Purification and structural characterization of compounds isolated from Cystoseira abies-marina

6th Spanish-Portuguese-Japanese Organic Chemistry Symposium, Lisboa, de 18 a 20 de Julho de 2012 (Poster Communication).

EVIV: An end-to-end verifiable Internet voting system

Traditionally, a country's electoral system requires the voter to vote at a specific day and place, which conflicts with the mobility usually seen in modern live styles. Thus, the widespread of Internet (mobile) broadband access can be seen as an opportunity to deal with this mobility problem, i.e. the adoption of an Internet voting system can make the live of voter's much more convenient; however, a widespread Internet voting systems adoption relies on the ability to develop trustworthy systems, i.e. systems that are verifiable and preserve the voter's privacy. Building such a system is still an open research problem. Our contribution is a new Internet voting system: EVIV, a highly sound End-to-end Verifiable Internet Voting system, which offers full voter's mobility and preserves the voter's privacy from the vote casting PC even if the voter votes from a public PC, such as a PC at a cybercafe or at a public library. Additionally, EVIV has private vote verification mechanisms, in which the voter just has to perform a simple match of two small strings (4-5 alphanumeric characters), that detect and protect against vote manipulations both at the insecure vote client platform and at the election server side. (c) 2012 Elsevier Ltd. All rights reserved.

Hexanuclear and undecanuclear iron(III) carboxylates as catalyst precursors for cyclohexane oxidation

Two multinuclear complexes [Fe-6(mu(3)-O)(2)(mu(4)-O-2)L-10(OAc)(2)(H2O)(2)]center dot 2.625Et(2)O center dot 2.375H(2)O (1) and [(Fe11Cl)-Cl-III-(mu(4)-O)(3)(mu(3)-O)(5)L-16(dmf)(2.5)(H2O)(0.5)]center dot Et2O center dot 1.25dmf center dot 3.8H(2)O (2), where HL = 3,4,5-trimethoxybenzoic acid and dmf = dimethylformamide, have been prepared from trinuclear iron(III) carboxylates via their structural rearrangement in dimethylformamide or diethyl ether-dimethylformamide 9:1, respectively, and slow vapor diffusion of diethyl ether into the reaction mixture. Both compounds have been characterized by X-ray diffraction, optical, Mossbauer spectroscopy, and magnetic measurements. Complex 1 possesses a hexanuclear ferric peroxido-dioxido {Fe-6(O-2)(O)(2)}(12+) core unit, which adopts a recliner conformation, while complex 2 contains an unprecedented {Fe11O8Cl}(16+) core, in which 9 ferric ions are six-coordinate and the remaining two are five-coordinate. Another structural feature of note of the undecanuclear core is the presence of a deformed cubane entity {Fe-4(mu(3)-O)(mu(4)-O)(3)}(4+). Both complexes act as catalyst precursors for the oxidation of cyclohexane to cyclohexanol and cyclohexanone with aqueous H2O2, in the presence of pyrazinecarboxylic acid. Remarkable TONs and TOFs (the latter mainly for 1) with concomitant quite good yields have been achieved under mild conditions. Moreover, 1 exhibits remarkably high activity in an exceptionally short reaction time (45 min), being unprecedented for any metal catalyzed alkane oxidation by H2O2. The catalytic reactions proceed via Fenton type chemistry.

Números curiosos: o azarento 13 (parte II)

Na sua obra "Unpopular Essays", de 1950, o conhecido matemático e filósofo Bertrand Russel refere que o ser humano é um animal crédulo que precisa acreditar em algo e que, na ausência de uma boa crença, ele fica satisfeito com a má. Na cultura ocidental, o 13 é um dos números com mais impacto no universo das superstições e das crenças populares. Há mesmo quem leve muito a sério a suposta influência negativa deste número e que, por isso mesmo, o evite a todo o custo. (...) Algumas companhias aéreas, como a Air France e a Lufthansa, ainda omitem a fila 13 nos seus aviões. Em algumas partes do mundo, é raro conseguir encontrar um Hotel que não tenha renumerado o seu décimo terceiro andar (substituindo o 13 pelo 14 ou por 12A). É o caso, por exemplo, de Nova Iorque. O curioso é que ainda antes dos prédios terem 13 andares, já se saltava do 12 para o 14 na numeração dos quartos. Mas há quem vá mais longe, recusando-se a pernoitar, por exemplo, num quarto 454, por entender que esse número está a camuflar o 13 (note-se que 4+5+4=13). Stephen King, conhecido autor de contos de horror fantástico e de ficção, revelou que, quando está a ler um livro, nunca pára nas páginas 94, 193, 283 e em todas as outras em que a soma dos algarismos seja 13. Os jogadores de críquete da Austrália costumam chamar ao 87 "o número do diabo", já que 87=100-13. Há também quem evite morar numa casa com o número 13 ou que não queira dar um nome ao seu filho com exatamente 13 letras. Outro aspeto referido com frequência tem a ver com o facto do décimo terceiro Arcano Maior do Tarot ser a carta da morte (...) Alguns acontecimentos históricos ajudaram a alimentar a fobia ao 13. Lançada no dia 11 de abril de 1970, às 13h13, a Apollo 13 consistiu na terceira missão tripulada do Projeto Apollo com destino à Lua (note-se que, se adicionarmos os algarismos de 11/04/70, obtém-se 13). Devido a um acidente causado por uma explosão num dos módulos, não foi possível concluir a missão. Mesmo assim, os tripulantes conseguiram regressar com a nave à Terra, após seis dias no espaço. (...)

