Syntheses, Molecular Structures, Electrochemical Behavior, Theoretical Study, and Antitumor Activities of Organotin(IV) Complexes Containing 1-(4-Chlorophenyl)-1-cyclopentanecarboxylato Ligands

The organotin(IV) compounds [Me2Sn(L)(2)] (1), [Et(2)sn(L)(2)] (2), [(Bu2Sn)-Bu-n(L)(2)] (3), [(n)Oct(2)Sn(L)(2)] (4), [Ph2Sn(L)(2)] (5), and [PhOSnL](6) (6) have been synthesized from the reactions of 1-(4-chlorophenyl)-1-cyclopentanecarboxylic acid (HL) with the corresponding diorganotin(IV) oxide or dichloride. They were characterized by IR and multinuclear NMR spectroscopies, elemental analysis, cyclic voltammetry, and, for 2, 3, 4 and 6, single crystal X-ray diffraction analysis. While 1-5 are mononuclear diorganotin (IV) compounds, the X-ray diffraction of 6 discloses a hexameric drumlike structure with a prismatic Sn6O6 core. All these complexes undergo irreversible reductions and were screened for their in vitro antitumor activities toward HL-60, BGC-823, Bel-7402, and KB human cancer cell lines. Within the mononuclear compounds, the most active ones (3, 5) are easiest to reduce (least cathodic reduction potentials), while the least active ones (1, 4) are the most difficult to reduce. Structural rearrangements (i.e., Sn-O bond cleavages and trans-to-cis isomerization) induced by reduction, which eventually can favor the bioactivity, are disclosed by theoretical/electrochemical studies.

Tsunamigenic earthquakes in the Gulf of Cadiz: fault model and recurrence

The Gulf of Cadiz, as part of the Azores-Gibraltar plate boundary, is recognized as a potential source of big earthquakes and tsunamis that may affect the bordering countries, as occurred on 1 November 1755. Preparing for the future, Portugal is establishing a national tsunami warning system in which the threat caused by any large-magnitude earthquake in the area is estimated from a comprehensive database of scenarios. In this paper we summarize the knowledge about the active tectonics in the Gulf of Cadiz and integrate the available seismological information in order to propose the generation model of destructive tsunamis to be applied in tsunami warnings. The fault model derived is then used to estimate the recurrence of large earthquakes using the fault slip rates obtained by Cunha et al. (2012) from thin-sheet neotectonic modelling. Finally we evaluate the consistency of seismicity rates derived from historical and instrumental catalogues with the convergence rates between Eurasia and Nubia given by plate kinematic models.

analytical model and measurements of the target erosion depth profile of balanced and unbalanced planar magnetron cathodes

The erosion depth profile of planar targets in balanced and unbalanced magnetron cathodes with cylindrical symmetry is measured along the target radius. The magnetic fields have rotational symmetry. The horizontal and vertical components of the magnetic field B are measured at points above the cathode target with z = 2 x 10(-3) m. The experimental data reveal that the target erosion depth profile is a function of the angle. made by B with a horizontal line defined by z = 2 x 10(-3) m. To explain this dependence a simplified model of the discharge is developed. In the scope of the model, the pathway lengths of the secondary electrons in the pre-sheath region are calculated by analytical integration of the Lorentz differential equations. Weighting these lengths by using the distribution law of the mean free path of the secondary electrons, we estimate the densities of the ionizing events over the cathode and the relative flux of the sputtered atoms. The expression so deduced correlates for the first time the erosion depth profile of the target with the angle theta. The model shows reasonably good fittings to the experimental target erosion depth profiles confirming that ionization occurs mainly in the pre-sheath zone.

Electrorheology study of a series of LC cyanobiphenyls: Experimental and theoretical treatment

In this work we study the electro-rheological behaviour of a series of four liquid crystal (LC) cyanobiphenyls with a number of carbon atoms in the alkyl group, ranging from five to eight (5CB–8CB). We present the flow curves for different temperatures and under the influence of an external electric field, ranging from 0 to 3 kV/mm, and the viscosity as a function of the temperature, for the same values of electric field, obtained for different shear rates. Theoretical interpretation of the observed behaviours is proposed in the framework of the continuum theory of Leslie–Ericksen for low molecular weight nematic LCs. In our analysis, the director alignment angle is only a function of the ratio between the shear rate and the square of the electric field – boundary conditions are neglected. By fitting the theoretical model to the experimental data, we are able to determine some viscosity coefficients and the dielectric anisotropy as a function of temperature. To interpret the behaviour of the flow curves near the nematic–isotropic transitions, we apply the continuum theory of Olmsted–Goldbart, which extends the theory of Leslie–Ericksen to the case where the degree of alignment of the LC molecules can also vary.

