalhos realizados por inúmeras organizações, onde pudemos observar e recolher distintas abordagens, políticas e técnicas da questão das LE em países com diferentes tipos de sistemas de saúde. Resultados Os resultados obtidos revelam que os peritos consideraram a disponibilidade de tempo no Bloco Operatório (BO) e a de anestesiologistas, como as determinantes com maior impacto no aumento das LE. Conclusões Dos dados recebidos relativos ao Sistema Integrado Gestão Inscritos Cirurgia (SIGIC), bem como dos retirados de relatórios oficiais, concluímos que as LE cirúrgicas tiveram evolução positiva, nomeadamente na redução da mediana do TE da Lista Inscritos Cirurgia (LIC) (meses), no entanto, os objectivos dos Tempos Máximos Resposta Garantidos (TMRG) não estão a ser cumpridos. A análise das diferentes iniciativas e estratégias políticas para combater as LE, permitiu-nos sugerir caminhos a explorar, tendo como objectivo minorar o problema das LE: cuidados integrados, optimização da eficiência na utilização da capacidade instalada e maior aposta na cirurgia de ambulatório.

Consumer perception of CSR in Portugal: The aftermath of the financial crisis

Corporate social responsibility (CSR) literature has largely neglected consumers’ perceptions in the debate regarding the role of CSR in the aftermath of the financial crisis. In that context, this study aims to test the possibility that consumers’ perceptions of CSR level, firm reputation and brand trust, might depend on the type of industry sector of a firm, the level of fit of an initiative or both. By conducting a survey on Portuguese consumers and running a two-way analysis of variance, it suggests that solely the type of industry sector has an effect on consumer perception and that consumers are less tolerable of controversial industries.

Experimental and modeling studies on reverse electrodialysis for sustainable power generation

A potentially renewable and sustainable source of energy is the chemical energy associated with solvation of salts. Mixing of two aqueous streams with different saline concentrations is spontaneous and releases energy. The global theoretically obtainable power from salinity gradient energy due to World’s rivers discharge into the oceans has been estimated to be within the range of 1.4-2.6 TW. Reverse electrodialysis (RED) is one of the emerging, membrane-based, technologies for harvesting the salinity gradient energy. A common RED stack is composed by alternately-arranged cation- and anion-exchange membranes, stacked between two electrodes. The compartments between the membranes are alternately fed with concentrated (e.g., sea water) and dilute (e.g., river water) saline solutions. Migration of the respective counter-ions through the membranes leads to ionic current between the electrodes, where an appropriate redox pair converts the chemical salinity gradient energy into electrical energy. Given the importance of the need for new sources of energy for power generation, the present study aims at better understanding and solving current challenges, associated with the RED stack design, fluid dynamics, ionic mass transfer and long-term RED stack performance with natural saline solutions as feedwaters. Chronopotentiometry was used to determinate diffusion boundary layer (DBL) thickness from diffusion relaxation data and the flow entrance effects on mass transfer were found to avail a power generation increase in RED stacks. Increasing the linear flow velocity also leads to a decrease of DBL thickness but on the cost of a higher pressure drop. Pressure drop inside RED stacks was successfully simulated by the developed mathematical model, in which contribution of several pressure drops, that until now have not been considered, was included. The effect of each pressure drop on the RED stack performance was identified and rationalized and guidelines for planning and/or optimization of RED stacks were derived. The design of new profiled membranes, with a chevron corrugation structure, was proposed using computational fluid dynamics (CFD) modeling. The performance of the suggested corrugation geometry was compared with the already existing ones, as well as with the use of conductive and non-conductive spacers. According to the estimations, use of chevron structures grants the highest net power density values, at the best compromise between the mass transfer coefficient and the pressure drop values. Finally, long-term experiments with natural waters were performed, during which fouling was experienced. For the first time, 2D fluorescence spectroscopy was used to monitor RED stack performance, with a dedicated focus on following fouling on ion-exchange membrane surfaces. To extract relevant information from fluorescence spectra, parallel factor analysis (PARAFAC) was performed. Moreover, the information obtained was then used to predict net power density, stack electric resistance and pressure drop by multivariate statistical models based on projection to latent structures (PLS) modeling. The use in such models of 2D fluorescence data, containing hidden, but extractable by PARAFAC, information about fouling on membrane surfaces, considerably improved the models fitting to the experimental data.

