Time-of-flight secondary ion mass spectrometry: new application for urinary stones analysis

Dissertação para obtenção do Grau de Doutor em Engenharia Física

Microanálise de cálculos urinários por espectrometria de massa de iões secundários

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para a obtenção do grau de Mestre em Engenharia Biomédica

Transístores de efeito de campo de silício cristalino obtidos pelo método de pré-deposição de dopante a baixa temperatura

Dissertação para obtenção do Grau de Mestre em Engenharia de Materiais

Toxicity of carcinogenic and non-carcinogenic Polycyclic Aromatic Hydrocarbons and their mixtures to aquatic organisms under ecologically-relevant scenarios

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous priority pollutants that tend to be trapped in aquatic sediments due to their high hydrophobicity. Nonetheless, the differential toxicological effects and mechanisms between the various classes of PAHs and their mixtures, as they invariably occur in the environment, are scarcely known, especially under ecologically-relevant scenarios. This thesis aimed at establishing a bridge between the study of mechanistic pathways and environmental monitoring of carcinogenic and non-carcinogenic PAHs, by introducing ecological-relevance in the research with model PAHs. A first bioassay conducted in situ with the mussel Mytilus edulis demonstrated that, dredging operations in harbours increase PAH bioavailability, eliciting genotoxicity, and showed that established environmental guidelines underestimate risk. Subsequent ex situ bioassays were performed with the carcinogenic benzo[b]fluoranthene (B[b]F) and non-carcinogenic phenantrene (Phe), selected following preceding results, and revealed that low-moderate concentrations of these PAHs in spiked sediments induce genotoxic effects to the clam Ruditapes decussatus, therefore contradicting the general notion that bivalves are less sensitive to PAHs than vertebrates due to inefficient bioactivation. Also, it was demonstrated that passive samplers permit inferring on PAH bioavailability but not on bioaccumulation or toxic effects. On the other hand, sea basses (Dicentrarchus labrax), yielded a complex pattern of effects and responses, relatively to genotoxicity, oxidative stress and production of specific metabolites, especially when exposed to mixtures of the PAHs which led to additive, if not synergistic, effects. It was shown that Phe may elicit significant genotoxicity especially in presence of B[b]F, even though the low, albeit realistic, exposure concentrations diluted dose- and time-independent relationships. The present work demonstrated that environmental quality guidelines underestimate the effects of PAHs in realistic scenarios and showed that the significant genotoxic and histopathological effects caused by mixed PAHs may not be reflected by oxidative stress- or CYP-related biomarkers. Besides important findings on the metabolism of PAH mixtures, the work calls for the need to re-evaluate the criteria for assessing risk and for the disclosure of more efficient indicators of toxicological hazard.

Ion-beam sources based on superionic solid electrolytes

An ion emitter consisting of a sharp silver tip covered in RbAg4I5 solid electrolyte film has been developed and studied. An accelerating potential is applied and Ag+ ions are emitted from the tip’s apex by field evaporation. The emitted ions are collected by a Faraday cup, producing a current on the pico/nanoampere level which is read by an electrometer. The tips were produced mechanically by sandpaper polishing. The sharpest tip produced had a 2:4 m apex radius. Two deposition methods were studied: thermal vacuum and pulsed laser deposition. The best tip produced a peak current value of 96nA at 180oC, and a quasi-stable 4nA emission current at 160oC, both using an extraction potential of 10kV . The emission dependence on time, temperature and accelerating potential has been studied. Deposited films were characterized by X-ray diffraction (XRD), profilometry, optical and Scanning Electron Microscope (SEM) and Secondary Ion Mass Spectroscopy (SIMS) measurements. Several ion emitters were developed, the latter ones were all able to maintain stable high ion emissions for long periods of time. This investigation was a continuation of an ongoing project backed by the European Space Agency, with the objective of making a proof of concept of this kind of ion emitter with potential application on ion thrusters for orbiting satellites. Going forward, it would be interesting to make a finer analysis of the electrolyte’s conductivity at high temperatures, explore Wien Effect-based emission and to further develop a multi-tip ion emitter prototype.

"Screening" de plantas nativas da Amazônia com potencial inibidor da fertilidade em ratas

São apresentados os resultados preliminares de um estudo sobre a potencialidade, como inibidoras de fertilidade, de plantas utilizadas por índios na região amazônica.Os testes iniciais detectaram atividade biológica positiva em três plantas: Cusparia toxicaria, Petiveria alliaceae Inga edulis.

Ants monopolise plant resources by shelter-construction

In Ecuadorean Amazonas, Crematogaster ants (Myrmicinae) were observed to construct shelters of debris and plant trichomes covering and hiding extrafloral nectaries of Passiflora auriculata vines. This is seen as an advanced way of excluding competing ants from a food source.

