Citrate selective electrodes for the flow injection analysis of soft drinks, beers and pharmaceutical products

Aiming the establishment of simple and accurate readings of citric acid (CA) in complex samples, citrate (CIT) selective electrodes with tubular configuration and polymeric membranes plus a quaternary ammonium ion exchanger were constructed. Several selective membranes were prepared for this purpose, having distinct mediator solvents (with quite different polarities) and, in some cases, p-tert-octylphenol (TOP) as additive. The latter was used regarding a possible increase in selectivity. The general working characteristics of all prepared electrodes were evaluated in a low dispersion flow injection analysis (FIA) manifold by injecting 500µl of citrate standard solutions into an ionic strength (IS) adjuster carrier (10−2 mol l−1) flowing at 3ml min−1. Good potentiometric response, with an average slope and a repeatability of 61.9mV per decade and ±0.8%, respectively, resulted from selective membranes comprising additive and bis(2-ethylhexyl)sebacate (bEHS) as mediator solvent. The same membranes conducted as well to the best selectivity characteristics, assessed by the separated solutions method and for several chemical species, such as chloride, nitrate, ascorbate, glucose, fructose and sucrose. Pharmaceutical preparations, soft drinks and beers were analyzed under conditions that enabled simultaneous pH and ionic strength adjustment (pH = 3.2; ionic strength = 10−2 mol l−1), and the attained results agreed well with the used reference method (relative error < 4%). The above experimental conditions promoted a significant increase in sensitivity of the potentiometric response, with a supra-Nernstian slope of 80.2mV per decade, and allowed the analysis of about 90 samples per hour, with a relative standard deviation <1.0%.

Exploring bioactive properties of marine cyanobacteria Isolated from the Portuguese coast: high potential as a source of anticancer compounds

The oceans remain a major source of natural compounds with potential in pharmacology. In particular, during the last few decades, marine cyanobacteria have been in focus as producers of interesting bioactive compounds, especially for the treatment of cancer. In this study, the anticancer potential of extracts from twenty eight marine cyanobacteria strains, belonging to the underexplored picoplanktonic genera, Cyanobium, Synechocystis and Synechococcus, and the filamentous genera, Nodosilinea, Leptolyngbya, Pseudanabaena and Romeria, were assessed in eight human tumor cell lines. First, a crude extract was obtained by dichloromethane:methanol extraction, and from it, three fractions were separated in a Si column chromatography. The crude extract and fractions were tested in eight human cancer cell lines for cell viability/toxicity, accessed with the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) and lactic dehydrogenase release (LDH) assays. Eight point nine percent of the strains revealed strong cytotoxicity; 17.8% showed moderate cytotoxicity, and 14.3% assays showed low toxicity. The results obtained revealed that the studied genera of marine cyanobacteria are a promising source of novel compounds with potential anticancer activity and highlight the interest in also exploring the smaller filamentous and picoplanktonic genera of cyanobacteria.

Structural modification of TiO2 nanorod films with an influence on the photovoltaic efficiency of a dye-sensitized solar cell (DSSC).

TiO2 nanorod films have been deposited on ITO substrates by dc reactive magnetron sputtering technique. The structures of these nanorod films were modified by the variation of the oxygen pressure during the sputtering process. Although all these TiO2 nanorod films deposited at different oxygen pressures show an anatase structure, the orientation of the nanorod films varies with the oxygen pressure. Only a very weak (101) diffraction peak can be observed for the TiO2 nanorod film prepared at low oxygen pressure. However, as the oxygen pressure is increased, the (220) diffraction peak appears and the intensity of this diffraction peak is increased with the oxygen pressure. The results of the SEM show that these TiO2 nanorods are perpendicular to the ITO substrate. At low oxygen pressure, these sputtered TiO2 nanorods stick together and have a dense structure. As the oxygen pressure is increased, these sputtered TiO2 nanorods get separated gradually and have a porous structure. The optical transmittance of these TiO2 nanorod films has been measured and then fitted by OJL model. The porosities of the TiO2 nanorod films have been calculated. The TiO2 nanorod film prepared at high oxygen pressure shows a high porosity. The dye-sensitized solar cells (DSSCs) have been assembled using these TiO2 nanorod films prepared at different oxygen pressures as photoelectrode. The optimum performance was achieved for the DSSC using the TiO2 nanorod film with the highest (220) diffraction peak and the highest porosity.

