Acrylic bone cements modified with bioactive and biodegradable fillers

O cimento ósseo acrílico é o único material utilizado para a fixação de próteses em cirurgias ortopédicas, surgindo como uma alternativa às técnicas não cimentadas. Cerca de um milhão de pacientes são anualmente tratados para a substituição total da articulação do quadril e do joelho. Com a maior expectativa de vida da população e o aumento do número de cirurgias realizadas por ano espera-se que o uso do cimento ósseo aumente substancialmente. A fraca ligação do cimento ao osso é um problema comum que pode causar perda asséptica da prótese. Assim, torna-se necessário investir no desenvolvimento de cimentos ósseos alternativos que permitam promover maior estabilidade e melhor desempenho do implante. O principal objetivo desta tese foi desenvolver um cimento ósseo bioativo, capaz de ligar-se ao osso, com propriedades melhoradas relativamente aos sistemas convencionais. A preparação dos materiais foi realizada por dois processos diferentes, a polimerização por via térmica e a polimerização por via química. Inicialmente, utilizando o processo térmico, foram desenvolvidos compósitos de PMMA-co-EHA reforçados com vidro de sílica (CSi) e vidro de boro (CB) e comparados em termos do seu comportamento in vitro em meio acelular e celular. A formação de precipitados de fosfato de cálcio foi observada sobre a superfície de todos os compósitos indicando que estes materiais são potencialmente bioativos. Em relação à avaliação biológica o CSi demonstrou um efeito indutor da proliferação das células. As células apresentaram uma morfologia normal e alta taxa de crescimento quando comparadas com o padrão de cultura. Por outro lado ocorreu inibição da proliferação celular para o CB provavelmente devido à sua elevada taxa de degradação, levando a uma elevada concentraçao de iões de B e de Mg no meio de cultura. O efeito do vidro nos cimentos curados por via química, incorporando um activador de baixa toxicidade, também foi avaliado. Os resultados sugerem que as novas formulações podem diminuir o efeito exotérmico na cura do cimento e melhorar as propriedades mecânicas (flexão e compressão). Outro estudo conduzido neste trabalho explorou a possibilidade de incorporar ibuprofeno (fármaco anti-inflamatório) no cimento, dando origem a um material capaz de ser simultaneamente, bioativo e promotor da libertação controlada de fármacos. Neste contexto foi evidenciado que o desempenho do cimento desenvolvido pode contribuir para minimizar o processo inflamatório associado a uma cirurgia ortopédica. Finalmente, a fase sólida do cimento ósseo bioativo foi modificada por diferentes polímeros biodegradáveis. A adição deste enchimento deu origem a um cimento parcialmente biodegradável que pode permitir a formação de poros e o crescimento ósseo para o interior do cimento, resultando numa melhor fixação da prótese.

Optimal control and numerical optimization applied to epidemiological models

A relação entre a epidemiologia, a modelação matemática e as ferramentas computacionais permite construir e testar teorias sobre o desenvolvimento e combate de uma doença. Esta tese tem como motivação o estudo de modelos epidemiológicos aplicados a doenças infeciosas numa perspetiva de Controlo Ótimo, dando particular relevância ao Dengue. Sendo uma doença tropical e subtropical transmitida por mosquitos, afecta cerca de 100 milhões de pessoas por ano, e é considerada pela Organização Mundial de Saúde como uma grande preocupação para a saúde pública. Os modelos matemáticos desenvolvidos e testados neste trabalho, baseiam-se em equações diferenciais ordinárias que descrevem a dinâmica subjacente à doença nomeadamente a interação entre humanos e mosquitos. É feito um estudo analítico dos mesmos relativamente aos pontos de equilíbrio, sua estabilidade e número básico de reprodução. A propagação do Dengue pode ser atenuada através de medidas de controlo do vetor transmissor, tais como o uso de inseticidas específicos e campanhas educacionais. Como o desenvolvimento de uma potencial vacina tem sido uma aposta mundial recente, são propostos modelos baseados na simulação de um hipotético processo de vacinação numa população. Tendo por base a teoria de Controlo Ótimo, são analisadas as estratégias ótimas para o uso destes controlos e respetivas repercussões na redução/erradicação da doença aquando de um surto na população, considerando uma abordagem bioeconómica. Os problemas formulados são resolvidos numericamente usando métodos diretos e indiretos. Os primeiros discretizam o problema reformulando-o num problema de optimização não linear. Os métodos indiretos usam o Princípio do Máximo de Pontryagin como condição necessária para encontrar a curva ótima para o respetivo controlo. Nestas duas estratégias utilizam-se vários pacotes de software numérico. Ao longo deste trabalho, houve sempre um compromisso entre o realismo dos modelos epidemiológicos e a sua tratabilidade em termos matemáticos.