Utilização dos recursos naturais por comunidades humanas do Parque Ecoturístico do Guamá, Belém, Pará

O trabalho apresenta dados sobre o uso dos recursos naturais por populações humanas em pequenas comunidades (vilas) localizadas no entorno (n = 6) e no interior (n = 1) do Parque Ecoturístico do Guamá (PEG), visando avaliar os impactos sobre a fauna e flora local, ante a implantação de um projeto de infra-estrutura rodoviária local. A metodologia consistiu da aplicação de dois modelos de questionários. Um direcionado a pessoas-chave, como: moradores mais antigos, presidentes de associações, agentes de saúde, etc, e o outro aplicado aleatoriamente aos adultos locais. Buscou-se atingir pelo menos 50% das famílias das pequenas localidades (<10 famílias) e 10-15% no caso de comunidades maiores ( >11 famílias). Em todos os casos é realizado o extrativismo da fauna e flora, principalmente com o objetivo de subsistência. As espécies mais caçadas foram Agouti paca,Dasyprocta agouti,Nasua nasua, Euphractus sexcintus e Hydrochaeris hydrochaeris. A complementação da renda familiar através do comércio de caça sob encomenda é realizada em todas as comunidades estudadas. Frutíferas como Euterpe oleracea Mart., Musa spp e Theobroma cacao foram encontradas em 100% das comunidades (n=7). Plantas medicinais são rotineiramente cultivadas e empregadas. As espécies madeireiras exploradas são utilizadas com o objetivo de produção de carvão, construção de casas e de meios de transporte, predominando o Inga edulis, Virola surinamensis (Rol.) Warb e Simaruba amara (Aubl.). O trabalho discute os resultados sob o aspecto da implantação do projeto viário, oferecendo recomendações para a minimização dos impactos do mesmo sobre a fauna, a flora e o modo tradicional de vida das comunidades.

Enraizamento de estacas de castanha-de-cutia com uso de ácido indolbutírico

A castanha-de-cutia (Couepia edulis Prance) é uma oleaginosa nativa da Amazônia encontrada na terra firme, com maior freqüência no Estado do Amazonas. A propagação da espécie se dá, normalmente, via semente, mas esse processo é demorado, pois a semente pode levar até 18 meses para germinar. A propagação vegetativa pode ser a solução para a produção de mudas. Este trabalho avaliou o uso de AIB para a propagação vegetativa de C. edulis, utilizando diferentes tipos de estacas e concentrações de AIB, em um delineamento experimental em blocos casualizados, seguindo o esquema fatorial 4 x 3, sendo os fatores: 4 tipos de estacas e 3 concentrações de AIB (0, 3.000 e 6.000 mg L-1). Ao final das avaliações, a maior porcentagem de emissão de brotos ocorreu nas concentrações de 0 mg L-1 (testemunha) e 3.000 mg L-1 de AIB. A emissão de brotos foi maior em estacas herbáceas sem folhas e semilenhosas. As maiores porcentagens de formação de calos foram obtidas na testemunha e em estacas herbáceas com folhas inteiras e folhas pela metade. A emissão de raízes mostrou uma tendência maior nas estacas sem o uso de AIB e na concentração de 6.000 mg L-1. A maior emissão de raízes ocorreu nas estacas herbáceas com folhas. No entanto, a porcentagem de sucesso ainda é baixa, mas sugere a utilização de concentrações menores de AIB.

Titanium oxide adhesion layer for high temperature annealed Si/Si3N4/TiOx/Pt/LiCoO2 battery structures

This work describes the influence of a high annealing temperature of about 700C on the Si(substrate)/Si3N4/TiOx/Pt/LiCoO2 multilayer system for the fabrication of all-solid-state lithium ion thin film microbatteries. Such microbatteries typically utilize lithium cobalt oxide (LiCoO2) as cathode material with a platinum (Pt) current collector. Silicon nitride (Si3N4) is used to act as a barrier against Li diffusion into the substrate. For a good adherence between Si3N4 and Pt, commonly titanium (Ti) is used as intermediate layer. However, to achieve crystalline LiCoO2 the multilayer system has to be annealed at high temperature. This post-treatment initiates Ti diffusion into the Pt-collector and an oxidation to TiOx, leading to volume expansion and adhesion failures. To solve this adhesion problem, we introduce titanium oxide (TiOx) as an adhesion layer, avoiding the diffusion during the annealing process. LiCoO2, Pt and Si3N4 layers were deposited by magnetron sputtering and the TiOx layer by thermal oxidation of Ti layers deposited by e-beam technique. Asdeposited and annealed multilayer systems using various TiOx layer thicknesses were studied by scanning electron microscopy (SEM) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) and x-ray photoelectron spectroscopy (XPS). The results revealed that an annealing process at temperature of 700C leads to different interactions of Ti atoms between the layers, for various TiOx layer thicknesses (25–45 nm).