Building a thinner gap in a gas-gap heat switch

25th International Cryogenic Engineering Conference and the International Cryogenic Materials Conference in 2014, ICEC 25–ICMC 2014

Evaluation of mechanical soft-abrasive blasting and chemical cleaning methods on alkyd-paint graffiti made on carbonate stones

In the context of this dissertation several studies were developed resulting in submission and publication “Evaluation of mechanical soft-abrasive blasting and chemical cleaning methods on alkyd-paint graffiti made on calcareous stones” to Journal of Cultural Heritage. (http://dx.doi.org/10.101 /j.culher.2014.10.004)

“The impact of online ratings on video game sales”

Online third-party reviews have been grown over the last decade and they now play an important role as a tool for helping customers evaluate products and services that in many cases offer more than tangible features. This study intends to quantify the impact online ratings have over video game sales by conducting a linear regression analysis on 300 titles for the previous console generation (PlayStation® 3 and Xbox® 360) using a data from the video game industry to understand the existing influence on this particular market. The findings showed that these variables have a weak linear relationship thus suggesting that quality of a title explains little the commercial success of a video game and instead this should cover a wider range of factors. Afterwards, we compare results to previous ones and discuss the managerial implications for upcoming gaming generations.

Lifetime-value creation through a customized offer adressed to diferent lifestyles

This paper purposes a method for marketing segmentation based on customers‟ lifestyle. A quantitative and qualitative segmentation established by the Whitaker Lifestyle™ Method was created in order to define a concrete and clear identification of the customer, by understanding the behavior, style and preferences of each segment. After conducting 18 in-depth interviews, it was concluded that four main personas characterize the customer base of the company. These four personas will be the support for the creation of „quick-wins‟ that address to the expectations of each lifestyle, projecting a significant impact on the lifetime-value of the company‟s customer base

Inovcity- Structure of trials evaluation

In 2007, the UK government commissioned the Energy Demand Research Project to conduct a large scale experiment of smart metering technologies to test the impacts from many different forms of feedback to residential consumers. A full evaluation of the results was completed in 2011. In Portugal, EDP is also conducting smart meter trials in a project called InovCity in the city of Évora whose results will be evaluated during 2012. In this work, the case of Great Britain is studied as a reference on how an evaluation of trial results should be conducted. I also discuss potential limitations of the experiments, implications for national roll-out decisions, and finally draw some lessons that can be applied to the Portuguese case.

As forças de tipo gendarmerie e as operações/missões de gestão de crises da União Europeia

The European Union has taken in recent years an increasingly important role in ensuring peace and stability in the international community, and the security and defence policy of the Union has become synonymous with crisis management. The Union has addressed the issue of crisis management through two sources: the military side and the civilian side, which consists in carrying out numerous crisis management operations and missions. This study discusses the role of the European Union in conducting crisis management operations and missions and how the gendarmerie forces contribute to the success of the same. It will discuss the evolution of the European Union's security policy and the concept of crisis management, and seek to demonstrate the added value of the commitment of gendarmerie forces in operations and missions of crisis management, particularly with regard to employment of the European Gendarmerie Force. On the other hand, it will study the planning process for crisis management of the European Union, featuring the entities and agencies involved in it, and presenting the products that result from this same process. The use of Gendarmerie forces in crisis management operations and missions has significant advantages. Its use is recommended to post - conflict scenarios, in complementarity with the armed forces, in order to overcome the "security gap" that mediates the transition from the state of conflict for the period of peace and reconstruction. Gendarmerie forces can also be engaged both in military crisis management operations and civilian crisis management missions.

