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.

Soldadura por fricção linear assistida por corrente eléctrica das ligas AA 6082-T6 a Ti6Al4V

A ligação dissimilar de ligas de alumínio a ligas de titânio tem elevado potencial para aplicações nas indústrias aeroespacial, automóvel e naval, devido à sua baixa razão peso/resistência mecânica. Contudo, soldar ligas de alumínio a ligas de titânio apresenta-se como um grande desafio, principalmente devido à formação de fases intermetálicas frágeis que têm um efeito negativo nas propriedades mecânicas da junta. Neste estudo, foram realizadas ligações dissimilares das ligas AA6082-T6 a Ti6Al4V, por Fricção Linear assistida por Corrente Eléctrica. Para a utilização de corrente eléctrica na Soldadura por Fricção Linear foram desenvolvidas, produzidas e testadas duas novas ferramentas. A estrutura da ligação foi analisada, por microscopia óptica e electrónica de varrimento. Controlando os parâmetros de soldadura foi possível obter soldaduras topo a topo e sobrepostas com um bom aspecto superficial e com continuidade metálica na interface. Nas ligações topo-a-topo observaram-se defeitos na raiz do cordão. As estruturas na zona soldada dependem fortemente da posição do pino em relação à interface. O uso da corrente eléctrica permitiu reduzir os defeitos na raiz, como vazios e falta de ligação na mesma, sem afectar as características metalúrgicas da interface. A utilização da corrente eléctrica permite aumentar a viscoplasticidade do material e facilitar a deformação plástica à volta do pino.

Modelação não linear de estruturas metálicas e mistas em situação de incêndio no software OpenSees

Os incêndios em edifícios representam um fenómeno que pode ter consequências devastadoras quando não controlado, não só em termos de perdas de vidas humanas, como em termos económicos. No passado, a ocorrência de incêndios de grandes dimensões mostrou os efeitos do fogo descontrolado nos edifícios, assim como a ineficiência dos meios de segurança ativa ao fogo. Nas últimas duas décadas, estas questões motivaram o estudo e compreensão da ação dos incêndios nas estruturas dos edifícios. Neste trabalho estuda-se a modelação da ação do fogo em estruturas metálicas e mistas, com o objetivo de contribuir para a sua melhor caracterização. A presente tese foca-se na validação e compreensão da implementação de análises termo-mecânicas a estruturas mistas no software de elementos finitos OpenSees (Open System for Earthquake Engineering Simulation), contribuindo assim para futuros estudos, não só de análises de estruturas mistas sujeitas a incêndio, mas também de análises de estruturas mistas sujeitas a eventos consecutivos, como sismo seguido de incêndio. Neste trabalho é feita uma breve descrição do fenómeno fogo, assim como dos processos inerentes à dinâmica de um incêndio que constituem uma fonte de incerteza para a modelação de cenários de incêndio num edifício. Posto isto, são abordados alguns modelos de incêndios presentes nos Eurocódigos, assim como o recente modelo de fogos móveis(“Travelling fires”). São realizados exemplos de aplicação no software e dois casos de estudo. O primeiro consiste na modelação de dois ensaios ao fogo realizados na Alemanha em 1986 em estruturas metálicas à escala 1/4. O segundo consiste na modelação de um ensaio ao fogo a uma viga de betão armado simplesmente apoiada, realizado no Instituto Superior Técnico em 2010. Os modelos numéricos desenvolvidos no OpenSees contabilizam as não linearidades físicas e geométricas, com elementos finitos de plasticidade distribuída e com uma formulação baseada em deslocamentos. Os resultados numéricos são então comparados com os experimentais, de modo a validar as análises termo-mecânicas no OpenSees.

Desenvolvimento experimental e simulação numérica em soldadura por fricção linear assistida por corrente elétrica

