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 solution for estimates in software development projects

The Corporate world is becoming more and more competitive. This leads organisations to adapt to this reality, by adopting more efficient processes, which result in a decrease in cost as well as an increase of product quality. One of these processes consists in making proposals to clients, which necessarily include a cost estimation of the project. This estimation is the main focus of this project. In particular, one of the goals is to evaluate which estimation models fit the Altran Portugal software factory the most, the organization where the fieldwork of this thesis will be carried out. There is no broad agreement about which is the type of estimation model more suitable to be used in software projects. Concerning contexts where there is plenty of objective information available to be used as input to an estimation model, model-based methods usually yield better results than the expert judgment. However, what happens more frequently is not having this volume and quality of information, which has a negative impact in the model-based methods performance, favouring the usage of expert judgement. In practice, most organisations use expert judgment, making themselves dependent on the expert. A common problem found is that the performance of the expert’s estimation depends on his previous experience with identical projects. This means that when new types of projects arrive, the estimation will have an unpredictable accuracy. Moreover, different experts will make different estimates, based on their individual experience. As a result, the company will not directly attain a continuous growing knowledge about how the estimate should be carried. Estimation models depend on the input information collected from previous projects, the size of the project database and the resources available. Altran currently does not store the input information from previous projects in a systematic way. It has a small project database and a team of experts. Our work is targeted to companies that operate in similar contexts. We start by gathering information from the organisation in order to identify which estimation approaches can be applied considering the organization’s context. A gap analysis is used to understand what type of information the company would have to collect so that other approaches would become available. Based on our assessment, in our opinion, expert judgment is the most adequate approach for Altran Portugal, in the current context. We analysed past development and evolution projects from Altran Portugal and assessed their estimates. This resulted in the identification of common estimation deviations, errors, and patterns, which lead to the proposal of metrics to help estimators produce estimates leveraging past projects quantitative and qualitative information in a convenient way. This dissertation aims to contribute to more realistic estimates, by identifying shortcomings in the current estimation process and supporting the self-improvement of the process, by gathering as much relevant information as possible from each finished project.

Context-based identification of energy consumption in industrial plants

Nowadays, reducing energy consumption is one of the highest priorities and biggest challenges faced worldwide and in particular in the industrial sector. Given the increasing trend of consumption and the current economical crisis, identifying cost reductions on the most energy-intensive sectors has become one of the main concerns among companies and researchers. Particularly in industrial environments, energy consumption is affected by several factors, namely production factors(e.g. equipments), human (e.g. operators experience), environmental (e.g. temperature), among others, which influence the way of how energy is used across the plant. Therefore, several approaches for identifying consumption causes have been suggested and discussed. However, the existing methods only provide guidelines for energy consumption and have shown difficulties in explaining certain energy consumption patterns due to the lack of structure to incorporate context influence, hence are not able to track down the causes of consumption to a process level, where optimization measures can actually take place. This dissertation proposes a new approach to tackle this issue, by on-line estimation of context-based energy consumption models, which are able to map operating context to consumption patterns. Context identification is performed by regression tree algorithms. Energy consumption estimation is achieved by means of a multi-model architecture using multiple RLS algorithms, locally estimated for each operating context. Lastly, the proposed approach is applied to a real cement plant grinding circuit. Experimental results prove the viability of the overall system, regarding both automatic context identification and energy consumption estimation.

Levantamento, identificação e classificação de dados para a gestão da manutenção numa empresa industrial

O presente trabalho refere-se à análise de conceitos gerais de manutenção e sua gestão, aplicados a uma indústria de produção de fibra têxtil sintética. Contempla uma primeira fase de organização e segmentação de um registo histórico de dados, para a identificação de equipamentos críticos e o seu impacto a nível capital na instalação industrial, e uma outra fase de caracterização de tipos de avaria comuns para a definição de um plano de acções. Neste contexto o trabalho visa o estudo de um equipamento essencial ao processo produtivo, pois a ocorrência de uma avaria/falha traduz-se na paragem da máquina e consequentemente perda na produção. Partindo dos dados organizados sobre avarias comuns identificam-se as causas raiz, com recurso a diagramas de causa e efeito. Acrescenta-se uma análise dos investimentos necessários para cumprir algumas das acções do plano. A estrutura de dados realizada permite à empresa dispor de uma nova ferramenta de apoio à gestão da manutenção, com vista a uma melhor preparação de trabalhos futuros e consequente aumento da produtividade.