Monte Carlo simulation of the basic features of the GE Millennium MG single photon emission computed tomography gamma camera

Objective - To describe and validate the simulation of the basic features of GE Millennium MG gamma camera using the GATE Monte Carlo platform. Material and methods - Crystal size and thickness, parallel-hole collimation and a realistic energy acquisition window were simulated in the GATE platform. GATE results were compared to experimental data in the following imaging conditions: a point source of 99mTc at different positions during static imaging and tomographic acquisitions using two different energy windows. The accuracy between the events expected and detected by simulation was obtained with the Mann–Whitney–Wilcoxon test. Comparisons were made regarding the measurement of sensitivity and spatial resolution, static and tomographic. Simulated and experimental spatial resolutions for tomographic data were compared with the Kruskal–Wallis test to assess simulation accuracy for this parameter. Results - There was good agreement between simulated and experimental data. The number of decays expected when compared with the number of decays registered, showed small deviation (≤0.007%). The sensitivity comparisons between static acquisitions for different distances from source to collimator (1, 5, 10, 20, 30cm) with energy windows of 126–154 keV and 130–158 keV showed differences of 4.4%, 5.5%, 4.2%, 5.5%, 4.5% and 5.4%, 6.3%, 6.3%, 5.8%, 5.3%, respectively. For the tomographic acquisitions, the mean differences were 7.5% and 9.8% for the energy window 126–154 keV and 130–158 keV. Comparison of simulated and experimental spatial resolutions for tomographic data showed no statistically significant differences with 95% confidence interval. Conclusions - Adequate simulation of the system basic features using GATE Monte Carlo simulation platform was achieved and validated.

OsRMC, a negative regulator of salt stress response in rice, is regulated by two AP2/ERF transcription factors

High salinity causes remarkable losses in rice productivity worldwide mainly because it inhibits growth and reduces grain yield. To cope with environmental changes, plants evolved several adaptive mechanisms, which involve the regulation of many stress-responsive genes. Among these, we have chosen OsRMC to study its transcriptional regulation in rice seedlings subjected to high salinity. Its transcription was highly induced by salt treatment and showed a stress-dose-dependent pattern. OsRMC encodes a receptor-like kinase described as a negative regulator of salt stress responses in rice. To investigate how OsRMC is regulated in response to high salinity, a salt-induced rice cDNA expression library was constructed and subsequently screened using the yeast one-hybrid system and the OsRMC promoter as bait. Thereby, two transcription factors (TFs), OsEREBP1 and OsEREBP2, belonging to the AP2/ERF family were identified. Both TFs were shown to bind to the same GCC-like DNA motif in OsRMC promoter and to negatively regulate its gene expression. The identified TFs were characterized regarding their gene expression under different abiotic stress conditions. This study revealed that OsEREBP1 transcript level is not significantly affected by salt, ABA or severe cold (5 °C) and is only slightly regulated by drought and moderate cold. On the other hand, the OsEREBP2 transcript level increased after cold, ABA, drought and high salinity treatments, indicating that OsEREBP2 may play a central role mediating the response to different abiotic stresses. Gene expression analysis in rice varieties with contrasting salt tolerance further suggests that OsEREBP2 is involved in salt stress response in rice.

Growth responses of Macrocystis pyrifera (Laminariales), Southern Chile, juvenile sporophytes to nutrient limitation

1st Mares Conference on Marine Ecosystems Health and Conservation. Olhão, Portugal 17-21 November 2014.