Conceptual analogy for modelling entrapped air action in hydraulic systems

Hydraulic systems are dynamically susceptible in the presence of entrapped air pockets, leading to amplified transient reactions. In order to model the dynamic action of an entrapped air pocket in a confined system, a heuristic mathematical formulation based on a conceptual analogy to a mechanical spring-damper system is proposed. The formulation is based on the polytropic relationship of an ideal gas and includes an additional term, which encompasses the combined damping effects associated with the thermodynamic deviations from the theoretical transformation, as well as those arising from the transient vorticity developed in both fluid domains (air and water). These effects represent the key factors that account for flow energy dissipation and pressure damping. Model validation was completed via numerical simulation of experimental measurements.

Simulation of wave action on a moored container carrier inside Sines’ Harbour

The integrated numerical tool SWAMS (Simulation of Wave Action on Moored Ships) is used to simulate the behavior of a moored container carrier inside Sines’ Harbour. Wave, wind, currents, floating ship and moorings interaction is discussed. Several case scenarios are compared differing in the layout of the harbour and wind and wave conditions. The several harbour layouts correspond to proposed alternatives for the future expansion of Sines’ terminal XXI that include the extension of the East breakwater and of the quay. Additionally, the influence of wind on the behavior of the ship moored and the introduction of pre tensioning the mooring lines was analyzed. Hydrodynamic forces acting on the ship are determined using a modified version of the WAMIT model. This modified model utilizes the Haskind relations and the non-linear wave field inside the harbour obtained with finite element numerical model, BOUSS-WMH (Boussinesq Wave Model for Harbors) to get the wave forces on the ship. The time series of the moored ship motions and forces on moorings are obtained using BAS solver. © 2015 Taylor & Francis Group, London.

Equilibrium self-assembly of colloids with distinct interaction sites: Thermodynamics, percolation, and cluster distribution functions

We calculate the equilibrium thermodynamic properties, percolation threshold, and cluster distribution functions for a model of associating colloids, which consists of hard spherical particles having on their surfaces three short-ranged attractive sites (sticky spots) of two different types, A and B. The thermodynamic properties are calculated using Wertheim's perturbation theory of associating fluids. This also allows us to find the onset of self-assembly, which can be quantified by the maxima of the specific heat at constant volume. The percolation threshold is derived, under the no-loop assumption, for the correlated bond model: In all cases it is two percolated phases that become identical at a critical point, when one exists. Finally, the cluster size distributions are calculated by mapping the model onto an effective model, characterized by a-state-dependent-functionality (f) over bar and unique bonding probability (p) over bar. The mapping is based on the asymptotic limit of the cluster distributions functions of the generic model and the effective parameters are defined through the requirement that the equilibrium cluster distributions of the true and effective models have the same number-averaged and weight-averaged sizes at all densities and temperatures. We also study the model numerically in the case where BB interactions are missing. In this limit, AB bonds either provide branching between A-chains (Y-junctions) if epsilon(AB)/epsilon(AA) is small, or drive the formation of a hyperbranched polymer if epsilon(AB)/epsilon(AA) is large. We find that the theoretical predictions describe quite accurately the numerical data, especially in the region where Y-junctions are present. There is fairly good agreement between theoretical and numerical results both for the thermodynamic (number of bonds and phase coexistence) and the connectivity properties of the model (cluster size distributions and percolation locus).

Mathematical modeling of pressurized system behaviour with entrapped air

The presence of entrapped air in pressurized hydraulic systems is considered a critical condition for the infrastructure security, due to the transient pressure enhancement related with its dynamic behaviour, similar to non-linear spring action. A mathematical model for the assessment of hydraulic transients resulting from rapid pressurizations, under referred condition is presented. Water movement was modeled through the elastic column theory considering a moving liquid boundary and the entrapped air pocket as lumped gas mass, where the acoustic effects are negligible. The method of characteristics was used to obtain the numerical solution of the liquid flow. The resulting model is applied to an experimental set-up having entrapped air in the top of a vertical pipe section and the numerical results are analyzed.

The US actuarial balance model for the pay-as-you-go system and its application to Spain

The aim of this paper is to formulate an approximation of the US actuarial balance model and apply it to the Spanish public retirement pension system under various scenarios in order to determine a consistent indicator of the system's financial state comparable to those used by the most advanced social security systems. This will enable us to answer the question as to whether there is any justification for reforming the pension system in Spain. This type of actuarial balance uses projections to show future challenges to the financial side of the pension system deriving basically from ageing, the projected increase in longevity and fluctuations in economic activity. If one is compiled periodically it can provide various indicators to help depoliticize the management of the pay-as-you-go system by bringing the planning horizons of politicians and the system itself closer together.