Sistema de reconhecimento de impressões digitais baseado em FPGA

Trabalho de Projeto para obtenção do grau de Mestre em Engenharia de Eletrónica e Telecomunicações

Application mapping in NoC-Based many-cores

Many-core platforms based on Network-on-Chip (NoC [Benini and De Micheli 2002]) present an emerging technology in the real-time embedded domain. Although the idea to group the applications previously executed on separated single-core devices, and accommodate them on an individual many-core chip offers various options for power savings, cost reductions and contributes to the overall system flexibility, its implementation is a non-trivial task. In this paper we address the issue of application mapping onto a NoCbased many-core platform when considering fundamentals and trends of current many-core operating systems, specifically, we elaborate on a limited migrative application model encompassing a message-passing paradigm as a communication primitive. As the main contribution, we formulate the problem of real-time application mapping, and propose a three-stage process to efficiently solve it. Through analysis it is assured that derived solutions guarantee the fulfilment of posed time constraints regarding worst-case communication latencies, and at the same time provide an environment to perform load balancing for e.g. thermal, energy, fault tolerance or performance reasons.We also propose several constraints regarding the topological structure of the application mapping, as well as the inter- and intra-application communication patterns, which efficiently solve the issues of pessimism and/or intractability when performing the analysis.

Les Plus Anciens Mastodontes Tetralophodontes (Langhien inférieur Vb), évolution et remarques sur la Tetralophodontie

This study deals with mastodont teeth found near Lisbon in Lower Langhian (lower Middle Miocene) fluviatile, feldspathic sands (Vb division). Conclusions are as follows: 1. Tetralophodont molars (even if at a still primitive stade of the tetralophodont condition) do exist at least since lower Langhian times, and not only since late Middle Miocene as was previously known. 2. Tri- and tetralophodont structures may (and indeed do) coexist in the same individual: such examples do not correspond to transitional forms, but instead to a mosaic of juxtaposed characters (however this does not mean there are no transitional forms in other instances). 3. So these structures coexisted in a population not yet genetically separated beyond fertile cross-breeding, i.e. beyond species' level. 4. Origin of the tetralophodont molar was due to some mutation (s). but without crossing species, limits and even more genus'ones. 5. At this times probably soon after the first appearance of tetralophodont mutants, animals with such characters were a small but significant minority among the population (17% if account is taken on D4's: only 2% after M2's). 6. There was not then any direct and clear correlation between number of lophs (transversal crests) and tooth size, even if the increase of such number goes along with length's increase. 7. Dimensions (length in special) in tetralophodont teeth tend to exceed those in «normal» trilophodont teeth, this being particularly clear in D4, even if there is no clear distinction: the situation is quite the same, maybe less marked, with the M2. 8. According to the preceding conclusions there are no reasons to segregate different taxa among such mastodont population on the grounds of the presence in D4, M1 and M2 of 3 or 4 crests (this character being regarded as diagnostic of the genus Tetralophodon). 9. On the contrary, if any natural (in biological sense) classification is disregarded and a morphological parataxonomy is adopted there should be considered both Gomphotherium angustidens and Tetralophodon sp.: however this is absolutely not our opinion.