Fatores associados à atividade física na população portuguesa

OBJETIVO: Avaliar como as características demográficas, sociais e comportamentais se associam a diferentes tipos de atividade física. MÉTODOS: Avaliaram-se 37.692 indivíduos de amostra representativa da população portuguesa, no âmbito do Inquérito Nacional de Saúde, 1998-99. A maioria era constituída por mulheres (53,1%) e idade 20 anos. A avaliação da atividade física diária foi baseada em questionário e classificada como: total, de lazer e exercício. Cada tipo foi dicotomizado em baixa intensidade (atividades leves/moderadas) e alta intensidade (atividades pesadas/muito pesadas). Calcularam-se odds ratios (OR) e respectivos intervalos de confiança de 95% por regressão logística não condicional. RESULTADOS: Em ambos os sexos, verificou-se associação inversa significativa entre idade e diferentes tipos de atividade física, e entre a obesidade e a atividade de lazer e exercício. A escolaridade (<4; 5-11; 12 anos) associou-se positivamente com a atividade física de lazer (OR 1; 1,58; 2,39 nas mulheres e OR 1; 1,44; 2,08 nos homens) e com o exercício (OR 1; 3,50; 9,77 nas mulheres e OR 1; 3,42; 7,61 nos homens) e de forma inversa com a AF total (OR 1; 0,65; 0,20 nas mulheres e 1; 0,47; 0,09 nos homens). Independentemente da idade, os solteiros eram frequentemente mais ativos. A atividade de lazer associou-se negativamente ao consumo de bebidas alcoólicas para ambos os sexos e nos homens, ao consumo de tabaco. CONCLUSÕES: Os jovens, normoponderais, solteiros, não-bebedores e os homens não-fumadores apresentaram maior probabilidade de serem fisicamente ativos. Em ambos os sexos, observou-se um efeito diferencial da escolaridade segundo os tipos de atividade física.

Clustering of variables with a three-way approach for health sciences

TPM Vol. 21, No. 4, December 2014, 435-447 – Special Issue © 2014 Cises.

Quality assurance and quality control in mammography: a review of available guidance worldwide

Objectives - Review available guidance for quality assurance (QA) in mammography and discuss its contribution to harmonise practices worldwide. Methods - Literature search was performed on different sources to identify guidance documents for QA in mammography available worldwide in international bodies, healthcare providers, professional/scientific associations. The guidance documents identified were reviewed and a selection was compared for type of guidance (clinical/technical), technology and proposed QA methodologies focusing on dose and image quality (IQ) performance assessment. Results - Fourteen protocols (targeted at conventional and digital mammography) were reviewed. All included recommendations for testing acquisition, processing and display systems associated with mammographic equipment. All guidance reviewed highlighted the importance of dose assessment and testing the Automatic Exposure Control (AEC) system. Recommended tests for assessment of IQ showed variations in the proposed methodologies. Recommended testing focused on assessment of low-contrast detection, spatial resolution and noise. QC of image display is recommended following the American Association of Physicists in Medicine guidelines. Conclusions - The existing QA guidance for mammography is derived from key documents (American College of Radiology and European Union guidelines) and proposes similar tests despite the variations in detail and methodologies. Studies reported on QA data should provide detail on experimental technique to allow robust data comparison. Countries aiming to implement a mammography/QA program may select/prioritise the tests depending on available technology and resources.

Sulfadiazine-potentiometric sensors for flow and batch determinations of sulfadiazine in drugs and biological fluids

New PVC membrane electrodes for the determination of sulfadiazine (SDZ) are presented. The electrodes are fabricated with conventional and tubular configurations with a graphite-based electrical contact, and no internal reference solution. The selective membranes consist of bis(triphenylphosphoranilidene)ammonium·SDZ (electrode A), tetraoctylammonium bromide (electrode B), or iron(II)-phthalocyanine (FePC) (electrode C) electroactive materials dispersed in a PVC matrix of o-nitrophenyl octyl ether (o-NPOE) plasticizer. The sensors A, B, and C displayed linear responses over the concentration ranges 1.0*10-2 – 1.0*10–5, 1.0*10–2 – 7.5*10–6, and 3.2*10–2 – 7.0* 10–6 mol l–1 (detection limits of 1.09, 2.04 and 0.87 mg ml–1) with anionic slopes of –57.3 ± 0.1, –46.7 ± 0.5, and –65.1 ± 0.2 mV decade–1, respectively. No effect from pH was observed within 4.0 – 5.5, 4.8 – 10, and 4.5 – 8, respectively, and good selectivity was found. The sensors were applied to the analysis of pharmaceuticals and biological fluids in steady state and in flow conditions.