O 1.º ciclo do ensino básico como problema de política educativa: definição de uma problemática em torno do conceito de “escola a tempo inteiro”

No centro desta reflexão teórica situa-se a conjuntura sociopolítica que fez (re)emergir o 1.º ciclo do ensino básico como “problema” de política educativa, ou seja, como terreno prioritário para o Estado, através do Governo, formular e executar um “modelo” de operacionalização da política de “Escola a Tempo Inteiro” (ETI). Analisamos esta política reportando-a a referenciais de representação de um “novo modelo educativo” (dimensão educativa), de um “novo paradigma de escola pública” (dimensão política) e de uma “nova conceção de administração da educação” (dimensão administrativa). O recurso ao quadro heurístico da “análise das políticas públicas” permite pôr em evidência as representações e a ação governativas. At the centre of this theoretical reflection is the socio-political conjuncture that (re)emerged the 1st. cycle of basic education as an education policy “problem”, that is to say, a priority ground to the State, through the Government, create and implement an operational “model” for “full-time school” policy. We analyse this policy by referring to the referential representation of a “new educational model” (educational dimension), a “new paradigm of public school” (political dimension) and a “new conception of educational administration” (administrative dimension). The use of the heuristic framework of “public policy analysis” allows us to highlight the representations and governmental action.

O 1º ciclo do ensino básico como "problema" de política educativa: definição de uma problemática em torno do conceito de "escola a tempo inteiro"

No centro desta reflexão teórica situa-se a conjuntura sociopolítica que fez (re)emergir o 1.º ciclo do ensino básico como “problema” de política educativa, ou seja, como terreno prioritário para o Estado, através do Governo, formular e executar um “modelo” de operacionalização da política de “Escola a Tempo Inteiro” (ETI). Analisamos esta política reportando-a a referenciais de representação de um “novo modelo educativo” (dimensão educativa), de um “novo paradigma de escola pública” (dimensão política) e de uma “nova conceção de administração da educação” (dimensão administrativa). O recurso ao quadro heurístico da “análise das políticas públicas” permite pôr em evidência as representações e a ação governativas.

Besnoitia besnoiti protein disulfide isomerase (BbPDI): molecular characterization, expression and in silico modelling

Besnoitia besnoiti is an apicomplexan parasite responsible for bovine besnoitiosis, a disease with a high prevalence in tropical and subtropical regions and re-emerging in Europe. Despite the great economical losses associated with besnoitiosis, this disease has been underestimated and poorly studied, and neither an effective therapy nor an efficacious vaccine is available. Protein disulfide isomerase (PDI) is an essential enzyme for the acquisition of the correct three-dimensional structure of proteins. Current evidence suggests that in Neosporacaninum and Toxoplasmagondii, which are closely related to B. besnoiti, PDI play an important role in host cell invasion, is a relevant target for the host immune response, and represents a promising drug target and/or vaccine candidate. In this work, we present the nucleotide sequence of the B. besnoiti PDI gene. BbPDI belongs to the thioredoxin-like superfamily (cluster 00388) and is included in the PDI_a family (cluster defined cd02961) and the PDI_a_PDI_a'_c subfamily (cd02995). A 3D theoretical model was built by comparative homology using Swiss-Model server, using as a template the crystallographic deduced model of Tapasin-ERp57 (PDB code 3F8U chain C). Analysis of the phylogenetic tree for PDI within the phylum apicomplexa reinforces the close relationship among B. besnoiti, N. caninum and T. gondii. When subjected to a PDI-assay based on the polymerisation of reduced insulin, recombinant BbPDI expressed in E. coli exhibited enzymatic activity, which was inhibited by bacitracin. Antiserum directed against recombinant BbPDI reacted with PDI in Western blots and by immunofluorescence with B. besnoiti tachyzoites and bradyzoites.

Newspaper coverage impact on cultural events: Porto 2001 and Guimarães 2012: European Cultural Capitals

Artigo baseado na comunicação proferida no 1st International Symposium on Media Studies, realizado na Akdeniz Universitesi Yayınları, Antalya, Turquia, 21-23 de novembro de 2013

A VLF to UHF propagation model for evaluation of high-speed railway electromagnetic interference in RF monitoring base-stations

Considering that recent european high-speed railway system has a traction power system of kV 50 Hz, which causes electromagnetic emission for the outside world, it is important to dimension the railway system emissions, using a frequency/distance dependent propagation model. This paper presents an enhanced theoretical model for VLF to UHF propagation, railway system oriented. It introduces the near field approach (crucial in low frequency propagation) and also considers the source characteristics and type of measuring antenna. Simulations are presented, and comparisons are set with earlier far field models. Using the developed model, a real case study was performed in partnership with Refer Telecom (portuguese telecom operator for railways). The new propagation model was used in order to predict the future high-speed railway electromagnetic emissions in the Lisbon north track. The results show the model's prediction capabilities and also its applicability to realistic scenarios.

Optimal offering strategies for wind power producers considering uncertainty and risk

This paper provides a two-stage stochastic programming approach for the development of optimal offering strategies for wind power producers. Uncertainty is related to electricity market prices and wind power production. A hybrid intelligent approach, combining wavelet transform, particle swarm optimization and adaptive-network-based fuzzy inference system, is used in this paper to generate plausible scenarios. Also, risk aversion is explicitly modeled using the conditional value-at-risk methodology. Results from a realistic case study, based on a wind farm in Portugal, are provided and analyzed. Finally, conclusions are duly drawn.