Synthesis of biodiesel from wastes of food industry via direct transesterification with methanol/carbon dioxide mixtures

Dissertation presented at Faculdade de Ciências e Tecnologia from Universidade Nova de Lisboa to obtain the degree of Master in Chemical and Biochemical Engineering

Direct electrochemistry of the Desulfovibrio gigas aldehyde oxidoreductase

Eur. J. Biochem. 271, 1329–1338 (2004)

Professions and inter-disciplinary teamwork in socially embedded bureaucracies: Synthesis and hypotheses on the impact of informal and formal organization

In order to maximize their productivity, inter-disciplinary multi-occupation teams of professionals need to maximize inter-occupational cooperation in team decision making. Cooperation, however, is challenged by status anxiety over organizational careers and identity politics among team members who differ by ethnicity-race, gender, religion, nativity, citizenship status, etc. The purpose of this paper is to develop hypotheses about how informal and formal features of bureaucracy influence the level of inter-occupation cooperation achieved by socially diverse, multi-occupation work teams of professionals in bureaucratic work organizations. The 18 hypotheses, which are developed with the heuristic empirical case of National Science Foundation-sponsored university school partnerships in math and science curriculum innovation in the United States, culminate in the argument that cooperation can be realized as a synthesis of tensions between informal and formal features of bureaucracy in the form of participatory, high performance work systems.

Synthesis, characterization and reactivity of new cobalt, palladium and nickel complexes bearing α-diimines and P, O ligands

This work describes the synthesis and characterization of a series of new α-diimine and P,O, β-keto and acetamide phosphines ligands, and their complexation to Ni(II), Co(II),Co(III) and Pd(II) to obtain a series of new compounds aiming to study their structural characteristics and to test their catalytic activity. All the compounds synthesized were characterized by the usual spectroscopic and spectrometric techniques: Elemental Analysis, MALDI-TOF-MS spectrometry, IR, UV-vis, 1H, 13C and 31P NMR spectroscopies. Some of the paramagnetic compounds were also characterized by EPR. For the majority of the compounds it was possible to solve their solid state structure by single crystal X-ray diffraction. Tests for olefin polymerization were performed in order to determine the catalytic activity of the Co(II) complexes. Chapter I presents a brief introduction to homogenous catalysis, highlighting the reactions catalyzed by the type of compounds described in this thesis, namely olefin polymerization and oligomerization and reactions catalyzed by the complexes bearing α-diimines and P,O type ligands. Chapter II is dedicated to the description of the synthesis of new α-diimines cobalt (II) complexes, of general formula [CoX2(α-diimine)], where X = Cl or I and the α-diimines are bis(aryl)acenaphthenequinonediimine) (Ar-BIAN) and 1,4-diaryl-2,3-dimethyl-1,4-diaza-1,3-butadiene (Ar-DAB). Structures solved by single crystal X-ray diffraction were obtained for all the described complexes. For some of the compounds, X-band EPR measurements were performed on polycrystalline samples, showing a high-spin Co(II) (S = 3/2) ion, in a distorted axial environment. EPR single crystal experiments on two of the compounds allowed us to determine the g tensor orientation in the molecular structure. In Chapter III we continue with the synthesis and characterization of more cobalt (II)complexes bearing α-diimines of general formula [CoX2(α-diimine)], with X = Cl or I and α-diimines are bis(aryl)acenaphthenequinonediimine) (Ar-BIAN) and 1,4-diaryl-2,3-dimethyl- 1,4-diaza-1,3-butadiene (Ar-DAB). The structures of three of the new compounds synthesized were determined by single crystal X-ray diffraction. A NMR paramagnetic characterization of all the compounds described is presented. Ethylene polymerization tests were done to determine the catalytic activity of several of the Co(II) complexes described in Chapter II and III and their results are shown. In Chapter IV a new rigid bidentate ligand, bis(1-naphthylimino)acenaphthene, and its complexes with Zn(II) and Pd(II), were synthesized. Both the ligand and its complexes show syn and anti isomers. Structures of the ligand and the anti isomer of the Pd(II) complex were solved by single crystal X-ray diffraction. All the compounds were characterized by elemental analysis, MALDI-TOF-MS spectrometry, and by IR, UV-vis, 1H, 13C, 1H-1H COSY, 1H-13C HSQC, 1H-13C HSQC-TOCSY and 1H-1H NOESY NMR when necessary. DFT studies showed that both conformers of [PdCl2(BIAN)] are isoenergetics and can be obtain experimentally. However, we can predict that the isomerization process is not available in square-planar complex, but is possible for the free ligand. The molecular geometry is very similar in both isomers, and only different orientations for naphthyl groups can be expected. Chapter V describes the synthesis of new P, O type ligands, β-keto phosphine, R2PCH2C(O)Ph, and acetamide phosphine R2PNHC(O)Me, as well as a series of new cobalt(III) complexes namely [(η5-C5H5)CoI2{Ph2PCH2C(O)Ph}], and [(η5- C5H5)CoI2{Ph2PNHC(O)Me}]. Treating these Co(III) compounds with an excess of Et3N, resulted in complexes η2-phosphinoenolate [(η5-C5H5)CoI{Ph2PCH…C(…O)Ph}] and η2- acetamide phosphine [(η5-C5H5)CoI{Ph2PN…C(…O)Me}]. Nickel (II) complexes were also obtained: cis-[Ni(Ph2PN…C(…O)Me)2] and cis-[Ni((i-Pr)2PN…C(…O)Me)2]. Their geometry and isomerism were discussed. Seven structures of the compounds described in this chapter were determined by single crystal X-ray diffraction. The general conclusions of this work can be found in Chapter VI.