Communication between nodes for autonomic and distributed management

Over the last decade, the most widespread approaches for traditional management were based on the Simple Network Management Protocol (SNMP) or Common Management Information Protocol (CMIP). However, they both have several problems in terms of scalability, due to their centralization characteristics. Although the distributed management approaches exhibit better performance in terms of scalability, they still underperform regarding communication costs, autonomy, extensibility, exibility, robustness, and cooperation between network nodes. The cooperation between network nodes normally requires excessive overheads for synchronization and dissemination of management information in the network. For emerging dynamic and large-scale networking environments, as envisioned in Next Generation Networks (NGNs), exponential growth in the number of network devices and mobile communications and application demands is expected. Thus, a high degree of management automation is an important requirement, along with new mechanisms that promote it optimally and e ciently, taking into account the need for high cooperation between the nodes. Current approaches for self and autonomic management allow the network administrator to manage large areas, performing fast reaction and e ciently facing unexpected problems. The management functionalities should be delegated to a self-organized plane operating within the network, that decrease the network complexity and the control information ow, as opposed to centralized or external servers. This Thesis aims to propose and develop a communication framework for distributed network management which integrates a set of mechanisms for initial communication, exchange of management information, network (re) organization and data dissemination, attempting to meet the autonomic and distributed management requirements posed by NGNs. The mechanisms are lightweight and portable, and they can operate in di erent hardware architectures and include all the requirements to maintain the basis for an e cient communication between nodes in order to ensure autonomic network management. Moreover, those mechanisms were explored in diverse network conditions and events, such as device and link errors, di erent tra c/network loads and requirements. The results obtained through simulation and real experimentation show that the proposed mechanisms provide a lower convergence time, smaller overhead impact in the network, faster dissemination of management information, increase stability and quality of the nodes associations, and enable the support for e cient data information delivery in comparison to the base mechanisms analyzed. Finally, all mechanisms for communication between nodes proposed in this Thesis, that support and distribute the management information and network control functionalities, were devised and developed to operate in completely decentralized scenarios.

Preparation and in vivo evaluation of insulin-loaded biodegradable nanoparticles prepared from diblock copolymers of PLGA and PEG

The aim of this study was to design a controlled release vehicle for insulin to preserve its stability and biological activity during fabrication and release. A modified, double emulsion, solvent evaporation, technique using homogenisation force optimised entrapment efficiency of insulin into biodegradable nanoparticles (NP) prepared from poly (dl-lactic-co-glycolic acid) (PLGA) and its PEGylated diblock copolymers. Formulation parameters (type of polymer and its concentration, stabiliser concentration and volume of internal aqueous phase) and physicochemical characteristics (size, zeta potential, encapsulation efficiency, in vitro release profiles and in vitro stability) were investigated. In vivo insulin sensitivity was tested by dietinduced type II diabetic mice. Bioactivity of insulin was studied using Swiss TO mice with streptozotocin-induced type I diabetic profile. Insulin-loaded NP were spherical and negatively charged with an average diameter of 200–400 nm. Insulin encapsulation efficiency increased significantly with increasing ratio of co-polymeric PEG. The internal aqueous phase volume had a significant impact on encapsulation efficiency, initial burst release and NP size. Optimised insulin NP formulated from 10% PEG-PLGA retained insulin integrity in vitro, insulin sensitivity in vivo and induced a sustained hypoglycaemic effect from 3 hours to 6 days in type I diabetic mice.

