Copper(II) aza-bis(oxazoline) complex immobilized onto ITQ-2 and MCM-22 based materials as heterogeneous catalysts for the cyclopropanation of styrene

A copper(II) chiral aza-bis(oxazoline) homogeneous catalyst (CuazaBox) was anchored onto the external surface of MCM-22 and ITQ-2 structures, as well as encapsulated into hierarchical MCM-22. The transition metal complex loading onto the porous solids was determined by ICP-AES and the materials were also characterized by elemental analysis (C, N, H, S), FTIR, XPS, TG and low temperature N-2 adsorption isotherms. The materials were tested as heterogeneous catalysts in the benchmark reaction of cyclopropanation of styrene to check the effect of the immobilization procedure on the catalytic parameters, as well as on their reutilization in several catalytic cycles. Catalyst CuazaBox anchored onto the external surface of MCM-22 and ITQ-2 materials were more active and enantioselective in the cyclopropanation of styrene than the corresponding homogeneous phase reaction run under similar experimental conditions. This is due to the propylation of the acidic aza-Box nitrogen. HMCM-22 was nevertheless the best heterogeneous catalyst. Encapsulation of CuazaBox on post-synthesis modified MCM-22 materials led to low activities and enantioselectivities. But reversal on the stereochemical course of the reaction was observed, probably due to confinement effect. (C) 2013 Elsevier Inc. All rights reserved.

Investigação dos efeitos das atividades de observação de cetáceos e natação com golfinhos: implicações para a conservação da natureza

Jornadas "Ciência nos Açores- que futuro?", Biblioteca Pública e Arquivo Regional de Ponta Delgada, Largo do Colégio, Ponta Delgada, 7-8 de junho de 2013.

Synthesis of meeting and recommendations from the Net-Biome round table discussion on "motivated" science on biodiversity management and use in support of overseas sutainable development

Net-Biome Final Meeting (Paris, 15 & 16 February, 2012).

Avaliação da integridade estrutural de uma prótese cimentada por emissão acústica

Mestrado em Engenharia Electrotécnica e de Computadores

New mitochondrial and nuclear evidences support recent demographic expansion and an atypical phylogeographic pattern in the Spittlebug Philaenus spumarius (Hemiptera, Aphrophoridae)

Copyright: © 2014 Rodrigues et al. This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

Climatic patterns and physical controls of chlorophyll-a in the Northeast Atlantic

Tese de Doutoramento, Física, 17 de Dezembro de 2013, Universidade dos Açores.

Metal accumulation and oxidative stress biomarkers in octopus (Octopus vulgaris) from Northwest Atlantic

Metals are ubiquitous in the environment and accumulate in aquatic organisms and are known for their ability to enhance the production of reactive oxygen species (ROS). In aquatic species, oxidative stress mechanisms have been studied by measuring antioxidant enzyme activities and oxidative damages in tissues. The aim of this study was to apply and validate a set of oxidative stress biomarkers and correlate responses with metal contents in tissues of common octopus (Octopus vulgaris). Antioxidant enzyme activity (catalase — CAT, superoxide dismutase — SOD and glutathione S-transferases — GST), oxidative damages (lipid peroxidation — LPO and protein carbonyl content — PCO) andmetal content (Cu, Zn, Pb, Cd and As) in the digestive gland and armof octopus, collected in the NWPortuguese coast in different periods, were assessed after capture and after 14 days in captivity. CAT and SOD activitieswere highly responsive to fluctuations inmetal concentrations and able to reduce oxidative damage, LPO and PCO in the digestive gland. CAT activity was also positively correlated with SOD and GST activities, which emphasizes that the three enzymes respond in a coordinated way to metal induced oxidative stress. Our results validate the use of oxidative stress biomarkers to assess metal pollution effects in this ecological and commercial relevant species.Moreover, octopus seems to have the ability to control oxidative damage by triggering an antioxidant enzyme coordinated response in the digestive gland.

Translation termination and protein folding pathway genes are not correlated in gastric cancer

Background: The eukaryotic release factor 3 (eRF3) has been shown to affect both tubulin and actin cytoskeleton, suggesting a role in cytoskeleton assembly, mitotic spindle formation and chromosome segregation. Also, direct interactions between eRF3 and subunits of the cytosolic chaperonin CCT have been described. Moreover, both eRF3a and CCT subunits have been described to be up-regulated in cancer tissues. Our aim was to evaluate the hypothesis that eRF3 expression levels are correlated with the expression of genes encoding proteins involved in the tubulin folding pathways. Methods: Relative expression levels of eRF1, eRF3a/GSPT1, PFDN4, CCT2, CCT4, and TBCA genes in tumour samples relative to their adjacent normal tissues were investigated using real time-polymerase chain reaction in 20 gastric cancer patients. Results: The expression levels of eRF3a/GSPT1 were not correlated with the expression levels of the other genes studied. However, significant correlations were detected between the other genes, both within intestinal and diffuse type tumours. Conclusions: eRF3a/GSPT1 expression at the mRNA level is independent from both cell translation rates and from the expression of the genes involved in tubulin-folding pathways. The differences in the patterns of expression of the genes studied support the hypothesis of genetically independent pathways in the origin of intestinal and diffuse type gastric tumours.