A soldadura por fricção linear (SFL) é um processo de ligação no estado sólido com capacidade para soldar materiais dissimilares e ligas metálicas de baixa soldabilidade. Contudo, nas juntas soldadas com uma configuração topo-a-topo é possível o aparecimento de defeitos na raiz do cordão, nomeadamente, de falta de penetração e de alinhamentos de óxidos. Estes defeitos são responsáveis pela diminuição da resistência mecânica das juntas, sobretudo quando sujeitas a esforços de fadiga. Existem variantes do processo para eliminar este tipo de defeitos, no entanto, verificam-se algumas dificuldades tecnológicas e a competitividade do processo é afetada. No âmbito deste trabalho desenvolveu-se uma variante do processo designado soldadura por fricção linear assistida por corrente elétrica (SFLAE). Esta variante consiste em introduzir uma corrente elétrica de elevada intensidade na zona da raiz do cordão, por forma a que o calor gerado por efeito de Joule aqueça o material e aumente o fluxo visco-plástico nessa zona, tendo em vista atenuar ou eliminar os defeitos na raiz. Foram concebidas e produzidas ferramentas de SFL dedicadas, melhorado um modelo analítico do processo, realizadas simulações numéricas para permitir compreender alguns fenómenos físicos envolvidos no processo, e realizados ensaios experimentais de validação. A análise aos cordões permitiu observar uma diminuição da espessura dos defeitos na raiz em três ensaios realizados na liga AA1100 e AA6084-T6 usando intensidades de corrente de 300 A. Dos resultados de microdureza e de medição de condutividade elétrica é possível concluir que a microestrutura do material não é significativamente alterada pela passagem de corrente elétrica.

Diffusional kurtosis imaging using a fast heuristic constrained linear least squares algorithm: a plugin for OsiriX

Diffusion Kurtosis Imaging (DKI) is a fairly new magnetic resonance imag-ing (MRI) technique that tackles the non-gaussian motion of water in biological tissues by taking into account the restrictions imposed by tissue microstructure, which are not considered in Diffusion Tensor Imaging (DTI), where the water diffusion is considered purely gaussian. As a result DKI provides more accurate information on biological structures and is able to detect important abnormalities which are not visible in standard DTI analysis. This work regards the development of a tool for DKI computation to be implemented as an OsiriX plugin. Thus, as OsiriX runs under Mac OS X, the pro-gram is written in Objective-C and also makes use of Apple’s Cocoa framework. The whole program is developed in the Xcode integrated development environ-ment (IDE). The plugin implements a fast heuristic constrained linear least squares al-gorithm (CLLS-H) for estimating the diffusion and kurtosis tensors, and offers the user the possibility to choose which maps are to be generated for not only standard DTI quantities such as Mean Diffusion (MD), Radial Diffusion (RD), Axial Diffusion (AD) and Fractional Anisotropy (FA), but also DKI metrics, Mean Kurtosis (MK), Radial Kurtosis (RK) and Axial Kurtosis (AK).The plugin was subjected to both a qualitative and a semi-quantitative analysis which yielded convincing results. A more accurate validation pro-cess is still being developed, after which, and with some few minor adjust-ments the plugin shall become a valid option for DKI computation