Flow injection potentiometric determination of chlorpromazine

New chlorpromazine selective electrodes with a tubular arrangement and no internal reference solution are proposed. Selective membranes are of poly(vinyl chloride) (PVC) with the tetraphenylborate•chlorpromazine (TPB•CPZ) ion-exchanger dissolved in o-nitrophenyl octyl ether (oNPOE). Analytical features of the electrodes were evaluated on a single-channel flow assembly having 500 µl injection volumes and flow-rates of 4.5 ml min−1. For a carrier solution of 3.3×10−3Min sodium sulphate, Nernstian responsewas observed over the concentration range 1.0×10−5 to 1.0×10−2 M. Average slopes were about 59mVdecade−1 and squared correlation coefficients were >0.9984. Slight hiper-Nernstian behaviour was observed in buffer solutions of 4.4 pH; average slopes were of 62.06mVdecade−1. The electrode displayed a good selectivity for CPZ, with respect to, several foreign inorganic and organic species. The selective electrodes were successfully applied to the analysis of pure solutions and pharmaceutical preparations. Proposed method allows the analysis of 84 samples h−1, producing wastewaters of low toxicity. The proposed method offers the advantage of simplicity, accuracy, applicability to coloured and turbid samples, and automation feasibility.

Ecophysiology of Ruditapes decussatus

The physiological responses of the clam R. decussatus from the Ria Formosa, southern Portugal, were examined in relation to normoxia, hypoxia (11, 6, 3 and 1.2 kPa) and anoxia; acute elevation of temperature (at 20, 27 and 32 °C), and its effect on the resistance to air exposure (at 20, 28 and 35 °C); current velocity (0.6, 3, 8 17, 24 and 36 cm. s-1) and turbidity (10, 100 and 300 mg. l-1 dry weight of particulate matter), and the efficiency of this species in retaining particles of different size (at 10 and 100 mg. l-1); and to copper contamination considering both short-term acute exposure to high levels (0.1-10 mg Cu. l-1) and chronic environmental levels (0.01 mg Cu. l-1). Clearance rates, respiration rates, absorption efficiency and excretion rates were assessed through the physiological energetics in terms of the energy budget and scope for growth (SFG). Stress independent respiration rates (R) and clearance rates (CR) were observed in relation to hypoxia down to 12 kPa and 6 kPa, respectively. Anoxic rates were 3.6 % of normoxic rates. Scope for growth was greatly reduced under extreme hypoxia (14 % of SFG in normoxia). Respiration rate was temperature independent in the range 20-32 °C but the decline in clearance rate resulted in negative SFG at 32 °C. Gaping during air exposure and the maintenance of faster aerobic metabolism led to 100 % mortality in 20 hours at 35 °C, 4 days at 28 °C and 5 days at 20 °C. Low current velocities (≤ 8 cm. s-1) supported high clearance rates. Shear stresses ≥ 0.9 Pa induced sediment movement and disturbed the feeding processes resulting in decreased clearance rates (at 36 cm. s-1, is 10 % of maximum CR). The observed ability of jetting out depleted water at a different level than the one of the inhalant current results is an important adaptation of clams to the slow currents of sheltered environments. Ingestion at high seston concentrations (> 100 mg. l-1) is controled by reducing the amount filtered, lowering CR (to 30 % of CR at low seston loads) and producing pseudofeces. Observed efficient retention of particles (70-100 %) in the range 3 to 8 μm is beneficial when algal cells are diluted by fine silt particles as it is likely to occur in the clams natural environment. R. decussatus in the short term escaped the exposure to copper by valve closure and therefore acute tests are not applicable to adult clams of this species. At environmental levels chronic exposure to copper did not induce lethal effects during the exposure period (20 days), but scope for growth was reduced to c. 30 %, indicating sustained impairment of physiological functions. The sensitivity of the physiological energetics and the integrated scope for growth measurement in assessing stress effects caused by natural environmental factors was highlighted.

