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.

A built-in self-test technique for high speed analog-to-digital converters

Fundação para a Ciência e a Tecnologia (FCT) - PhD grant (SFRH/BD/62568/2009)

Map-it – Mapeamento tridimensional de interiores

A perceção tridimensional é uma área em crescente desenvolvimento. Não existindo uma tecnologia ideal capaz de percecionar todo o tipo de cenários, têm surgido estudos sobre a aplicabilidade de diferentes tecnologias de forma a obter modelos que melhor se aproximem da realidade. Propõe-se nesta dissertação o desenvolvimento de um sistema de baixo-custo de percepção tridimensional que seja portátil e acessível na sua aplicabilidade, de forma a ter a capacidade de percecionar tridimensionalmente espaços interiores com pouca iluminação, tais como as divisões de um edifício ou os canais de uma mina subterrânea. Utilizou-se a triangulação entre uma câmara digital, os pontos de uma linha laser e um emissor laser para a obtenção dos dados tridimensionais do cenário. Para isso, recorreu-se a metodologias de processamento digital de imagens para a construção dos modelos dos cenários. Para se obter a validação desta dissertação, realizaram-se testes do protótipo de forma a determinar as suas capacidades percecionais. Em primeiro lugar realizou-se uma bateria de testes de calibração onde, repetidamente, se estudaram isoladamente pontos do cenário para verificar a precisão do sensor. Após esta calibração, estudou-se a capacidade de transformação de uma linha laser projetada num conjunto de coordenadas. Finalmente testou-se a capacidade de perceção tridimensional por rotação do sensor, de forma a realizar a transformação de múltiplas projeções de linhas laser num conjunto de coordenadas em torno do sensor. Verificou-se: no teste de calibração, a obtenção de distâncias com erro médio relativo inferior a 1%; no teste da linha laser, a capacidade de perceção de profundidade de múltiplos pontos ao longo da mesma; no teste de rotação, a aquisição de múltiplos conjuntos de linhas de profundidade no cenário, por rotação do sensor. Os resultados dos testes de validação permitiram concluir a viabilidade de utilizar a triangulação na aquisição de conjuntos de coordenadas de espaços interiores.

Untitled: Figurations of memory

The next pages will describe my experience and results of making connections between cognitive sciences and art; the transformations of my memories being the object of study and motivation for this process of self-discovery. The human body reacts according to innumerable neural functions and external stimuli. Neurons respond to the evocation of experienced events, building virtual images, map-like constellations sometimes fulfilled by imagination, desires or knowledge promoting in this way their constant reshaping. This document offers an insight into my recollections as matter. As matter these recollections take on different states and I hope to give you a better sense of my personal voice using my experience with glass to explore this transformation and accompanying my journey with lectures and scientific readings about the mind functions.

Self-initiation expatriation: A focus on Italian and Portuguese students

The purpose of this work project is to analyze the phenomenon of self-initiated expatriation (SIE) through its link to the Protean Career and Career Capital theories, focusing in particular on Italian and Portuguese students attending a Master in the business area. The main research questions are to understand the reasons driving the intention to expatriate, after the conclusion of the academic path, using three main categories (Adventure Motivation, Work Characteristic Motivation and instrumental Motivation) and the intention to repatriate. A sample of Italian and Portuguese students was obtained. Italians show a higher intention to expatriate relative to Portuguese; nevertheless, no other significant differences were found among the two populations, because of the similar cultural background and economic situation. Additionally, several heterogeneities were observed considering other clusters defined by Gender, Teaching Language of the Master and Past International Experiences, across the two nationalities. Furthermore, possible future researches and practical implications were discussed.

Secondary bronchiolitis obliterans organizing pneumonia during treatment of chronic hepatitis C: role of pegylated interferon alfa-2a

The treatment of chronic hepatitis C has frequent side effects such as cytopenias and neuropsychiatric symptoms. However, pulmonary toxicity associated with interferon is rarely described. This paper describes the clinical case of a 67-year-old female patient with chronic hepatitis C who presented an acute onset of dry cough, dyspnoea, and fever 36 weeks after the use of pegylated interferon alfa-2a and ribavirin. The lung biopsy confirmed the diagnosis of a bronchiolitis obliterans organizing pneumonia (BOOP). Corticotherapy was initiated, with clinical and radiological improvement. This paper aims to advise physicians to this occasional, though severe, adverse event related to hepatitis C virus (HCV) treatment.