Determinants of mother-baby relationship evaluated during pregnancy

ABSTRACT Background Mental health promotion is supported by a strong body of knowledge and is a matter of public health with the potential of a large impact on society. Mental health promotion programs should be implemented as soon as possible in life, preferably starting during pregnancy. Programs should focus on malleable determinants, introducing strategies to reduce risk factors or their impact on mother and child, and also on strengthening protective factors to increase resilience. The ambition of early detecting risk situations requires the development and use of tools to assess risk, and the creation of a responsive network of services based in primary health care, especially maternal consultation during pregnancy and the first months of the born child. The number of risk factors and the way they interact and are buffered by protective factors are relevant for the final impact. Maternal-fetal attachment (MFA) is not yet a totally understood and well operationalized concept. Methodological problems limit the comparison of data as many studies used small size samples, had an exploratory character or used different selection criteria and different measures. There is still a lack of studies in high risk populations evaluating the consequences of a weak MFA. Instead, the available studies are not very conclusive, but suggest that social support, anxiety and depression, self-esteem and self-control and sense of coherence are correlated with MFA. MFA is also correlated with health practices during pregnancy, that influence pregnancy and baby outcomes. MFA seems a relevant concept for the future mother baby interaction, but more studies are needed to clarify the concept and its operationalization. Attachment is a strong scientific concept with multiple implications for future child development, personality and relationship with others. Secure attachment is considered an essential basis of good mental health, and promoting mother-baby interaction offers an excellent opportunity to intervention programmes targeted at enhancing mental health and well-being. Understanding the process of attachment and intervening to improve attachment requires a comprehension of more proximal factors, but also a broader approach that assesses the impact of more distal social conditions on attachment and how this social impact is mediated by family functioning and mother-baby interaction. Finally, it is essential to understand how this knowledge could be translated in effective mental health promoting interventions and measures that could reach large populations of pregnant mothers and families. Strengthening emotional availability (EA) seems to be a relevant approach to improve the mother-baby relationship. In this review we have offered evidence suggesting a range of determinants of mother-infant relationship, including age, marital relationship, social disadvantages, migration, parental psychiatric disorders and the situations of abuse or neglect. Based on this theoretical background we constructed a theoretical model that included proximal and distal factors, risk and protective factors, including variables related to the mother, the father, their social support and mother baby interaction from early pregnancy until six months after birth. We selected the Antenatal Psychosocial Health Assessment (ALPHA) for use as an instrument to detect psychosocial risk during pregnancy. Method Ninety two pregnant women were recruited from the Maternal Health Consultation in Primary Health Care (PHC) at Amadora. They had three moments of assessment: at T1 (until 12 weeks of pregnancy) they filed out a questionnaire that included socio-demographic data, ALPHA, Edinburgh post-natal Depression Scale (EDPS), General Health Questionnaire (GHQ) and Sense of Coherence (SOC); at T2 (after the 20th weeks of pregnancy) they answered EDPS, SOC and MFA Scale (MFAS), and finally at T3 (6 months after birth), they repeated EDPS and SOC, and their interaction with their babies was videotaped and later evaluated using EA Scales. A statistical analysis has been done using descriptive statistics, correlation analysis, univariate logistic regression and multiple linear regression. Results The study has increased our knowledge on this particular population living in a multicultural, suburb community. It allow us to identify specific groups with a higher level of psychosocial risk, such as single or divorced women, young couples, mothers with a low level of education and those who are depressed or have a low SOC. The hypothesis that psychosocial risk is directly correlated with MFAS and that MFA is directly correlated with EA was not confirmed, neither the correlation between prenatal psychosocial risk and mother-baby EA. The study identified depression as a relevant risk factor in pregnancy and its higher prevalence in single or divorced women, immigrants and in those who have a higher global psychosocial risk. Depressed women have a poor MFA, and a lower structuring capacity and a higher hostility to their babies. In average, depression seems to reduce among pregnant women in the second part of their pregnancy. The children of immigrant mothers show a lower level of responsiveness to their mothers what could be transmitted through depression, as immigrant mothers have a higher risk of depression in the beginning of pregnancy and six months after birth. Young mothers have a low MFA and are more intrusive. Women who have a higher level of education are more sensitive and their babies showed to be more responsive. Women who are or have been submitted to abuse were found to have a higher level of MFA but their babies are less responsive to them. The study highlights the relevance of SOC as a potential protective factor while it is strongly and negatively related with a wide range of risk factors and mental health outcomes especially depression before, during and after pregnancy. Conclusions ALPHA proved to be a valid, feasible and reliable instrument to Primary Health Care (PHC) that can be used as a total sum score. We could not prove the association between psychosocial risk factors and MFA, neither between MFA and EA, or between psychosocial risk and EA. Depression and SOC seems to have a clear and opposite relevance on this process. Pregnancy can be considered as a maturational process and an opportunity to change, where adaptation processes occur, buffering risk, decreasing depression and increasing SOC. Further research is necessary to better understand interactions between variables and also to clarify a better operationalization of MFA. We recommend the use of ALPHA, SOC and EDPS in early pregnancy as a way of identifying more vulnerable women that will require additional interventions and support in order to decrease risk. At political level we recommend the reinforcement of Immigrant integration and the increment of education in women. We recommend more focus in health care and public health in mental health condition and psychosocial risk of specific groups at high risk. In PHC special attention should be paid to pregnant women who are single or divorced, very young, low educated and to immigrant mothers. This study provides the basis for an intervention programme for this population, that aims to reduce broad spectrum risk factors and to promote Mental Health in women who become pregnant. Health and mental health policies should facilitate the implementation of the suggested measures.