Vulnerability of mediterranean watersheds to climate change

Desertification is a critical issue for Mediterranean drylands. Climate change is expected to aggravate its extension and severity by reinforcing the biophysical driving forces behind desertification processes: hydrology, vegetation cover and soil erosion. The main objective of this thesis is to assess the vulnerability of Mediterranean watersheds to climate change, by estimating impacts on desertification drivers and the watersheds’ resilience to them. To achieve this objective, a modeling framework capable of analyzing the processes linking climate and the main drivers is developed. The framework couples different models adapted to different spatial and temporal scales. A new model for the event scale is developed, the MEFIDIS model, with a focus on the particular processes governing Mediterranean watersheds. Model results are compared with desertification thresholds to estimate resilience. This methodology is applied to two contrasting study areas: the Guadiana and the Tejo, which currently present a semi-arid and humid climate. The main conclusions taken from this work can be summarized as follows: • hydrological processes show a high sensitivity to climate change, leading to a significant decrease in runoff and an increase in temporal variability; • vegetation processes appear to be less sensitive, with negative impacts for agricultural species and forests, and positive impacts for Mediterranean species; • changes to soil erosion processes appear to depend on the balance between changes to surface runoff and vegetation cover, itself governed by relationship between changes to temperature and rainfall; • as the magnitude of changes to climate increases, desertification thresholds are surpassed in a sequential way, starting with the watersheds’ ability to sustain current water demands and followed by the vegetation support capacity; • the most important thresholds appear to be a temperature increase of +3.5 to +4.5 ºC and a rainfall decrease of -10 to -20 %; • rainfall changes beyond this threshold could lead to severe water stress occurring even if current water uses are moderated, with droughts occurring in 1 out of 4 years; • temperature changes beyond this threshold could lead to a decrease in agricultural yield accompanied by an increase in soil erosion for croplands; • combined changes of temperature and rainfall beyond the thresholds could shift both systems towards a more arid state, leading to severe water stresses and significant changes to the support capacity for current agriculture and natural vegetation in both study areas.

Multi-criteria optimization manipulator trajectory planning

In the last twenty years genetic algorithms (GAs) were applied in a plethora of fields such as: control, system identification, robotics, planning and scheduling, image processing, and pattern and speech recognition (Bäck et al., 1997). In robotics the problems of trajectory planning, collision avoidance and manipulator structure design considering a single criteria has been solved using several techniques (Alander, 2003). Most engineering applications require the optimization of several criteria simultaneously. Often the problems are complex, include discrete and continuous variables and there is no prior knowledge about the search space. These kind of problems are very more complex, since they consider multiple design criteria simultaneously within the optimization procedure. This is known as a multi-criteria (or multiobjective) optimization, that has been addressed successfully through GAs (Deb, 2001). The overall aim of multi-criteria evolutionary algorithms is to achieve a set of non-dominated optimal solutions known as Pareto front. At the end of the optimization procedure, instead of a single optimal (or near optimal) solution, the decision maker can select a solution from the Pareto front. Some of the key issues in multi-criteria GAs are: i) the number of objectives, ii) to obtain a Pareto front as wide as possible and iii) to achieve a Pareto front uniformly spread. Indeed, multi-objective techniques using GAs have been increasing in relevance as a research area. In 1989, Goldberg suggested the use of a GA to solve multi-objective problems and since then other researchers have been developing new methods, such as the multi-objective genetic algorithm (MOGA) (Fonseca & Fleming, 1995), the non-dominated sorted genetic algorithm (NSGA) (Deb, 2001), and the niched Pareto genetic algorithm (NPGA) (Horn et al., 1994), among several other variants (Coello, 1998). In this work the trajectory planning problem considers: i) robots with 2 and 3 degrees of freedom (dof ), ii) the inclusion of obstacles in the workspace and iii) up to five criteria that are used to qualify the evolving trajectory, namely the: joint traveling distance, joint velocity, end effector / Cartesian distance, end effector / Cartesian velocity and energy involved. These criteria are used to minimize the joint and end effector traveled distance, trajectory ripple and energy required by the manipulator to reach at destination point. Bearing this ideas in mind, the paper addresses the planning of robot trajectories, meaning the development of an algorithm to find a continuous motion that takes the manipulator from a given starting configuration up to a desired end position without colliding with any obstacle in the workspace. The chapter is organized as follows. Section 2 describes the trajectory planning and several approaches proposed in the literature. Section 3 formulates the problem, namely the representation adopted to solve the trajectory planning and the objectives considered in the optimization. Section 4 studies the algorithm convergence. Section 5 studies a 2R manipulator (i.e., a robot with two rotational joints/links) when the optimization trajectory considers two and five objectives. Sections 6 and 7 show the results for the 3R redundant manipulator with five goals and for other complementary experiments are described, respectively. Finally, section 8 draws the main conclusions.