Synthesis of the Piacenzian onshore record between the Aveiro and Setubal parallels (Western portuguese margin)

Onshore, the Piacenzianof the Mondego and Lower Tagus Tertiary basins comprises siliciclastic sediments deposited in shallow marine to continental environments. The outcrops of the deposits are relatively widespread in the Aveiro and Seuibal region. A lithostratigraphic synthesis based on the correlation of geological sections, is presented for the two basins. In general, the Piacenzian sediments display a regressive sucession. The Late Tortonian-Zanclean (?) confined drainage pattern changed at the beginning of Piazencian, to fluvial systems draining to the Atlantic, and capturing the drainage of the inner parts of the Hesperic Meseta. The Piacenzian sedimentary sequence post-dates one of the uprising phases during Neogene compression, recorded by a strong regional unconformity. Some local active faulting - as in Lousa, Rio Maior and Senibal- Pinhal Novo - allowed the local thickening of the sedimentary record. Later compressive tectonism continues to generate reverse faulting and diapiric reactivation, affecting those sediments. Currently, the Piacenzian deposits culminates the marginal piedmonts, widely eroded by the Quaternary fluvial dissection.

Direct torque control em máquinas assíncronas

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

Estudo descritivo do perfil de utilizador da linha Saúde 24 com análise de impacto ao nível da eficiência, equidade e empowerment em comparação com o modelo inglês NHS Direct

RESUMO - A 8 de Maio de 2008 surgiu o centro de atendimento “Linha Saúde24” (S24) no sentido de modernizar o SNS, aproximando-o do cidadão. O serviço surge baseado no modelo inglês – o NHS Direct – que pode ser encarado como um serviço de informação telefónico apoiado por enfermeiros, disponível 24h por dia, concebido para expandir os serviços púbicos de acesso à rede prestadora de cuidados com intuito de aliviar a pressão da procura na rede de urgências hospitalares e médicos de família, assim como diluir as iniquidades regionais na prestação de serviços. A S24 assenta na perspectiva de ser um ponto de contacto inicial do utente com a rede de prestação de cuidados de saúde com capacidade de orientação. O objectivo da linha está na tentativa mais eficiente no uso dos recursos disponíveis, ao mesmo tempo que delega responsabilidade no cidadão na forma como este utiliza os recursos disponíveis, com melhor racionalização financeira na área da saúde aliada a uma melhor qualidade de serviço prestada e adequada, colocando os cidadãos no mesmo patamar, diluindo as dificuldades de acesso a aqueles que necessitam na tentativa de harmonizar e racionalizar o consumo de serviços de saúde. Esta estrutura permite ao cidadão conhecer melhor o seu estado de saúde e decidir mais acertadamente quanto à decisão a tomar. Com este estudo, e com base na literatura nacional e internacional, pretende-se descrever o perfil de utilizador que acede à S24 – definir o tipo de utilizador, disposição geográfica, motivos pelo qual acede ao serviço e qual o seu destino final, fazendo comparação com o perfil do NHS Direct. Assim, e com os dados obtidos, far-se-á uma avaliação preliminar em termos do contributo da linha S24 no que concerne à sua eficiência, equidade e empowerment dado ao utilizador. --- ------------------------------ABSTRACT - Saúde 24 (S24) is a national 24-hour health line initiated in May 2008 aiming at modernizing the Portuguese NHS by bringing it closer to the citizen. Indeed, S24 be seen as an initial contact point between the patient and the healthcare network, facilitating a better a management of health care demand. The service is inspired on the UK NHS Direct – a nurse-led telephone line to provide easier and faster advice information to people about health, illness and NHS services. It is expected to provide information so that people can deal with their health problems or their families´ on their own, with the purpose of reducing demand to A&E department and out-of-hours GP services. Additionally it can contribute to a reduction in regional inequities in healthcare provision through bringing health care advice to remote areas. The purpose of S24 is to handle more efficiently the available resources by enabling responsibilities in citizens. By doing so, S24 encourages a more appropriate use of available resources, with better financial outcomes and a better quality of care. It is meant, in terms of empowerment, to help people to be in control of their health and healthcare interactions by participating in the final decision. Based on quantitative data, this study defines the S24 caller user profile in terms of type, geographical reference, reasons for calling and outcome. This analysis allows us to perform a preliminary evaluation of the S24 in terms of its contribution to efficiency, equity and empowerment. Then the S24 is compared to