Positive serology for viral hepatitis and donor self-exclusion in Southern Brazil

Introduction Despite the great advances in serological testing for transfusion-transmitted infections, the selection of blood donors by blood bank operators remains the only way to avoid transmission within the testing window period. Part of this selection is the self-exclusion form, on which the donors can exclude their blood from donation without any explanation. This study assessed the clinical and epidemiological characteristics related to positivity for viral hepatitis and to the use of the confidential self-exclusion (CSE) form. Methods This transversal study analyzed the data collected from blood donors' files in a hospital in Southern Brazil. Univariate and multivariate analyses identified the clinical and epidemiological variables related to positive serologies of viral hepatitis and to whether the donor was self-excluded. Results Of the 3,180 donors included in this study, 0.1% tested positive for HBsAg, 2.1% for anti-HBc, and 0.9% for anti-HCV. When the 93 donors with positive serologies for viral hepatitis were compared with those who were negative, a greater proportion of the positive serology group was found to have had a history of blood transfusions (OR=4.908; 95%CI=1.628 - 14.799; p<0.01), had repeatedly donated (OR=2.147; 95%CI=1.236 - 3.729; p<0.01), and used the CSE form for self-exclusion (OR=7.139; 95%CI=2.045 - 24.923; p<0.01). No variables were independently associated with self-exclusion. Conclusions A history of blood transfusion, repeated donations, and self-exclusion are factors that should be considered during viral hepatitis screenings in blood banks.

Fate map of zebrafish left-right organizer

The organizer is a ciliated signalling transient organ, responsible for the patterning of embryo tissues during embryonic development. In higher vertebrates, such as mouse and chick, this organizer (the node and the Hensen’s node, respectively) performs dorsalventral and anteriorposterior axis definition, as well as left-right patterning of the internal organs. In lower vertebrates, such as frog and zebrafish, there is a separate specialized organ for left-right purposes called the Gastrocoel Roof Plate (GRP) and Kupffer’s Vesicle (KV), respectively. It is known that mouse and chick organizer cells give rise to structures like floor plate, notochord, hypochord and somites. Frog GRP originates all these but floor plate. In zebrafish, at 13-14 somite stage (ss) the KV finished its left-right patterning but what happens to this organizer’ cells is still poorly studied. This research attempts to understand the fate and behaviour of the KV cells. We followed the fate of KV cells by live imaging and by tight time-courses with fixed larvae. We assessed in detail their proliferative and death profile, as well as cilia length progression from 9-10 ss until 29-30 ss. We conclude that the KV cells mostly follow the evolutionarily conserved fates described for other organizers. These cells mainly incorporate the notochord and hypochord; few cells incorporate the floor plate and the somites. As a novelty, it is also hypothesized that the hypural cell fate may be among the KV cell fates.

Illness perception, knowledge and self-care about cervical cancer

Prevention plays a central role in early detection of cervical cancer. Common Sense Model proposes that the nature and organization of illness representations can guide actions related to health and how self-care is exercised. The aim of this study was to describe and compare illness perception, knowledge and self-care in women with and without cancer precursor lesions. Participants were 92 women (aged 18-59) from primary care unity divided into two groups: women with and without premalignant lesion. Measures for illness perception, knowledge and self-care were used. There was no statistically signifi cant difference (t test e chi-square test) between groups in the variables analyzed. Despite the risk for cervical cancer, women with precursor lesions do not adjust their illness perceptions, knowledge and self-care to the situation. These data show the need to warn women against the cervical cancer risks, because their distorted perceptions and lack of knowledge about the disease may hamper the screening and control of cervical cancer.