Nutritional value, bioactive compounds and antioxidant properties of three edible mushrooms from Poland

Mushrooms contain a multitude of biomolecules with nutritional and/or biological activity. Among the bioactive molecules, phenolic compounds and tocopherols are the most responsible for their antioxidant activity. In the present work, Boletus edulis, Lentinus edodes and Xerocomus badius, three edible mushroom species originated from Poland, were analyzed for their chemical composition and antioxidant activity. Carbohydrates were the most abundant macronutrients, followed by proteins and ash. Fructose, mannitol and trehalose were the prevalent sugars, but glucose was only found in B. edulis. Polyunsaturated fatty acids predominated over mono and saturated fatty acids. Palmitic, oleic and linoleic acids were abundant in the three samples. α- and β- Tocopherols were quantified in all the samples, but γ-tocopherol was only identified in X. badius. Oxalic and fumaric acids were quantified in the three samples; quinic acid was only present in L. edodes, and malic and citric acids were only found in X. badius. p-Hydroxybenzoic, protocatechuic and cinnamic acids were quantified in all the species, while p-coumaric acid was only found in B. edulis. This species and X. badius revealed the highest antioxidant properties, being B. edulis more effective in radicals scavenging activity and reducing power, and X. badius in lipid peroxidation inhibition, which is related with the highest amounts in phenolic compounds and tocopherols, respectively.

Synchronous reproduction may facilitate introgression in a hybrid mussel (Mytilus) population

Mussel populations on the Irish Atlantic coast comprise an interbreeding mixture of the blue mussel, Mytilus edulis (L.) and the Mediterranean mussel, Mytilus galloprovincialis (Lmk.). The occurrence of hybrid genotypes varies between sites but can be as high 80%. This study compares the reproductive cycle of M. edulis, M. galloprovincialis and their hybrids to determine if the extensive hybridisation observed at Irish Atlantic coast sites is linked to spawning synchrony between the two taxa. Mussels (40-45 mm size class) were collected monthly from a sheltered shore in Galway Bay from January to December 2005. Two major spawning events (March- June and September-October) were observed and gametogenesis took place throughout the year. The spawning cycles of the three taxa were largely overlapping. Small differences were observed in the timing of peak spawning which occurred in March and October in M. galloprovincialis and in May-June and September in M.edulis. Spawning of hybrid individuals was intermediate between the parental genotypes. Fecundity was slightly higher in M. galloprovincialis females compared to the other taxa (up to 30% difference, p<0.05). This apparent advantage is not shared by the sexes and is likely being offset by high numbers of hybrid genotypes releasing gametes during peak spawning of M. galloprovincialis. There was no evidence for increased mortality in hybrid males; sex ratios did not deviate from the 1:1 ratio. The results show that in this region of the hybrid zone the timing of reproduction does not present a barrier to gene flow between M. edulis and M. galloprovincialis. Nonetheless, small differences in the timing of peak spawning may increase the likelihood of conspecific fertilisation at certain times of the year. Hybrids outnumber the parental genotypes, undergo complete gametogenesis and show no evidence of depressed fitness (i.e. hybrids are reproductively competent suggesting a high degree of introgression.

Ocorrência do órgão cupuliforme com bordos pelífenos, no colo dos "seedlings" de algumas Myrtaceae

After verifing the presence of the cupuliform organ on the seedlings from 105 species of Eucalyptus (ACCORSI, 1955-56), the author concluded that it is a morphological characteristic of the genus, which is peculiar to the plants only in first stages of their life. In this paper, the author resumes his study carried out on 20 species of Myrtaceae, distributed among 13 genus and he could certify, until now, that, in relation to the cupuliform organ, they may divided in three groups: 1.° Group - Without cupuliform organ 1. Campomanesia aurea Berg 2. Eugenia campestris DC. 3. Eugenia tomentosa Camb. 4. Eugenia uniflora L. 5. Myrciaria edulis Berg 6. Myrciaria trunciflora Berg 7. Pitangueira-gigante - As it was difficulty to identify this species, I use its common name. 2.° Group - With rudiment of cupuli orm organ 1. Eugenia uvalha Camb. 2. Jambosa vulgaris DC. 3. Myrciaria cauliflora Berg 3.° Group - With full cupuliform organ 1. Amomyrtus luma (Mol) Legr. et Kaus. 2. Blepharocalyx angustifolius Berg 3. Britoa acida Berg 4. Callistemon speciosus DC. o. Callistemon viminalis Cheel. 6. Feijoa sellowiana Berg 7. Myrceugenia glaucescens (Camb.) Legrand 8. Myrrhinium rubriflorum Berg 9. Psidium guayava Raddi 10. Psidium littorale Raddi During his observations, he could identify also in many, seeds an "operculum", further observations about it will be published opportunely.

Ocorrência das domácias na família Rubiaceae

The author has studied the domatia appearing in the Rubiaceae family by examining 622 species distributed among 113 genera; and has verified that 88 species belonging to 35 genera have domatia fitting in the "touffe de poils", "en pertuis" and "em pochette" types according to the Chevalier's Classification. 39 species present domatia that display chamber, duct and outlet orifice. The other 46 species present domatia either as hair-agglomerates, hair-clusters or scattered hairs. The domatia in Paveta indica L. and Vangueria edulis Vahl. are in the shape of a little holow in the blade tissue and have no hairs. In Borreria verbenoides Cham & Schl. the domatia are formed by an elevation in the limb and presents abundant and short hairs. In Bqthryopora corymbosa Hook f. and Gardenia Thumbergii L. the domatia appear also in the nervure axils of several orders and also in Rudgea lanceolata Benth., Rudgea subsessilis Benth. and Rudgea gardenoides Muell. Arg. are they located7 in the axilla of the angle directed toward the leaf base.