Relating the spatial component and users interests to improve applications based on questions, petitions and participatory processes

Nowadays, participatory processes attending the need for real democracy and transparency in governments and collectives are more needed than ever. Immediate participation through channels like social networks enable people to give their opinion and become pro-active citizens, seeking applications to interact with each other. The application described in this dissertation is a hybrid channel of communication of questions, petitions and participatory processes based on Public Participation Geographic Information System (PPGIS), Participation Geographic Information System (PGIS) and ‘soft’ (subjective data) Geographic Information System (SoftGIS) methodologies. To achieve a new approach to an application, its entire design is focused on the spatial component related with user interests. The spatial component is treated as main feature of the system to develop all others depending on it, enabling new features never seen before in social actions (questions, petitions and participatory processes). Results prove that it is possible to develop a working application mainly using open source software, with the possibility of spatial and subject filtering, visualizing and free download of actions within application. The resulting application empowers society by releasing soft data and defines a new breaking approach, unseen so far.

Analysis of temporal and spatial variations of forest. A case of study in notheastern Armenia

The forest has a crucial ecological role and the continuous forest loss can cause colossal effects on the environment. As Armenia is one of the low forest covered countries in the world, this problem is more critical. Continuous forest disturbances mainly caused by illegal logging started from the early 1990s had a huge damage on the forest ecosystem by decreasing the forest productivity and making more areas vulnerable to erosion. Another aspect of the Armenian forest is the lack of continuous monitoring and absence of accurate estimation of the level of cuts in some years. In order to have insight about the forest and the disturbances in the long period of time we used Landsat TM/ETM + images. Google Earth Engine JavaScript API was used, which is an online tool enabling the access and analysis of a great amount of satellite imagery. To overcome the data availability problem caused by the gap in the Landsat series in 1988- 1998, extensive cloud cover in the study area and the missing scan lines, we used pixel based compositing for the temporal window of leaf on vegetation (June-late September). Subsequently, pixel based linear regression analyses were performed. Vegetation indices derived from the 10 biannual composites for the years 1984-2014 were used for trend analysis. In order to derive the disturbances only in forests, forest cover layer was aggregated and the original composites were masked. It has been found, that around 23% of forests were disturbed during the study period.

Enhancement of an implemented rating model and impact on existing risk management processes: A hands-on approach from financial supplier risk management within the automotive industry

The purpose of this paper is to conduct a methodical drawback analysis of a financial supplier risk management approach which is currently implemented in the automotive industry. Based on identified methodical flaws, the risk assessment model is further developed by introducing a malus system which incorporates hidden risks into the model and by revising the derivation of the most central risk measure in the current model. Both methodical changes lead to significant enhancements in terms of risk assessment accuracy, supplier identification and workload efficiency.

Lévy processes and the Brazilian market

No presente artigo apresentamos processos de Levy usados na literatura para modelar os retornos dos ativos financeiros, estes processos sao gerados pelas distribuições Pareto-Estaveis e Hiperbolicas. Estudamos algumas propriedades destas distribui<;oes, em particular a propriedade da invariancia da escala temporal. Por ultimo apresentamos evidencias empiricas da aplicabilidade destes processos para modelar retornos de ativos Brasileiros, para isto usamos 0 Ibovespa, o recibo da Telebras e Petrobras, na amostra usamos dados dos periodos de 1 de janeiro de 1995 a 31 de dezembro de 1998 (Gl) e de 12 de janeiro de 1996 a 31 de dezembro de 1997(G2).

How to improve Sonae's processes of suppliers of services' management?

Sonae is one of the greatest retailers in Portugal. As the business got bigger, it centralized operations. Direcção de Serviços Administrativos processes all invoices sent by suppliers. However, there are many which deliver errors and are not processed automatically. As a result, there are lost invoices and suppliers who are not paid, while the company’s accountability becomes less transparent. Such is due to a lack of proactive attitude towards suppliers as well as to a lack of incentives for employees to perform well. Great savings may be achieved with little effort, if the right things are measured so that the right tools may be applied.

How to monitor and improve Unilever JM Supply Chain processes to become the best of Portugal’s sector in 2015?

Unilever Jerónimo Martins is a Portuguese joint-venture leading firm in what concerns the supply chain industry of fast-moving consumer goods in Portugal. The scope of analysis of this Work Project is focusing on Unilever-JM operations and services in the Portuguese market regarding quality, efficiency and effectiveness over B2B customers. It will be analysed the possibility of development and implementation of a performance measurement system, Tableau de Bord, which will be crucial for the identification of potential opportunities of improvement with impact in the supply chain processes. This will be completed through the establishment of KPI’s to monitor and manage periodically logistics, planning and customer service processes’ performance, which are the ones where the bottlenecks are impacting more in the supply chain. In this work project the nexus causality for the problems will also be discussed and some recommendations will be prepared to tackle the inefficiencies found through the monitoring of the previous core processes, in order to improve efficacy and quality service of the supply chain.