Evolução tectónica mesozóica da Bacia Lusitaniana

The evolution of the Lusitanian Basin, localized on the western Iberian margin, is closely associated with the first opening phases of the North Atlantic. It persisted from the Late Triassic to the Early Cretaceous, more precisely until the end of the Early Aptian, and its evolution was conditioned by inherited structures from the variscan basement. The part played by the faults that establish its boundaries, as regards the geometric and kinematic evolution and the organization of the sedimentary bodies, is discussed here, as well as with respect to important faults transversal to the Basin. A basin evolution model is proposed consisting of four rifting episodes which show: i) periods of symmetrical (horst and graben organization) and asymmetrical (half graben organization) geometric evolution; ii) diachronous fracturing; iii) rotation of the main extensional direction; iv) rooting in the variscan basement of the main faults of the basin (predominantly thick skinned style). The analysis and regional comparison, particularly with the Algarve Basin, of the time intervals represented by important basin scale hiatuses near to the renovation of the rifting episodes, have led to assume the occurrence of early tectonic inversions (Callovian–Oxfordian and Tithonian–Berriasian). The latter, however, had a subsequent evolution distinct from the first: there is no subsidence renovation, which is discussed here, and it is related to a magmatic event. Although the Lusitanian Basin is located on a rift margin which is considered non-volcanic, the three magmatic cycles as defined by many authors, particularly the second (approx. 130 to 110 My ?), performed a fundamental part in the mobilization of the Hettangian evaporites, resulting in the main diapiric events of the Lusitanian Basin. The manner and time in which the basin definitely ends its evolution (Early Aptian) is discussed here. Comparisons are established with other west Iberian margin basins and with Newfoundland basins. A model of oceanization of this area of the North Atlantic is also presented, consisting of two events separated by approximately 10 My, and of distinct areas separated by the Nazaré fault. The elaboration of this synthesis was based on: - information contained in previously published papers (1990 – 2000); - field-work carried out over the last years, the results of which have not yet been published; - information gathered from the reinterpretation of geological mapping and geophysical (seismic and well logs) elements, and from generic literature concerning the Mesozoic of the west iberian margin.

Le monument de “Pedras da Granja” ou de “Pedras Altas” dans la “Várzea de Sintra"

In the present work, the authors describe the excavation of the monument of "Pedras da Granja" or "Pedras Altas", in the Várzea de Sintra. The first part consists of the diary of the excavations, a description of the stratigraphy encountered and of the position of the finds. An inventory of all the material found in this monument is given in the second part. The conclusions show that the monument was built on the surface of a lapiás whose crevices were used for the insertion of the standing stones, and for the deposition of the dead. Three archaeological levels were shown to exist: - upper level: Bell Beaker level; - intermediate level containing some artifacts of the Bell Beaker culture; - lower, older level with human remains more or less in situ, belonging to a local Neolithic-culture influenced by cultural imports of foreign origin. The three levels are separated, at the southern edge of the site, by layers of fallen stones. The human remains belong to some old people, but mostly to young men, women and children.

A reconnaissance study of Upper Jurassic sediments of the Lusitanian Basin

The Upper Jurassic evolution of the Lusitanian Basin is shown to be linked to the rifting phase which preceded the separation of Iberia and the Grand Banks. Structural controls on sedimentation include both NNE-SSW trending faults in the Hercynian basement, and contemporaneous movement of salt diapirs. At the beginning of Upper Oxfordian times, the entire basin had been levelled to within a few metres of sea level, so that the freshwater algal marsh and marginal marine facies of the Cabaços and Vale Verde Beds rest on Triassic to Callovian strata. In the latter part of the Upper Oxfordian. carbonate sedimentation continued, with fluctuating salinity lagoons in the north (Pholodomya protei Beds) separated from shallow open marine carbonates in the south (Montejunto Beds) by the Caldas da Rainha diapir-barrier island complex. The commencement of rifting is recorded in the Kimmeridgian by the sudden influx of terrigenous clastics (developed in both fluviatile and deltaic/submarine fan environments) and accelerated depositional rates in excess of 10cm/10 k.yrs in association with contemporaneous faulting along the SE margin of the Arruda sub-basin. The Caldas-Santa Cruz chain of diapiric structures continued to influence the distribution of carbonate and clastic sediments. In the Portlandian, a simpler facies pattern occurs, with fluviatile clastics interfingering to the south with shallow low energy carbonates.

Notes sur la géologie et la paleontology du Miocène de Lisbonne; (XX) les plus anciens mastodontes tetralophodontes (Langhien inférieur Vb), évolution et remarques sur la tetralophodontie