O papel de Nikita Khrushchev no Complexo Militar e Industrial, no quadro da Guerra Fria

A presente dissertação visa aferir a dimensão e a relevância das alterações operadas por Nikita Khrushchev, enquanto líder da União Soviética, no Complexo Militar e Industrial deste país, no período da Guerra Fria. Neste contexto, as mesmas serão analisadas e proceder-se-á, paralelamente, ao estudo do impacto das mesmas a nível interno, bem como a nível externo, na interacção da União Soviética com os restantes actores da comunidade internacional, nomeadamente os Estados Unidos. Mormente, como forma de contextualizar as referidas alterações, proceder-se-á também ao apuramento dos motivos que estiveram subjacentes à transmutação de uma componente relevante nas Relações Internacionais, o Complexo Militar e Industrial Soviético.

Um olhar sobre a Descrição a partir das Séries " Licenciamento Industrial" e "Registo do Trabalho Nacional" da Direcção Regional de Economia do Centro

O presente trabalho resulta do estágio realizada na Secretaria Geral do Ministério da Economia e do Emprego. O estágio consistiu na descrição de duas Séries documentais. Com o presente trabalho pretende-se demonstrar a importância do uso das normas de descrição arquivística, mostrando a importância da descrição dos produtores, das funções e das entidades responsáveis pela sua custódia, conjugada com a descrição dos documentos.

Product relatedness role on driving industrial policy success

This thesis aims to study how product relatedness to the current pattern of specialization influences the success of industrial policies in underdeveloped sectors. Drawing from Hausmann and Klinger (2006), this work extends the existing literature on the importance of proximity spillovers to explain economic development by focusing on underdeveloped sectors. We find that investment's success in an underdeveloped sector is more likely if it is highly related to the current pattern of specialization. However, heterogeneity amongst sectors is remarkable. Moreover, industrial policy cases are sometimes successful despite the bad odds provided by this criterion, suggesting further factors should be considered.

Optimal choice between even- and uneven-aged forestry: the case of non-industrial private forest owners

An infinite-horizon discrete time model with multiple size-class structures using a transition matrix is built to assess optimal harvesting schedules in the context of Non-Industrial Private Forest (NIPF) owners. Three model specifications accounting for forest income, financial return on an asset and amenity valuations are considered. Numerical simulations suggest uneven-aged forest management where a rational forest owner adapts her or his forest policy by influencing the regeneration of trees or adjusting consumption dynamics depending on subjective time preference and market return rate dynamics on the financial asset. Moreover she or he does not value significantly non-market benefits captured by amenity valuations relatively to forest income.

A Cidade do Trabalho: usos do património industrial (S. João da Madeira)

S. João da Madeira é uma localidade que desde cedo construiu os seus discursos em torno da identidade local sob o epíteto de Cidade do Trabalho. Mais recentemente, desde a última década do século XX, a cidade começou a olhar para a sua dimensão industrial do ponto de vista do seu cunho patrimonial, dentro do quadro emergente das políticas culturais e de identidade, no qual as identidades particulares – como à escala local – se querem afirmar no plano global. Partindo de uma primeira análise dos processos contemporâneos de patrimonialização do industrial no contexto de S. João da Madeira, concretizados pela via dos museus e do turismo, num trabalho de projeto que se apresenta como fase de investigação preliminar de um futuro trabalho de doutoramento, questiona-se como a antropologia poderá pensar o conceito de cultura popular fora dos contextos normalmente a estes atribuídos e como, consequentemente, poderá problematizar as fronteiras daquilo que poderá ser considerado ou não Património Cultural Imaterial (PCI), categoria com a qual a disciplina está historicamente comprometida.

A business model for an entertainment solution to the in-vehicle infotainment industry

The evolution of mobile technologies that make its presence something ubiquitous and the idea of internet connectivity in every device, often called as the Internet of Things, are pushing a disruption in other industry: the in-vehicle infotainment (IVI). Many companies are trying to enter this new industry that comprises information (weather, news, location services) and entertainment solutions in just one. For that purpose, company X developed a new entertainment solution and intends to bring it to market. This Work Project focuses on creating a business model and an entry mode for the company.

Solution processed quantum dot photodetectors

To find sustainable solutions for the production of energy, it is necessary to create photovoltaic technologies that make every photon count. To pursue this necessity, in the present work photodetectors of zinc oxide embedded with nano-structured materials, that significantly raise the conversion of solar energy to electric energy, were developed. The novelty of this work is on the development of processing methodologies in which all steps are in solution: quantum dots synthesis, passivation of their surface and sol-gel deposition. The quantum dot solutions with different capping agents were characterized by UVvisible absorption spectroscopy, spectrofluorimetry, dynamic light scattering and transmission electron microscopy. The obtained quantum dots have dimensions between 2 and 3nm. These particles were suspended in zinc acetate solutions and used to produce doped zinc oxide films with embedded quantum dots, whose electric response was tested. The produced nano-structured zinc oxide materials have a superior performance than the bulk, in terms of the produced photo-current. This indicates that an intermediate band material should have been produced that acts as a photovoltaic medium for solar cells. The results are currently being compiled in a scientific article, that is being prepared for possible submission to Energy and Environmental Science or Nanoscale journals.

