Stochastic modeling of the thermal and catalytic degradation of polyethylene using simultaneous DSC/TG analysis

Dissertação para obtenção do Grau de Mestre em Engenharia Química e Bioquímica

Caraterização estatística dos valores percentuais de sangue do grupo AB0 colhido pelo Centro Regional de Sangue de Lisboa e respetivo emparelhamento com a distribuição a nível hospitalar

RESUMO: A Medicina Transfusional está a mudar rapidamente em resposta a um número de diferentes catástrofes, patologias e novas técnicas da ciência. Por detrás de uma transfusão de sangue existe todo um conjunto de procedimentos, técnicas e atuações que salvaguardam o rigor e segurança científicas resultando numa maior eficiência na diminuição da morbilidade/mortalidade humana. Todo o processo de colheita, análise, processamento e distribuição de concentrados de eritrócitos comporta um capital elevado em termos da economia para a saúde e os requisitos básicos de uma gestão de qualidade, na área da saúde em geral e da hemoterapia em particular, tem de compreender, com rigor, estas condições de gestão parceria de forma a evitar um aumento nos custos da saúde. Para identificar as discrepâncias nos pedidos efetuados pelos Hospitais Públicos e Privados ao Centro de Sangue e Transplantação de Lisboa, no que diz respeito ao Sistema AB0 dos concentrados de Eritrócitos, foi feito um estudo quantitativo, com fins descritivos simples, aos 95 984 concentrados de eritrócitos enviados às 32 Instituições de Saúde da abrangência do CST de Lisboa. Tendo em conta o Sistema AB0 RhD, confirma-se que o grupo sanguíneo prevalente, tanto na população portuguesa como nos dadores de sangue que efetuaram a sua dádiva de sangue em 2011, é o grupo A Rh+. Observou-se no entanto que o grupo sanguíneo mais pedido e enviado pertence ao grupo 0 Rh positivo. Assim, apurou-se que existe uma disparidade, mesmo que pouco acentuada, nos pedidos efetuados pelos Hospitais Públicos e Privados ao Centro de Sangue e Transplantação de Lisboa no que configura ao Sistema AB0 dos concentrados de eritrócitos. Os Hospitais Públicos Sem Serviço de Colheita de Sangue e os Hospitais Privados são responsáveis por este desencontro de valores. No que se refere às inutilizações por prazo de validade ressalva-se que os desaproveitamentos de CE’s não são tão acentuados como se esperaria numa primeira fase de estudo. No entanto, e em termos económicos, se existem inutilizações por prazo de validade, existe igualmente despojo financeiro. Por detrás de cada unidade inutilizada existe um alto investimento que será desperdiçado por carência de solicitação. De forma a minimizar gastos e a salvaguardar um Banco de Sangue capaz de suportar qualquer eventualidade de rutura de stock estão patentes propostas de estratégias capazes de impedir constrangimentos diários e futuros no que diz respeito à disponibilidade de sangue e componentes sanguíneos.--------------ABSTRACT: The Transfusion Medicine it is changing fast in response to a number of different catastrophes, disease and new techniques of science. From behind a blood transfusion there is a whole set of procedures, techniques and actions that safeguard the safety and scientific rigor resulting in greater efficiency in reducing morbidity / mortality human. The entire process of procurement, testing, processing and distribution of concentrated erythrocytes involves a high capital in terms of the economy to health and the basic requirements of a quality management in healthcare in general and hemotherapy in particular has to understand with rigor, this partnership in order to avoid an increase in health costs. In order to identify discrepancies in the orders placed by the Government and Private Hospitals Center Blood and Transplant Lisbon regarding the AB0 system of concentrated erythrocytes was made a quantitative study with simple descriptive purposes to 95,984 erythrocytes concentrates sent to 32 Health Institutions of the scope of CST Lisbon. Having regard to the system AB0 blood group RhD prevalent both in the Portuguese population as blood donors, who made his blood donation in 2011, confirms that belong to group A Rh +. It was found that blood group most requested and sent belongs to group 0 Rh positive. Thus, it was found that there is a disparity, even a little sharp, requests made by the Government and Private Hospitals Blood Center and Transplantation in Lisbon that configures the system AB0 erythrocyte concentrates. The Public Hospitals without Blood Harvest and Private Hospitals are responsible for this clash of values. With regard the expiry date by disables proviso that the wastes of CE's are not as sharp as one would expect in a first phase of the study. However, in economic terms, if there is disables by expiry date, there is also financial squandering. Behind every unused unit is a high investment to be wasted by shortage of request. To minimize costs and safeguarding a Blood Bank can support any event of rupture of stock patents are proposed strategies to prevent future and diaries constraints with regard to the availability of blood and blood components.