This study deals with mastodont teeth found near Lisbon in Lower Langhian (lower Middle Miocene) fluviatile, feldspathic sands (Vb division). Conclusions are as follows: 1. Tetralophodont molars (even if at a still primitive stade of the tetralophodont condition) do exist at least since lower Langhian times, and not only since late Middle Miocene as was previously known. 2. Tri- and tetralophodont structures may (and indeed do) coexist in the same individual: such examples do not correspond to transitional forms, but instead to a mosaic of juxtaposed characters (however this does not mean there are no transitional forms in other instances). 3. So these structures coexisted in a population not yet geneticaliy separated beyond fertile cross-breeding, i.e. beyond species'level. 4. Origin of the tetralophodont molar was due to some mutation (s). but without crossing species, limits and even more genus' ones. 5. At this times probably soon after the first appearance of tetralophodont mutants, animals with such characters were a small but signifiant minority among the population (17% if account is taken on D4's: only 2% after M2's). 6. There was not then any direct and clear correlation between number of lophs (transversal crests) and tooth size, even if the increase of such number goes along with length's increase. 7. Dimensions (length in special) in tetralophodont teeth tend to exceed those in «normal» trilophodont teeth, this being particularly clear in D4, even if there is no clear distinction: the situation is quite the same, maybe less marked, with the M2. 8. According to the preceding conclusions there are no reasons to segregate different taxa among such mastodont population on the grounds of the presence in D4, M1 and M2 of 3 or 4 crests (this character being regarded as diagnostic of the genus Tetralophodon). 9. On the contrary, if any natural (in biological sense) classification is disregarded and a morphological parataxonomy is adopted there should be considered both Gomphotherium angustidens and Tetralophodon sp.: however this is absolutely not our opinion.

Validação de um método de cromatografia de alta eficiência para determinação de conservantes em géneros alimentícios

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química e Biológica

Zinc-substituted desulfovibrio gigas desulforedoxins

Protein Science (2002), 11:2464–2470

The Neogene of Portugal

After a briefhistorical introduction, this paper deals with the main concerned geotectonic units: the Lower Tagus and Alvalade basins, the Western and Southern borders, and their infillings. Most of the Neogene events and record concern areas South of the Iberian Central Chain, a nearly inverse situation as that of Paleogene times. In the most important of these units, the Lower Tagus basin, there are quite thick detrital series, mostly marine in its distal part near Lisboa (albeit with several continental intercalations), and mainly continental in its inner part. Sedimentological record is almost complete since Lowermost to Upper Miocene. The richness ofdata (paleontology, isotope chronology, paleoclimate, etc.) it gives and the possibility of direct marine-continental correlations render this basin one of the more interesting ones in Western Europe. Alvalade basin is separated from the previous one by a barrier ofPaleozoic rocks. Two transgressions events (Upper Tortonian and Messinian in age) are recorded. Active sedimentation may be correlated to Late Miocene tectonics events. In Algarve, chiefly marine units from Lower to Upper Miocene are well developped. The Lower unit (Lagos-Portimao Formation) is best exposed in Western Algarve, but desappears eastwards. Middle Miocene is not as well known, whereas Upper Miocene main outcrops are in Eastern Algarve. Cacela Formation is remarquable for its beautiful fossils. Sedimentation as a whole refletcts the tectonic activity and in special the evolution of the Algarve flexures. There is scant evidence of post-Lower Miocene volcanism, the latest known in Portugal. Pliocene has not been recognized there beyond doubt. . Miocene sediments are much less important to the North of the Central Iberian Chain. Continental beds near Leiria that yielded the well-known "Hisp anotherium fauna" are lower Middle Miocene. Pliocene corresponds to dramatic changes in paleogeography. At Setiibal Peninsula there is some evidence of a minor Lower Pliocene transgression. Continental detrital sediments, often coarse, occupy rather large areas. In Western Portugal between the Seta hal Peninsula and Pombal there is good evidence of a marine Upper Pliocene transgression, followed up by dune sands overlain by marsh clays, diatomites, lignites and boghead levels that can be partly Pleistocene in age.

Segmentation of striatal brain structures from high resolution pet images

Dissertation presented at the Faculty of Science and Technology of the New University of Lisbon in fulfillment of the requirements for the Masters degree in Electrical Engineering and Computers

Paired indices for clustering evaluation correction for agreement by chance

In the present paper we focus on the performance of clustering algorithms using indices of paired agreement to measure the accordance between clusters and an a priori known structure. We specifically propose a method to correct all indices considered for agreement by chance - the adjusted indices are meant to provide a realistic measure of clustering performance. The proposed method enables the correction of virtually any index - overcoming previous limitations known in the literature - and provides very precise results. We use simulated datasets under diverse scenarios and discuss the pertinence of our proposal which is particularly relevant when poorly separated clusters are considered. Finally we compare the performance of EM and KMeans algorithms, within each of the simulated scenarios and generally conclude that EM generally yields best results.