Estudo exploratório dos comportamentos interativos mãe – filho(a) e pai – filho(a) aos 15 meses de vida.

Dissertação apresentada à Escola Superior de Educação de Lisboa para obtenção do grau de Mestre em Intervenção Precoce

Procedimentos e dinâmicas inerentes ao processo dos concursos públicos e à realização de "empreitadas de obras públicas, em Portugal"

Trabalho de relatório de Estágio de natureza científica para obtenção do grau de Mestre em Engenharia Civil na Área de Especialização em Edificações

Metal deposition using Ionic liquids

There is an interest to create zinc/tin alloys to replace cadmium as a corrosion protective coating material. Existing aqueous electroplating systems for these alloys are commercially available but have several limitations. Dangerous and highly toxic complexing agents are uses e.g. cyanides. To overcome these problems, ionic liquids could provide a solution to obtain an alloy containing 20 to 30% of zinc. Ionic liquids (IL’s) often have wider electrochemical windows which allow the deposition of e.g. refractive metals that can not be deposited from aqueous solutions. In IL’s it is often not necessary to add complexing agents. The Zn/Sn alloy deposition from IL’s is therefore a promising application for the plating industry. Nevertheless, there are some issues with this alternative for aqueous systems. The degradation of the organic components, the control of the concentration of two metals and the risk of a two phase deposition instead of an alloy had to be overcome first. It is the main purpose of this thesis to obtain a Zn/Sn alloy with 20% zinc using IL’s as an electrolyte. First a separate study was performed on both the zinc and the tin deposition. Afterwards, an attempt to deposit a Zn/Sn alloy was made. An introduction to a study about the electrodeposition of refractive metals concludes this work. It initiated the research for oxygen-free IL’s to deposit molybdenum or tungsten. Several parameters (temperature, metal source and concentration, organic complexing agents,…) were optimized for both the zinc, tin and zinc/tin deposition. Experiments were performed both in a parallel plate cell and a Hull cell, so as to investigate the effect of current density as well. Ethaline200 was selected as electrolyte. As substrate, brass and iron were selected, while as anode a plate of the metal to deposit was chosen, tin for the alloy. The best efficiencies were always obtained on brass; however the iron substrate resulted in the best depositions. A concentration of 0.27M ZnCl2, 0.07M SnCl2 with 0.015M of K3-HEDTA as complexant resulted in a deposition containing the desired alloy with the amount of 20% zinc and 80% tin with good appearance. Refractory metals as molybdenum and tungsten cannot be electrodeposited from aqueous solutions without forming a co-deposition with Ni, Co or Fe. Here, IL’s could again provide a solution. A first requirement is the dissolution of a metal source. MoO3 could be suitable, however there are doubts about using oxides. Oxygen-free IL’s were sought for. A first attempt was the combination of ZnCl2 with chlormequat (CCC), which gave liquids below 150°C in molar ratios of 2 : 1 and 3 : 1. Unfortuna tely, MoO3 didn’t dissolve in these IL’s. Another route to design oxygen-free IL’s was the synthesis of quaternary ammonium salts. None of the methods used, proved viable as reaction time was long and resulted in very low yields. Therefore, no sufficient quantities were obtained to perform the possible electrochemical behavior of refractive metals.