Al-doped ZnO ceramic sputtering targets based on nanocrystalline powders produced by emulsion detonation synthesis – deposition and application as a transparent conductive oxide material

Transparent conducting oxides (TCOs) have been largely used in the optoelectronic industry due to their singular combination of low electrical resistivity and high optical transmittance. They are usually deposited by magnetron sputtering systems being applied in several devices, specifically thin film solar cells (TFSCs). Sputtering targets are crucial components of the sputtering process, with many of the sputtered films properties dependent on the targets characteristics. The present thesis focuses on the development of high quality conductive Al-doped ZnO (AZO) ceramic sputtering targets based on nanostructured powders produced by emulsion detonation synthesis method (EDSM), and their application as a TCO. In this sense, the influence of several processing parameters was investigated from the targets raw-materials synthesis to the application of sputtered films in optoelectronic devices. The optimized manufactured AZO targets present a final density above 99 % with controlled grain size, an homogeneous microstructure with a well dispersed ZnAl2O4 spinel phase, and electrical resistivities of ~4 × 10-4 Ωcm independently on the Al-doping level among 0.5 and 2.0 wt. % Al2O3. Sintering conditions proved to have a great influence on the properties of the targets and their performance as a sputtering target. It was demonstrated that both deposition process and final properties of the films are related with the targets characteristics, which in turn depends on the initial powder properties. In parallel, the influence of several deposition parameters in the film´s properties sputtered from these targets was investigated. The sputtered AZO TCOs showed electrical properties at room temperature that are superior to simple oxides and comparable to a reference TCO – indium tin oxide (ITO), namely low electrical resistivity of 5.45 × 10-4 Ωcm, high carrier mobility (29.4 cm2V-1s-1), and high charge carrier concentration (3.97 × 1020 cm-3), and also average transmittance in the visible region > 80 %. These superior properties allowed their successful application in different optoelectronic devices.

Optimization of wastewater quality in the Sines refinery

In order to address and resolve the wastewater contamination problem of the Sines refinery with the main objective of optimizing the quality of this stream and reducing the costs charged to the refinery, a dynamic mass balance was developed nd implemented for ammonia and polar oil and grease (O&G) contamination in the wastewater circuit. The inadequate routing of sour gas from the sour water stripping unit and the kerosene caustic washing unit, were identified respectively as the major source of ammonia and polar substances present in the industrial wastewater effluent. For the O&G content, a predictive model was developed for the kerosene caustic washing unit, following the Projection to Latent Structures (PLS) approach. Comparison between analytical data for ammonia and polar O&G concentrations in refinery wastewater originating from the Dissolved Air Flotation (DAF) effluent and the model predictions of the dynamic mass balance calculations are in a very good agreement and highlights the dominant impact of the identified streams for the wastewater contamination levels. The ammonia contamination problem was solved by rerouting the sour gas through an existing clogged line with ammonia salts due to a non-insulated line section, while for the O&G a dynamic mass balance was implemented as an online tool, which allows for prevision of possible contamination situations and taking the required preventive actions, and can also serve as a basis for establishing relationships between the O&G contamination in the refinery wastewater with the properties of the refined crude oils and the process operating conditions. The PLS model developed could be of great asset in both optimizing the existing and designing new refinery wastewater treatment units or reuse schemes. In order to find a possible treatment solution for the spent caustic problem, an on-site pilot plant experiments for NaOH recovery from the refinery kerosene caustic washing unit effluent using an alkaline-resistant nanofiltration (NF) polymeric membrane were performed in order to evaluate its applicability for treating these highly alkaline and contaminated streams. For a constant operating pressure and temperature and adequate operating conditions, 99.9% of oil and grease rejection and 97.7% of chemical oxygen demand (COD) rejection were observed. No noticeable membrane fouling or flux decrease were registered until a volume concentration factor of 3. These results allow for NF permeate reuse instead of fresh caustic and for significant reduction of the wastewater contamination, which can result in savings of 1.5 M€ per year at the current prices for the largest Portuguese oil refinery. The capital investments needed for implementation of the required NF membrane system are less than 10% of those associated with the traditional wet air oxidation solution of the spent caustic problem. The operating costs are very similar, but can be less than half if reusing the NF concentrate in refinery pH control applications. The payback period was estimated to be 1.1 years. Overall, the pilot plant experimental results obtained and the process economic evaluation data indicate a very competitive solution through the proposed NF treatment process, which represents a highly promising alternative to conventional and existing spent caustic treatment units.