Electrical characterization of organic based transistors: stability issues

An investigation into the stability of metal insulator semiconductor (MIS) transistors based on alpha-sexithiophene is reported. In particular the kinetics of the threshold voltage shift upon application of a gate bias has been determined. The kinetics follow a stretched-hyperbola type behavior, in agreement with the formalism developed to explain metastability in amorphous-silicon thin film transistors. Using this model, quantification of device stability is possible. Temperature-dependent measurements show that there are two processes involved in the threshold voltage shift, one occurring at T approximate to 220 K and the other at T approximate to 300 K. The latter process is found to be sample dependent. This suggests a relation between device stability and alpha-sexithiophene deposition parameters. Copyright (c) 2005 John Wiley A Sons, Ltd.

Why are we Waiting? Research, Policy and Practice in Recruiting and Supporting Same Gender Couples in Child Adoption

The adoption process is renowned for its difficulties, however gay and lesbian couples face unique, additional challenges when choosing parenthood through adoption. The Adoption and Children’s Act (2002), Equality Act (2006) and the Sexual Orientation Regulations act (2007) are some of the recent policy changes aimed at ‘smoothing out’ the adoption process for same-gender couples (Cosis-Brown & Kershaw, 2008). Resultantly, there appear to be more cases of gay adoption than ever before (Equality Britain, 2005), however, anecdotal evidence suggests that across the UK the practice of recruiting and supporting gay and lesbian adopters is inconsistent. Whilst some local authorities encourage and emphasise the importance of stability and high quality care for vulnerable looked after children regardless of parental sexuality (Mallon, 2007); yet case studies of gay and lesbian couples seeking adoption demonstrate the unique challenges they encounter in the adoption process because of religious views (Hicks, 2005) or the attitudes towards same gender parenting of adoption panels and social workers within an unspoken hierarchy (Ahmed, 2008; Dennis, 2006). Government’s drive towards adoption (Unwin and Misca, 2013) of children in care as a favoured alternative should lead to recognition of same-gender couples as an under-utilised resource of potential adopters to be used in the best interest of the children who are looked after. The poster will present the results of research undertaken by the authors during 2012-13 highlighting how research on same-gender parenthood over the past decades has influenced the recent developments in the adoption policy and practice in the UK and worldwide. The poster will identify areas of potential barriers encountered in translating these policy changes in the current practice of adoption with a particular focus on professionals’ attitudes towards same-gender couples as potential adopters.

Reciprocal relations across time between basic values and value-expressive behaviors: A longitudinal study among children

Tracing children’s values and value-expressive behavior over a sixth-month period, we examined stability and change of values and behavior and the reciprocal relations between them. Three hundred and ten sixth-grade students in Italy completed value and value-expressive behavior questionnaires three times in three-month intervals during the scholastic year. We assessed Schwartz's (1992) higher-order values of conservation, openness to change, self-enhancement, and self-transcendence, as well as their respective expressive behaviors. Reciprocal relations over time between values and behaviors were examined using a cross-lagged longitudinal design. Results showed that values and behaviors had reciprocal longitudinal effects on one another, after the stability of the variables was taken into account (i.e., values predicted change in behaviors, but also behaviors predicted change in values). Our findings also revealed that: (1) values were more stable over time than behaviors, and (2) the longitudinal effect of values on behaviors tended to be stronger than the longitudinal effect of behaviors on values. Findings are discussed in light of the recent developmental literature on value change.