Mixed extractant systems for metal recovery

Hoje em dia, a prevenção dos resíduos de metais é uma questão muito importante para um grande número de empresas, pois necessitam optimizar o seu sistema de tratamento de águas residuais a fim de alcançarem os limites legais dos teores em iões metálicos e poderem efectuar a descarga das águas residuais no domínio hídrico público. Devido a esta problemática foram efectuados estudos inovadores relacionados com a remoção de iões metálicos de águas residuais, verificando-se que as tecnologias de membrana oferecem uma série de vantagens para o efeito. Uma dessas tecnologias, referida como Membrana Líquida de Suporte (SLM), é baseada num mecanismo de extracção. A membrana hidrofóbica, impregnada com uma solução extractora, funciona como barreira entre a água residual e uma solução, geralmente ácida. A diferença de pH entre a água residual e a solução actua como força motriz para o transporte de iões metálicos da água residual para a referida solução. Poderá ocorrer um problema de falta de estabilidade, resultante da possível fuga da solução extractora para fora dos poros das membranas. Estudos anteriores mostraram que os ácidos alquilfosfóricos ou ácidos fosfónicos, como os reagentes D2EHPA e CYANEX e hidroxioximas como o LIX 860-I podem ser muito úteis para a extração de iões metálicos como ferro, cobre, níquel, zinco e outros. A clássica extracção líquido-líquido também tem mostrado que a mistura de diferentes extractores pode ter um efeito sinergético. No entanto, não é claro que haja um efeito óptimo da razão de extractor ou que tipo de complexo é formado durante o processo de extracção. O objectivo deste projecto é investigar este comportamento sinergético e as complexas formações por meio de um método espectrofotométrico, o “Job’s method” e “Mole-ratio method”. Estes métodos são utilizados para estimar a estequiometria dos vários complexos entre dois solutos, a partir da variação de absorvância dos complexos quando comparado com a absorvância do soluto. Com este projecto, o Job’s method e mole-ratio method serão aplicados a um sistema de três componentes, para conseguir mais informações sobre a complexação de níquel (II) e a fim de determinar a razão extractor: metal dos complexos formados durante a aplicação de mistura de extractores D2EHPA e LIX 860-I. Segundo Job’s method a elavada absorvância situa-se na região de 0,015-0,040 M de LIX 860-I e uma baixa concentração de D2EHPA. Quando as diferentes experiências são encontradas num conjunto experimental foram avaliadas de acordo com o método de trabalho, o valor máximo do gráfico foi encontrado para uma baixa fração molar do ião metálico e uma maior concentração de D2EHPA. Esta mudança foi encontrado de 0,50 até 0,30, que poderia apontar para a direção da formação de diferentes complexos. Para o Mole-Ratio method, a estequiometria dos complexos metal pode ser determinada a partir do ponto de intersecção das linhas tangente do gráfico da absorbância versus a concentração do ligante. Em todos os casos, o máximo foi obtido em torno de uma concentração total de 0,010 M. Quando D2EHPA foi aplicado sozinho, absorvâncias muito baixos foram obtidas.

Facebook vs moodle : Surveying university students on the use of learning management systems to support learning activities outside the classroom

CISTI'2015 - 10ª Conferência Ibérica de Sistemas e Tecnologias de Informação, 17 a 20 de junho de 2015, Águeda, Aveiro, Portugal.

Long-term modifications of coastal defences enhance marine biodiversity

Realization that hard coastal infrastructures support lower biodiversity than natural habitats has prompted a wealth of research seeking to identify design enhancements offering ecological benefits. Some studies showed that artificial structures could be modified to increase levels of diversity. Most studies, however, only considered the short-term ecological effects of such modifications, even though reliance on results from short-term studies may lead to serious misjudgements in conservation. In this study, a sevenyear experiment examined how the addition of small pits to otherwise featureless seawalls may enhance the stocks of a highly-exploited limpet. Modified areas of the seawall supported enhanced stocks of limpets seven years after the addition of pits. Modified areas of the seawall also supported a community that differed in the abundance of littorinids, barnacles andmacroalgae compared to the controls. Responses to different treatments (numbers and size of pits) were speciesspecific and, while some species responded directly to differences among treatments, others might have responded indirectly via changes in the distribution of competing species. This type of habitat enhancement can have positive long-lasting effects on the ecology of urban seascapes.Understanding of species interactions could be used to develop a rule-based approach to enhance biodiversity.

Gestão técnica de edifícios: aplicação em edifício escolar

Esta dissertação, enquadra-se na área da Gestão técnica centralizada ou Building Management Systems (BMS), procura reunir informação relevante acerca desta matéria evidenciando as suas potencialidades e questões técnicas a ter em conta. Este trabalho propõe a implementação de um projecto de BMS numa Escola Secundária da qual foram fornecidos elementos que conduziram ao levantamento de necessidades dos serviços de BMS a implementar. Actualmente, a utilização de sistemas de Gestão Técnica têm sido amplamente utilizados na construção de Edifícios, possuindo uma elevada integração com outros subsistemas. A função da Gestão Técnica é controlar um sistema que lhe seja integrado, esta tecnologia tem sido muito utilizada em Edifícios Comerciais em Portugal. No entanto, os sistemas que são aplicados a outros sistemas integrados podem ter problemas de comunicação, devido á multi-variedade que existe de componentes para esta área. O objectivo deste trabalho é a implementação de um Sistema de Gestão técnica num Edifício escolar, dando ênfase aos serviços e às suas interacções e chamando a atenção para os enormes potenciais em termos de valor acrescentado que é possível retirar destes conceitos. Apresentar noções fundamentais de integração, flexibilidade, adaptabilidade capacidade de oferecer um suporte eficaz à actividade das organizações sediadas no edifício. Para alcançar as informações de pesquisa, para este projecto, o autor irá obter dados de várias fontes. O método de elaboração deste trabalho pode ser classificados em duas partes. Primeira parte, recolha de informação e pesquisa de conhecimento na internet, artigos, livros de referência, cadernos técnicos e teses. Segunda parte, baseado em reflexão, estudo do caso do edifício proposto e alguns conhecimentos prévios.