Self-transcendence is related to higher female sexual desire

One facet of self-transcendence is creative self-forgetfulness (CSF; tendency to be attentionally absorbed in mindaltering experiences). Proneness to mind-altering attentional absorption and other aspects of self-transcendence were previously related to vaginal intercourse frequency, sexual arousability, and female coital orgasm. Given that sexual responsiveness is enhanced by focused attention, itwas testedwhether CSF correlates with sexual responsiveness, and if maladaptive defenses, openness to experience, and testosterone explain the hypothesized relationships. One hundred thirty-nine Portuguese (98 women) provided saliva samples for testosterone determination by luminescence immunoassays before and after a romantic movie scene and reported how intensely they felt sexual desire and arousal during the movie. CSF was measured by the Temperament and Character Inventory– Revised, maladaptive defenses by the immature defenses subscale of the Defense Style Questionnaire (DSQ-40), male and female past month desire by the desire dimensions of the International Index of Erectile Function (IIEF), and Female Sexual Function Index (FSFI). Female desire and arousal during themoviewere independently predicted by CSF, openness to experience and testosterone, but not by immature defenses. Female past month desire was independently predicted by CSF, testosterone, and less immature defenses. Possible psychobiological processes linking self-transcendence and sexual responsiveness are discussed.

Appreciating the power of words and imaginative organizing: A triadic model of ethics practiced in everyday conversations

This thesis provides an alternative framework to analyze power and ethics practiced in everyday conversations, which constitute processes of organizing. Drawing upon narrative frameworks, the analyses of messages posted on an online message board demonstrate people’s imaginative capacity to create relevant stories, in respect of their precise grasp of factual understandings, contextual relevance and evaluative/moral appropriateness, by appropriating others’ words. Based on the empirical analyses, the thesis indicates that studies on power and ethics in organizations can be re-oriented towards appreciating irremediable power imbalances by offering alternative ways of member’s denoting experiences of power.

Design and implementation of an assurance map at Sonae retail business

The present Working Project aims at studying the topic of assurance mapping in a specific organizational context of a Portuguese retail company. For this purpose, an assurance map framework was designed to support the decision making process of stakeholders, through the delivery of comfort concerning risks, operations and control. In the end, the framework was successfully implemented for the process sourcing of goods in two business units of the company. Although, further implementation of the framework proved not to be feasible during the project’s timespan, it is expected to occur in the near future.

Empowerment and intentions to resist future change: the moderating effect organization-based self-esteem

Nowadays, organizations face a constant need for adaptability, increasing the importance of change management. Our study focuses of how empowering leadership influences intentions to resist future changes, mediated by the effects of psychological and structural empowerment. From the responses of the two questionnaires (N1=230; Ntf=113), we found that empowering leadership fosters psychological and structural empowerment. Structural empowerment was the main driver in reducing intentions to resist future change when an employee has high organization-based self-esteem. Our findings add to the literature by examining how we can anticipate and manage change under an empowering context, building on social exchange and uncertainty reduction theories

How to reduce the causes of call center contact by implementing web self-service at Sonae MC?

This project aims to provide feasible solutions to improve customer´s Help Area at Continente Online. The goal is to increase satisfaction and loyalty by reducing the main causes that lead customers to appeal to Call Center or abandon the website. The pursued solution is the implementation of Web Self-Service and the vision taken is focused not only on providing customers basic help tools but also innovate with international best practices to sustain Sonae MC´s present and future market leader position. Customer´s feedback, costs and impact are taken in consideration to find the best fit for the company.

The influence of fibre orientation on the post-cracking tensile behaviour of steel fibre reinforced self-compacting concrete

Adding fibres to concrete provides several advantages, especially in terms of controlling the crack opening width and propagation after the cracking onset. However, distribution and orientation of the fibres toward the active crack plane are significantly important in order to maximize its benefits. Therefore, in this study, the effect of the fibre distribution and orientation on the post-cracking tensile behaviour of the steel fibre reinforced self-compacting concrete (SFRSCC) specimens is investigated. For this purpose, several cores were extracted from distinct locations of a panel and were subjected to indirect (splitting) and direct tensile tests. The local stress-crack opening relationship (σ-w) was obtained by modelling the splitting tensile test under the finite element framework and by performing an Inverse Analysis (IA) procedure. Afterwards the σ-w law obtained from IA is then compared with the one ascertained directly from the uniaxial tensile tests. Finally, the fibre distribution/orientation parameters were determined adopting an image analysis technique.