A volumetric hybrid representation for obstacle detection in all-terrain robots

This dissertation presents an approach aimed at three-dimensional perception’s obstacle detection on all-terrain robots. Given the huge amount of acquired information, the adversities such environments present to an autonomous system and the swiftness, thus required, from each of its navigation decisions, it becomes imperative that the 3-D perceptional system to be able to map obstacles and passageways in the most swift and detailed manner. In this document, a hybrid approach is presented bringing the best of several methods together, combining the lightness of lesser meticulous analyses with the detail brought by more thorough ones. Realizing the former, a terrain’s slope mapping system upon a low resolute volumetric representation of the surrounding occupancy. For the latter’s detailed evaluation, two novel metrics were conceived to discriminate the little depth discrepancies found in between range scanner’s beam distance measurements. The hybrid solution resulting from the conjunction of these two representations provides a reliable answer to traversability mapping and a robust discrimination of penetrable vegetation from that constituting real obstructions. Two distinct robotic platforms offered the possibility to test the hybrid approach on very different applications: a boat, under an European project, the ECHORD Riverwatch, and a terrestrial four-wheeled robot for a national project, the Introsys Robot.

Design and characterization of Chitin- Glucan polymeric structures for wound dressing materials

The main objective of this work was the development of polymeric structures, gel and films, generated from the dissolution of the Chitin-Glucan Complex (CGC) in biocompatible ionic liquids for biomedical applications. Similar as chitin, CGC is only soluble in some special solvents which are toxic and corrosive. Due to this fact and the urgent development of biomedical applications, the need to use biocompatible ionic liquids to dissolve the CGC is indispensable. For the dissolution of CGC, the biocompatible ionic liquid used was Choline acetate. Two different CGC’s, KiOnutrime from KitoZyme and biologically produced CGC from Faculdade de Ciencias e Tecnologia (FCT) - Universidade Nova de Lisboa, were characterized in order to develop biocompatible wound dressing materials. The similar result is shown in term of the ratio of chitin:glucan, which is 1:1.72 for CGC-FCT and 1:1.69 for CGC-Commercial. For the analysis of metal element content, water and inorganic salts content and protein content, both polymers showed some discrepancies, where the content in CGC-FCT is always higher compared to the commercial one. The different characterization results between CGC-FCT and CGC-Commercial could be addressed to differences in the purification method, and the difference of its original strain yeast, whereas CGC-FCT is derived from P.pastoris and the commercial CGC is from A.niger. This work also investigated the effect of biopolymers, temperature dissolution, non-solvent composition on the characteristics of generated polymeric structure with biocompatible ionic liquid. The films were prepared by casting a polymer mixture, immersion in a non-solvent, followed by drying at ambient temperature. Three different non-solvents were tested in phase inversion method, i.e. water, methanol, and glycerol. The results indicate that the composition of non-solvent in the coagulation bath has great influence in generated polymeric structure. Water was found to be the best coagulant for producing a CGC polymeric film structure. The characterizations that have been done include the analysis of viscosity and viscoelasticity measurement, as well as sugar composition in the membrane and total sugar that was released during the phase inversion method. The rheology test showed that both polymer mixtures exhibit a non- Newtonian shear thinning behaviour. Where the viscosity and viscoelasticity test reveal that CGCFCT mixture has a typical behaviour of a viscous solution with entangled polymer chains and CGCCommercial mixture has true gel behaviour. The experimental results show us that the generated CGC solution from choline acetate could be used to develop both polymeric film structure and gel. The generated structures are thermally stable at 100° C, and are hydrophilic. The produced films have dense structure and mechanical stabilities against puncture up to 60 kPa.

