Study of forbidden transitions in atomic systems

A Thesis submitted for the co-tutelle degree of Doctor in Physics at Universidade Nova de Lisboa and Université Pierre et Marie Curie

Neolithic transitions: can genetic data help us understand a major demographic event in human prehistory?

Dissertation presented to obtain the Ph.D degree in Biology

Low-Spin Heme b3 in the Catalytic Center of Nitric Oxide Reductase from Pseudomonas nautica

Biochemistry, 2011, 50 (20), pp 4251–4262 DOI: 10.1021/bi101605p

Long-term behaviour of railway transitions under dynamic loading application to soft soil sites

Dissertação para obtenção do Grau de Doutor em Engenharia Civil

Functional brain perfusion evaluation with Arterial Spin Labeling at 3 Tesla

Dissertation submitted in Faculdade de Ciências e Tecnologia of Universidade Nova de Lisboa for the degree of Master of Biomedical Engineering

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.

The Impact of income support programs on transitions to employment

The income support programs are created with the purpose of fighting both, the poverty trap and the inactivity trap. The balance between both is fragile and hard to find. Thus, the goal of this work is to contribute to solve this issue by finding how income support programs, particularly the Portuguese RSI, affect transitions to employment. This is made through duration analysis, namely using Cox and Competing Risks models. A particular feature is introduced in this work as it incorporates the possibility of Defective Risks. The estimated hazard elasticity with respect to the amount of RSI received for individuals who move to employment is -0,41. More than a half of RSI receivers stays for more than a year and the probability of never leaving to employment is 44%. The results appear to indicate that RSI has affected negatively transitions to employment.

The spin-off of Sonae Capital

The purpose of this project is to study the spin-off of Sonae Capital, which took place in January 2008. Taking the form of a case study, this project is divided between the case narrative and a teaching note. I study the background and motivation of the transaction, along with its outcome. With the available information at the time of the case, I value Sonae Capital at the date of the spin-off and describe a possible trading strategy involving both the spun-off and the demerged companies. Finally, I conclude that the transaction was more beneficial for the parent company, Sonae SGPS, and that it did not follow the typical outperformance pattern observed in other spin-offs.

Construction sector: Need for strategic reorientation

The construction sector in Portugal declined sharply over the past 10 years. The current crisis can wiped out the entire industry. Can the industry survive? What lessons can we learn? What can be done to revive the sector? These are questions this study intends to answer. By analyzing the best practices of the industry and of the largest construction companies in Portugal, as well as the difficulties and constrains that they all faced, I found that retrenchment (operational costs and selling assets) are the main measures companies resort to, and that strategic reorientation is essential to turnaround. I found that internationalization is a key driver on strategic reorientation and diversification and concentration are complementary strategies that can enforce and strengthen the main one.

Introducing spin-off stocks into the NSP’s risk parity strategy

Field lab: Nova Student Portfolio

Carl Icahn pushes ebay to spin-off paypal

The following case-study describes the situation involving eBay, PayPal and Carl Icahn as of February 2014. Its structure is divided between the narrative and a teaching note. The case narrative describes all the events between the three parties until the 24th of February 2014, when the activist investor Carl Icahn sends a public shareholder letter strongly criticizing eBay’s board and corporate governance practices while proposing at the same time the spin-off of PayPal from eBay. The teaching note intends to analyse the possibility of spinning-off PayPal, while at the same time analysing the Corporate Governance issues in eBay’s board. The final conclusion in the teaching note is favourable towards the spin-off of PayPal.