Modelo hidrogeológico e rede de monitorização da água subterrânea na Zona Industrial e Logística de Sines (ZILS)

Na Zona Industrial e Logística de Sines (ZILS) estão instaladas empresas e indústrias que interferem na quantidade e qualidade da água subterrânea de aquíferos da região. Estas utilizam e libertam poluentes que, consequentemente, quando não cumpridas as normas de segurança, podem causar impactes no ambiente. A ZILS situa-se no Sistema Aquífero de Sines, na Massa de Água 032-Sines, este é constituído por dois aquíferos, um superficial detrítico livre e outro carbonatado profundo confinado. Apesar de se encontrarem separados em grande parte da sua extensão, na região sul, estes aquíferos encontram-se em conexão hidráulica. Esta ocorre a este da falha da Maria das Moitas onde, a partir da qual e até ao limite com o Paleozóico, não foi reconhecida a unidade argilosa do Miocénico, aumentado assim a vulnerabilidade do sistema e a pertinente otimização da rede de monitorização. Para a realização de um estudo mais aprofundado e avaliação dos efeitos sobre as águas subterrâneas na área de estudo, definiu-se uma metodologia de trabalho que engloba 4 etapas: (i) revisão bibliográfica; (ii) recolha de dados geológicos e hidrogeológicos dos arquivos da aicep Global Parques, S.A., SNIRH e LNEG; (iii) tratamento e análise dos dados obtidos em ArcGIS e traçado de perfis geológicos interpretativos; (iv) realização do modelo geológico e hidrogeológico e respetiva adequação da rede de monitorização. O modelo hidrogeológico concebido mostra que o escoamento no Sistema Aquífero de Sines se processa, predominantemente, de E para W a partir do limite situado no contacto por falha entre as unidades do Paleozóico e Meso-Cenozóico com orientação, quase perpendicular, à ribeira dos Moinhos. A este deste alinhamento é assinalada a presença de um aquífero fissurado sob as areias do Plio-Plistocénico localizado na Formação de Mira. O escoamento neste aquífero faz-se de NE para SW, em direção ao oceano, para a praia de S. Torpes.

A reindustrialização de Portugal num contexto de crise e hegemonia industrial dos países emergentes

O presente estudo teve como motivação compreender a importância e o papel da indústria para a retoma do crescimento económico de Portugal, integrado num contexto de desindustrialização progressiva nos últimos anos, e a um crescimento da importância e domínio de sectores de produção por parte de países emergentes, associado à crise surgida em 2008. Pretendeu-se enquadrar a problemática a nível nacional e europeu, contextualizando a indústria nacional, apontando as principais causas da desindustrialização e as suas consequências. Identificar os principais actores-chave e a sua participação no processo de reindustrialização. Identificar políticas e instrumentos de fomento da reindustrialização e principais conclusões.

Estudo e sugestões de melhorias de eficiência energética numa empresa do sector industrial de carnes

Desta dissertação resultou uma análise ao consumo energético associado aos produtos mais comerci-alizados por uma Empresa, inserida no sector industrial de carnes, e de respectivas medidas de ges-tão de energia eléctrica e de implementação de tecnologia térmica para optimizara a eficiência ener-gética da instalação. A avaliação realizada nesta dissertação permitiu identificar os processos que mais energia consomem, nomeadamente todos os produtos que envolvem a fumagem. Com base nes-tes resultados a empresa pode identificar as prioridades em termos de redução e melhoria da eficiên-cia energética. O estudo de gestão da energia eléctrica permitiu concluir que é mais proveitoso man-ter em funcionamento os processos pontuais durante os períodos nocturnos ou durante o fim-de-semana, permitindo, no segundo caso, obter uma poupança de 16% nos custos associados de cada vez que se colocar a linha de produção de peito de peru fumado entre o período semanal para o perí-odo entre sexta-feira e domingo, visto ser a linha de produção estudada que mais energia eléctrica consome. Na análise de pré-aquecimento dos fluidos utilizados na empresa através de recuperadores de calor, concluiu-se que é mais benéfico pré-aquecer a água utilizada para o processo de fumagem, visto obter-se uma poupança económica de 6 € e 11,8 m3 de gás natural por aplicação, ou seja, de cada vez que é utilizada água pré-aquecida através deste procedimento, tendo-se obtido valores de poupança energética entre 24 e 60% para os vários fluidos estudados.

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.