Desperdício de medicamentos em ambiente hospitalar : identificação dos pontos críticos no circuito, impacto no consumo de recursos e estratégias de controlo

RESUMO - Numa época de constrangimento orçamental, os hospitais do SNS vêm-se na obrigação de melhorar a eficiência de utilização dos recursos disponíveis, por forma a contribuir para o seu equilíbrio financeiro. Cabe a cada prestador analisar a sua posição, avaliar as suas oportunidades e adoptar estratégias que a curto, médio ou longo prazo se traduzam numa efetiva melhoria na eficiência. A análise e o controlo do desperdício associado à prestação de cuidados de saúde apresentam-se, globalmente, como uma dessas oportunidades. Neste trabalho são exploradas oportunidades de redução de desperdício em medicamentos, numa perspectiva meramente operacional, a nível das funções desempenhadas pelos Serviços Farmacêuticos (SF). No hospital em estudo acompanhou-se as diferentes linhas de produção dos SF, nomeadamente as tarefas envolvidas no processo de Distribuição Individual Diária em Dose Unitária, na distribuição de medicamentos para o Serviço de Urgências (SU) e na preparação de citotóxicos e imunomoduladores para o Hospital de Dia de Oncologia. Durante o ano de 2013, os SF devolveram aos fornecedores 0,07% e abateram 0,05% da despesa em medicamentos. A análise dos erros de medicação registados reflete o tipo de distribuição adotado para a maioria dos serviços de internamento do hospital. As melhorias encontradas a este nível passam pelo reforço de recursos humanos a desempenhar as tarefas de dispensa de medicamentos mas também pela implementação de uma cultura de registo de erros e acidentes, baseada no sistema de informação, para que se consiga quantificar o desperdício associado e agir com vista à optimização do circuito. A relação entre o método de distribuição adotado para o SU e a utilização do medicamento neste serviço foi apenas investigada para os medicamentos de registo individual de administração. Foi determinado um índice de eficiência de utilização de 67,7%, entre o dispensado e o administrado. Às discrepâncias encontradas está associado um custo de 32 229,6 € para o ano de 2013. Constatou-se também que, a nível do consumo de citotóxicos e imunomoduladores houve, durante o mês de abril de 2013, um índice de desperdício médio de 14,7%, entre o prescrito e o consumido, que se traduziu num custo do desperdício mensal de 13 070,9 €. Com base no desperdício mensal estimou-se que o desperdício anual associado à manipulação de citotóxicos e imunomoduladores deverá corresponder a 5,5% da despesa anual do serviço com estes medicamentos. Não obstante as limitações encontradas durantes o trabalho, e parte do desperdício apurado ser inevitável, demonstrou-se que o desperdício em medicamentos pode traduzir-se numa fatia não negligenciável mas controlável da despesa do hospital em estudo. No seguimento do seu conhecimento, a sua contenção pode ter um impacto na redução de despesa a curto-médio prazo, sem a necessidade de racionamento da utilização de medicamentos e sem alterar os padrões de qualidade assistencial exigidos pela tutela e pelos doentes. Por último, são apresentadas recomendações para a redução do desperdício em medicamentos, adequadas a cada uma das dimensões analisadas.

An economic appraisal of the wealth-health gradient

In this study we aim to investigate the health discrepancies arising from unequal economic status, known as the “wealth-health gradient”. Our sample comprises 47,163 individuals from 14 European countries in the SHARE Wave 4 (2011), representing the population aged 50 and older. Through a cross-sectional OLS regression model, we have tested the impact of country-level indicators to infer their effect on personal health and on the magnitude of the gradient. The results find that private expenditure yields, on average, a higher, but fast decreasing, health benefit than public expenditure; and that income inequality is irrelevant for reducing health inequalities.