A logical foundation for session-based concurrent computation

Linear logic has long been heralded for its potential of providing a logical basis for concurrency. While over the years many research attempts were made in this regard, a Curry-Howard correspondence between linear logic and concurrent computation was only found recently, bridging the proof theory of linear logic and session-typed process calculus. Building upon this work, we have developed a theory of intuitionistic linear logic as a logical foundation for session-based concurrent computation, exploring several concurrency related phenomena such as value-dependent session types and polymorphic sessions within our logical framework in an arguably clean and elegant way, establishing with relative ease strong typing guarantees due to the logical basis, which ensure the fundamental properties of type preservation and global progress, entailing the absence of deadlocks in communication. We develop a general purpose concurrent programming language based on the logical interpretation, combining functional programming with a concurrent, session-based process layer through the form of a contextual monad, preserving our strong typing guarantees of type preservation and deadlock-freedom in the presence of general recursion and higher-order process communication. We introduce a notion of linear logical relations for session typed concurrent processes, developing an arguably uniform technique for reasoning about sophisticated properties of session-based concurrent computation such as termination or equivalence based on our logical approach, further supporting our goal of establishing intuitionistic linear logic as a logical foundation for sessionbased concurrency.

Modelação não-linear do comportamento de vigas-parede

Com a evolução dos recursos computacionais e o desenvolvimento dos modelos constitutivos disponíveis na avaliação do comportamento estrutural de elementos de betão armado, é comum recorrer-se cada vez mais a modelos numéricos que consideram a não-linearidade física e geométrica. As simulações numéricas obtidas com recurso a este tipo de modelos computacionais permitem obter um historial completo do comportamento estrutural, desde o início da aplicação do carregamento, até ao colapso total da estrutura. Contudo, verifica-se que em zonas de descontinuidade geométrica em estruturas de betão armado, a evolução do padrão de fendilhação é um fenómeno relativamente complexo, cuja simulação numérica representa um desafio considerável. O objectivo deste trabalho é o de verificar a aplicabilidade do Método dos Elementos Aplicados no estudo do desenvolvimento do padrão de fendilhação em paredes de betão armado, solicitadas por um carregamento monotónico. Foi analisado um conjunto de dez paredes, todas com uma abertura que provoca uma zona de descontinuidade geométrica e, consequentemente, um padrão de fendilhação mais complexo. Cada parede tem uma pormenorização de armadura diferente, permitindo verificar a fiabilidade do modelo computacional. Os resultados numéricos foram comparados com ensaios experimentais realizados por Bounassar Filho [8], permitindo tirar conclusões sobre as vantagens e as limitações deste método, quando aplicado ao estudo de estruturas de betão armado solicitadas por cargas monotónicas.

Sintonização de controladores difusos através de técnicas de optimização não-linear com restrições

A presente dissertação tem como objetivo principal a implementação de uma arquitetura baseada em algoritmos evolutivos para a sintonização dos parâmetros do controlador PID (Proporcional-Integral-Derivativo) difuso, sendo o conceito de desempenho em malha fechada explicitamente tido em conta. A sintonização dos parâmetros do controlador difuso é realizada tendo em conta um problema de otimização com restrições, em que a função de custo a ser minimizada é descrita em termos do desempenho em malha fechada, com a dinâmica do sistema a ser aproximada por um modelo não linear. Como nas metodologias de otimização existentes, a incorporação de mecanismos de adaptação referentes às funções de pertença não é comum, na presente dissertação é tido em conta, para além da usual sintonização dos fatores de escala, a sintonização dos fatores de escala e funções de pertença em simultâneo. Os resultados experimentais realizados num sistema de referência, visam demonstrar os benefícios de incorporar as funções de pertença no processo de otimização em diferido. É também utilizado um método analítico de segunda ordem como referência, por forma a comparar o desempenho de uma abordagem de otimização global contra uma de otimização local. Finalmente é implementada uma abordagem em-linha, usando o método analítico de segunda ordem, na otimização dos fatores de escala e funções de pertença.