Synthesis of the Piacenzian onshore record between the Aveiro and Setúbal parallels (Western portuguese margin)

Onshore, the Piacenzian of the Mondego and Lower Tagus Tertiary basins comprises siliciclastic sediments deposited in shallow marine to continental environments. The outcrops of the deposits are relatively widespread in the Aveiro and Setúbal region. A lithostratigraphic synthesis based on the correlation of geological sections, is presented for the two basins. In general, the Piacenzian sediments display a regressive sucession. The Late Tortonian-Zanclean (?) confined drainage pattern changed at the beginning of Piazencian, to fluvial systems draining to the Atlantic, and capturing the drainage of the inner parts of the Hesperic Meseta. The Piacenzian sedimentary sequence post-dates one of the uprising phases during Neogene compression, recorded by a strong regional unconformity. Some local active faulting - as in Lousa, Rio Maior and Senibal- Pinhal Novo - allowed the local thickening of the sedimentary record. Later compressive tectonism continues to generate reverse faulting and diapiric reactivation, affecting those sediments. Currently, the Piacenzian deposits culminates the marginal piedmonts, widely eroded by the Quaternary fluvial dissection.

Light controlled synthesis of nucleic acids

Dissertação apresentada para obtenção do grau de Doutor em Bioquímica - especialidade Biotecnologia, pela Universidade Nova de Lisboa,Faculdade de Ciências e Tecnologia

Synthesis about a collaborative project on “Technology Assessment of Autonomous System

The project started in 2009 with the support of DAAD in Germany and CRUP in Portugal under the “Collaborative German-Portuguese University Actions” programme. One central goal is the further development of a theory of technology assessment applied to robotics and autonomous systems in general that reflects in its methodology the changing conditions of knowledge production in modern societies and the emergence of new robotic technologies and of associated disruptive changes. Relevant topics here are handling broadened future horizons and new clusters of science and technology (medicine, engineering, interfaces, industrial automation, micro-devices, security and safety), as well as new governance structures in policy decision making concerning research and development (R

Cyclopentadienyl-functionalised N-heterocyclic carbenes: synthesis, coordination to Mo, Ru, Rh

Dissertation presented to obtain the Ph.D degree in Chemistry

Selective synthesis under microwave irradiation of new monomers for potential applications in PDLC films

Dissertation to obtain the degree of master in Bioorganic

Insights into cell wall synthesis and cell division in Staphylococcus aureus

Dissertation presented to obtain the Ph.D degree in Biology

Quantum dots: synthesis, functionalization and bioconjugation for biological applications

Dissertation presented to obtain the Ph.D degree in Engineering Sciences and Technology

Kinetic, Structural, and EPR Studies Reveal That Aldehyde Oxidoreductase from Desulfovibrio gigas Does Not Need a Sulfido Ligand for Catalysis and Give Evidence for a Direct Mo-C Interaction in a Biological System

J. Am. Chem. Soc., 2009, 131 (23), pp 7990–7998 DOI: 10.1021/ja809448r