A equidade na indeminização dos danos não patrimoniais

This study examines the quantification of compensation for non-pecuniary damage, awarded by means of judicial decisions based on equity, and seeks to verify whether such calculation safeguards legal certainty and predictability when applying the law, as well as whether it observes the principles of proportionality and equality. Firstly, the limits for discretionary judgment permitted to the judge were determined, by evaluating the criteria established under the law. Then, by examining the grounds of the judicial decisions in cases that had been selected beforehand, this study sought to detect operation modes in concrete considerations of equity used by judges. The examination of the grounds on which these judicial decisions are based permitted the comprehension of the calculation method used in each case and the observation that the criteria of compensatory nature, such as the extent of the damage and the respective consequences, assumed a primary role. Despite discrepancies in viewpoints with regard to certain issues of law, the jurisprudence examined reveals that great care is taken to consider the solutions reached in similar cases, in an attempt to ensure that the different criteria applied in the quantification of compensation are given uniform relevance. The comparison of decisions, reported to cases with similar legal contours, did not reveal relevant discrepancies in the calculation criteria used, nor are they disproportionate regarding the amount of compensation awarded, which means that resorting to equity, in determining the compensation to be awarded due to nonpecuniary damage, does not jeopardize legal certainty or predictability when applying the law, and observes the principle of proportionality, which is anchored in the constitutional principle of equality. The study performed, led to the conclusion that the grounds on which judicial decisions are based, by itemising the elements which are taken into account and the criteria adopted by the judge, allow these to be taken into consideration in similar cases, contributing towards uniform interpretation and application of the law, ensuring legal certainty and predictability when resorting to equity while quantifying compensation.

Formação e avaliação de desempenho: contributos para o desenvolvimento profissional

Tese de Doutoramento em Ciências da Educação (Especialidade em Desenvolvimento Curricular)

Concepts and objects of awareness in Alzheimer’s disease: an updated systematic review

ABSTRACT Objectives To compare and discuss the objects of awareness in Alzheimer’s disease (AD): awareness of cognitive deficits, of functional activities, of social-emotional functioning and behavioral impairment. Methods A search in the PsycINFo, Pilots, PubMed/Medline and ISI electronic databases according to Prisma methodology was performed. We included studies about awareness in people with AD published between 2010 and 2015, with the combination of keywords: “Alzheimer AND awareness of deficits”, “Alzheimer AND anosognosia”, “Alzheimer AND insight”, “dementia AND awareness of deficits”, “dementia AND anosognosia”, “dementia AND insight”. The articles were categorized according to the specific object of awareness. Results Seven hundred and ten records were identified and, after application of the exclusion criteria, 191 studies were retrieved for potential use. After excluding the duplicates, 46 studies were included. Most studies assessed the cognitive domain of awareness, followed by the functional, social-emotional, and behavioral impairment domains. Memory deficits were not sufficient to explain impaired awareness in AD. Longitudinal studies did not find discrepancies between patients and caregivers’ reports, indicating that awareness is not related to cognition. Conflicting findings were observed, including the relation between awareness, mood, severity of disease, and personal characteristics. Conclusions The studies show lack of conceptual consensus and significant methodological differences. The inclusion of samples without differentiation of dementia etiology is associated to symptomatic differences, which affect awareness domains. Awareness in AD is a complex and multidimensional construct. Different objects elicit different levels of awareness.

Comportamentos de risco na juventude: Uma perspetiva de género e interseccional

Tese de Doutoramento em Psicologia - Especialidade em Psicologia Social

A proteção cumulativa do design pelo Direito de Autor e pelo Direito da Propriedade Industrial: o caso especial do contrato de trabalho

Dissertação de mestrado em Direito dos Contratos e das Empresas

The Phenomenon of international new ventures, global start-ups, and born-globals: what do we know after a decade (1993-2002) of exhaustive scientific inquiry?