Withdrawing from Atmosphere: An Ontology of Air partitioning and Affective Engineering

The main objective of this text is to warn against atmospherics. However comfortable it might appear, an atmosphere is politically suspicious because it numbs a body into an affective embrace of stability and permanence. It becomes doubly suspicious because a body desires to be part of the atmosphere. For this reason, I rethink both affect and atmosphere ontologically rather than phenomenologically. I argue that an atmosphere is engineered by subsuming individual affects to what I call, following Sloterdijk, an atmospheric glasshouse. I suggest that this happens in four steps: a distinction between inside and outside through partitioning; inclusion of the outside inside; illusion of synthesis; and dissimulation. In order to do this, I begin with air as the elemental paradox of ontological continuum and rupture. I carry on with the passage from air to atmosphere while retaining the discourse around continuum and rupture. Finally, I indicate a way of rupturing the atmospheric continuum through the ontological movement of withdrawal from the atmosphere. The ultimate goal of the article is to sketch a problematic of atmospherics that puts together without synthesising an elemental ontology of continuum and rupture.

Withdrawing from atmosphere: An ontology of air partitioning and affective engineering

The main objective of this text is to warn against atmospherics. However comfortable it might appear, an atmosphere is politically suspicious because it numbs a body into an affective embrace of stability and permanence. It becomes doubly suspicious because a body desires to be part of the atmosphere. For this reason, I rethink both affect and atmosphere ontologically rather than phenomenologically. I argue that an atmosphere is engineered by subsuming individual affects to what I call, following Sloterdijk, an atmospheric glasshouse. I suggest that this happens in four steps: a distinction between inside and outside through partitioning; inclusion of the outside inside; illusion of synthesis; and dissimulation. In order to do this, I begin with air as the elemental paradox of ontological continuum and rupture. I carry on with the passage from air to atmosphere while retaining the discourse around continuum and rupture. Finally, I indicate a way of rupturing the atmospheric continuum through the ontological movement of withdrawal from the atmosphere. The ultimate goal of the article is to sketch a problematic of atmospherics that puts together without synthesising an elemental ontology of continuum and rupture.

Macroeconomic information, structural change, and the prediction of fiscal aggregates

Previous research on the prediction of fiscal aggregates has shown evidence that simple autoregressive models often provide better forecasts of fiscal variables than multivariate specifications. We argue that the multivariate models considered by previous studies are small-scale, probably burdened by overparameterization, and not robust to structural changes. Bayesian Vector Autoregressions (BVARs), on the other hand, allow the information contained in a large data set to be summarized efficiently, and can also allow for time variation in both the coefficients and the volatilities. In this paper we explore the performance of BVARs with constant and drifting coefficients for forecasting key fiscal variables such as government revenues, expenditures, and interest payments on the outstanding debt. We focus on both point and density forecasting, as assessments of a country’s fiscal stability and overall credit risk should typically be based on the specification of a whole probability distribution for the future state of the economy. Using data from the US and the largest European countries, we show that both the adoption of a large system and the introduction of time variation help in forecasting, with the former playing a relatively more important role in point forecasting, and the latter being more important for density forecasting.

Transient analysis of variable-speed wind turbines at wind speed disturbances and a pitch control malfunction

As wind power generation undergoes rapid growth, new technical challenges emerge: dynamic stability and power quality. The influence of wind speed disturbances and a pitch control malfunction on the quality of the energy injected into the electric grid is studied for variable-speed wind turbines with different power-electronic converter topologies. Additionally, a new control strategy is proposed for the variable-speed operation of wind turbines with permanent magnet synchronous generators. The performance of disturbance attenuation and system robustness is ascertained. Simulation results are presented and conclusions are duly drawn. (C) 2010 Elsevier Ltd. All rights reserved.

GuideMe: service for consulting, publication and recommendation of touristic locations

Trabalho de Projeto realizado para obtenção do grau de Mestre em Engenharia Informática e de Computadores

Hydrogen peroxide sensing, signaling and regulation of transcription factors

The regulatory mechanisms by which hydrogen peroxide (H2O2) modulates the activity of transcription factors in bacteria (OxyR and PerR), lower eukaryotes (Yap1, Maf1, Hsf1 and Msn2/4) and mammalian cells (AP-1, NRF2, CREB, HSF1, HIF-1, TP53, NF-κB, NOTCH, SP1 and SCREB-1) are reviewed. The complexity of regulatory networks increases throughout the phylogenetic tree, reaching a high level of complexity in mammalians. Multiple H2O2 sensors and pathways are triggered converging in the regulation of transcription factors at several levels: (1) synthesis of the transcription factor by upregulating transcription or increasing both mRNA stability and translation; (ii) stability of the transcription factor by decreasing its association with the ubiquitin E3 ligase complex or by inhibiting this complex; (iii) cytoplasm-nuclear traffic by exposing/masking nuclear localization signals, or by releasing the transcription factor from partners or from membrane anchors; and, (iv) DNA binding and nuclear transactivation by modulating transcription factor affinity towards DNA, co-activators or repressors, and by targeting specific regions of chromatin to activate individual genes. We also discuss how H2O2 biological specificity results from diverse thiol protein sensors, with different reactivity of their sulfhydryl groups towards H2O2, being activated by different concentrations and times of exposure to H2O2. The specific regulation of local H2O2 concentrations is also crucial and results from H2O2 localized production and removal controlled by signals. Finally, we formulate equations to extract from typical experiments quantitative data concerning H2O2 reactivity with sensor molecules. Rate constants of 140 M-1s−1 and ≥ 1.3 × 103 M-1s−1 were estimated, respectively, for the reaction of H2O2 with KEAP1 and with an unknown target that mediates NRF2 protein synthesis. In conclusion, the multitude of H2O2 targets and mechanisms provides an opportunity for highly specific effects on gene regulation that depend on the cell type and on signals received from the cellular microenvironment.

New and low cost plastic membrane electrode with low detection limits for sulfadimethoxine determination in aquaculture waters

Sulfadimethoxine (SDM) is one of the drugs, often used in the aquaculture sector to prevent the spread of disease in freshwater fish aquaculture. Its spread through the soil and surface water can contribute to an increase in bacterial resistance. It is therefore important to control this product in the environment. This work proposes a simple and low-cost potentiometric device to monitor the levels of SDM in aquaculture waters, thus avoiding its unnecessary release throughout the environment. The device combines a micropipette tip with a PVC membrane selective to SDM, prepared from an appropriate cocktail, and an inner reference solution. The membrane includes 1% of a porphyrin derivative acting as ionophore and a small amount of a lipophilic cationic additive (corresponding to 0.2% in molar ratio). The composition of the inner solution was optimized with regard to the kind and/or concentration of primary ion, chelating agent and/or a specific interfering charged species, in different concentration ranges. Electrodes constructed with inner reference solutions of 1 × 10−8 mol/L SDM and 1 × 10−4 mol/L chromate ion showed the best analytical features. Near-Nernstian response was obtained with slopes of −54.1 mV/decade, an extraordinary detection limit of 7.5 ng/mL (2.4 × 10−8 mol/L) when compared with other electrodes of the same type. The reproducibility, stability and response time are good and even better than those obtained by liquid contact ISEs. Recovery values of 98.9% were obtained from the analysis of aquaculture water samples.

A New ROV Design: Issues on Low Drag and Mechanical Symmetry

This paper reports the design of a new remotely operated underwater vehicle (ROV), which has been developed at the Underwater Systems and Technology Laboratory (USTL) - University of Porto. This design is contextualized on the KOS project (Kits for underwater operations). The main issues addressed here concern directional drag minimization, symmetry, optimized thruster positioning, stability and layout of ROV components. This design is aimed at optimizing ROV performance for a set of different operational scenarios. This is achieved through modular configurations which are optimized for each different scenario.