In this paper, 27 studies from the last decade which deal more or less explicitly with the International New Venture, global start-up or born-global phenomenon are first identified, and then fully examined and critically assessed as a basis for obtaining an adequate view of the state-of-the-art of this increasingly important research avenue in the field of International Entrepreneurship (IE). The methodology used for this synthetic review allow us to analyze a number of recent, purposefully-chosen studies that are systematically compared along the following criteria: 1) main objective and type of research; 2) theoretical framework/s of reference, 3) methodological issues, and 4) main findings and/or conclusions. As a result of this literature review, a critical assessment follows in which the most relevant benefits and contributions as well as potential drawbacks, limitations or major discrepancies in the research activities conducted so far are discussed. Finally, some suggestions and implications are provided in the form of future research directions.

Effects of competition over quality-adjusted price indexes: an application to the Spanish automobile market

Using a newly constructed data set, we calculate quality-adjusted price indexes after estimating hedonic price regressions from 1988 to 2004 in the Spanish automobile market. The increasing competition was favoured by the removal of trade restrictions and the special plans for the renewal of the Spanish automobile fleet. We find that the increasing degree of competition during those years led to an overall drop in automobile prices by 20 percent which implied considerable consumer gains thanks to higher market efficiency. Additionally, our results indicate that loyalty relevance and discrepancies in automobile reliability declined during those years. This is captured.

Results of a collaborative study of the EDNAP group regarding mitochondrial DNA heteroplasmy and segregation in hair shafts.

A collaborative exercise was carried out by the European DNA Profiling Group (EDNAP) in order to evaluate the distribution of mitochondrial DNA (mtDNA) heteroplasmy amongst the hairs of an individual who displays point heteroplasmy in blood and buccal cells. A second aim of the exercise was to study reproducibility of mtDNA sequencing of hairs between laboratories using differing chemistries, further to the first mtDNA reproducibility study carried out by the EDNAP group. Laboratories were asked to type 2 sections from each of 10 hairs, such that each hair was typed by at least two laboratories. Ten laboratories participated in the study, and a total of 55 hairs were typed. The results showed that the C/T point heteroplasmy observed in blood and buccal cells at position 16234 segregated differentially between hairs, such that some hairs showed only C, others only T and the remainder, C/T heteroplasmy at varying ratios. Additionally, differential segregation of heteroplasmic variants was confirmed in independent extracts at positions 16093 and the poly(C) tract at 302-309, whilst a complete A-G transition was confirmed at position 16129 in one hair. Heteroplasmy was observed at position 16195 on both strands of a single extract from one hair segment, but was not observed in the extracts from any other segment of the same hair. Similarly, heteroplasmy at position 16304 was observed on both strands of a single extract from one hair. Additional variants at positions 73, 249 and the HVII poly(C) region were reported by one laboratory; as these were not confirmed in independent extracts, the possibility of contamination cannot be excluded. Additionally, the electrophoresis and detection equipment used by this laboratory was different to those of the other laboratories, and the discrepancies at position 249 and the HVII poly(C) region appear to be due to reading errors that may be associated with this technology. The results, and their implications for forensic mtDNA typing, are discussed in the light of the biology of hair formation.

Le code-switching comme ressource stratégique pour la gestion de l'interaction multilingue : coordination et leadership dans un groupe de travail

In this article, we analyze a multilingual interaction in a students' working group and hypothesize a correlation between management of languages in interaction and leadership. We consider Codeswitching as one of the most relevant observables in multilingual interaction and attempt to analyze how it is used by speakers. After a brief presentation of three theoretical and analytical conceptions of Code-switching in interaction (Auer, Mondada & Myers Scotton), we define Code-switching as an interactional, strategical, multilingual resource exploited by speakers to achieve various interactionaland non interactional goals. We then show in two CA-like analysis how multilingual strategical resources occur in the interactional practices of the analyzed working group, and how they are exploited by speakers in order to organize interaction, work, tasks, and to construct one's leadership.We also consider the metadiscourses of the students about their own practices and multilingualism in general, in order to confront them to their actual multilingual practices. We draw the hypothesis that discrepancies observed between metadiscourses and practices can be explained through the development of (meta)discourses showing a unilingual conception in describing multilingual practices.