Redox-active cytotoxic diorganotin(IV) cycloalkylhydroxamate complexes with different ring sizes: Reduction behaviour and theoretical interpretation

Two series of new diorganotin(IV) cycloalkylhydroxamate complexes with different ring sizes (cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl), formulated as the mononuclear [R2Sn(HL)(2)] (1:2) (a, R=Bu-n and Ph) and the polymeric [R2SnL](n) (1:1) (b, R=Bu-n) compounds, were prepared and fully characterized. Single crystal X-ray diffraction for [(Bu2Sn)-Bu-n{C5H9C(O)NHO}(2)] (3a) discloses the cis geometry and strong intermolecular NH center dot center dot center dot O interactions. The in vitro cytotoxic activities of the complexes were evaluated against HL-60, Bel-7402, BGC-823 and KB human tumour cell lines, the greater activity concerning [(Bu2Sn)-Bu-n(HL)(2)] [HL=C3H5C(O)NHO (1a), C6H11C(O)NHO (4a)] towards BGC-823. The complexes undergo, by cyclic voltammetry and controlled-potential electrolysis, one irreversible overall two-electron cathodic process at a reduction potential that does not appear to correlate with the antitumour activity. The electrochemical behaviour of [R2Sn(C5H9C(O)NHO)(2)] [R=Bu-n (3a), Ph (7a)] was also investigated using density functional theory (DFT) methods, showing that the ultimate complex structure and the mechanism of its formation are R dependent: for the aromatic (R = Ph) complex, the initial reduction step is centred on the phenyl ligands and at the metal, being followed by a second reduction with Sn-O and Sn-C ruptures, whereas for the alkyl (R=Bu-n) complex the first reduction step is centred on one of the hydroxamate ligands and is followed by a second reduction with Sn-O bond cleavages and preservation of the alkyl ligands. In both cases, the final complexes are highly coordinative unsaturated Sn-II species with the cis geometry, features that can be of biological significance.

Three-Dimensional patchy lattice model for empty fluids

The phase diagram of a simple model with two patches of type A and ten patches of type B (2A10B) on the face centred cubic lattice has been calculated by simulations and theory. Assuming that there is no interaction between the B patches the behavior of the system can be described in terms of the ratio of the AB and AA interactions, r. Our results show that, similarly to what happens for related off-lattice and two-dimensional lattice models, the liquid-vapor phase equilibria exhibit reentrant behavior for some values of the interaction parameters. However, for the model studied here the liquid-vapor phase equilibria occur for values of r lower than 1/3, a threshold value which was previously thought to be universal for 2AnB models. In addition, the theory predicts that below r = 1/3 (and above a new condensation threshold which is < 1/3) the reentrant liquid-vapor equilibria are so extreme that it exhibits a closed loop with a lower critical point, a very unusual behavior in single-component systems. An order-disorder transition is also observed at higher densities than the liquid-vapor equilibria, which shows that the liquid-vapor reentrancy occurs in an equilibrium region of the phase diagram. These findings may have implications in the understanding of the condensation of dipolar hard spheres given the analogy between that system and the 2AnB models considered here.

Constrains on the structure of Maio Island (Cape Verde) by a three-dimensional gravity model: Imaging partially exhumed magma chambers

We propose a 3-D gravity model for the volcanic structure of the island of Maio (Cape Verde archipelago) with the objective of solving some open questions concerning the geometry and depth of the intrusive Central Igneous Complex. A gravity survey was made covering almost the entire surface of the island. The gravity data was inverted through a non-linear 3-D approach which provided a model constructed in a random growth process. The residual Bouguer gravity field shows a single positive anomaly presenting an elliptic shape with a NWSE trending long axis. This Bouguer gravity anomaly is slightly off-centred with the island but its outline is concordant with the surface exposure of the Central Igneous Complex. The gravimetric modelling shows a high-density volume whose centre of mass is about 4500 m deep. With increasing depth, and despite the restricted gravimetric resolution, the horizontal sections of the model suggest the presence of two distinct bodies, whose relative position accounts for the elongated shape of the high positive Bouguer gravity anomaly. These bodies are interpreted as magma chambers whose coeval volcanic counterparts are no longer preserved. The orientation defined by the two bodies is similar to that of other structures known in the southern group of the Cape Verde islands, thus suggesting a possible structural control constraining the location of the plutonic intrusions.

Competência intercultural: conteúdos culturais na aquisição da língua estrangeira e sua integração didáctica no ensino do alemão

Dissertação apresentada à Faculdade de Ciências Sociais e Humanas da Universidade Nova de Lisboa para obtenção do grau de Doutor em Cultura Alemã.

Desenvolvendo a comunicação matemática

Relatório de Estágio apresentado à Escola Superior de Educação de Lisboa para obtenção de grau de mestre em Ensino do 1º e 2º ciclo do Ensino Básico

CrimsonHex: a service oriented repository of specialised learning objects

The corner stone of the interoperability of eLearning systems is the standard definition of learning objects. Nevertheless, for some domains this standard is insufficient to fully describe all the assets, especially when they are used as input for other eLearning services. On the other hand, a standard definition of learning objects in not enough to ensure interoperability among eLearning systems; they must also use a standard API to exchange learning objects. This paper presents the design and implementation of a service oriented repository of learning objects called crimsonHex. This repository is fully compliant with the existing interoperability standards and supports new definitions of learning objects for specialized domains. We illustrate this feature with the definition of programming problems as learning objects and its validation by the repository. This repository is also prepared to store usage data on learning objects to tailor the presentation order and adapt it to learner profiles.

Interoperability in pedagogical e-learning services

The ultimate goal of this research plan is to improve the learning experience of students through the combination of pedagogical eLearning services. Service oriented architectures are already being used in eLearning but in this work the focus is on services of pedagogical value, rather then on generic services adapted from other business systems. This approach to the architecture of eLearning platforms raises challenges addressed by this work, namely: conceptual modeling of the pedagogical eLearning services domain; interoperability and coordination of pedagogical eLearning service; conversion of existing eLearning systems to pedagogical services; adaptation of eLearning services to individual learners. An improved eLearning platform will incorporate learning tools adequate to the domains it covers and will focus on the individual learner that uses it. With this approach we expect to raise the pedagogical value of eLearning platforms.

Work and citizenship: crises and alternatives

Enterprise and Work Innovation Studies, 5

Preventing human trafficking for the purpose of sexual exploitation: the need for a bottom-up approach : the case-study of Brazilians trafficked to Portugal

Masters Thesis – Academic Year 2007/2008 - European Master’s Degree in Human Rights and Democratization (E.MA) - European Inter-university Centre for Human Rights and Democratization (EIUC) -Faculdade de Direito, Universidade Nova de Lisboa (UNL)

"Gestão Oficinal no Setor Automóvel” - Caso de estudo na AMC, Lda.

A indústria automóvel no que respeita à gestão oficinal de qualidade é uma referência de dimensão e nível mundial. O constante avanço da indústria automóvel, o ciclo de vida dos produtos (automóveis) cada vez mais curtos e a competitividade entre empresas, requer uma procura constante de novas ferramentas de melhoria na gestão oficinal. Neste trabalho, centrado na gestão oficinal no setor automóvel, procuram-se introduzir novas abordagens que visem combater o decréscimo da rentabilidade neste setor. Como se depreende do exposto anteriormente, o objetivo principal desta dissertação é propor e avaliar (validar) propostas de melhoria que visem o aumento da rentabilidade financeira da empresa AMC – Auto Mecânica de Cambra, Lda. Com vista à prossecução deste objetivo foram definidos os seguintes objetivos intercalares na AMC: - Análise e levantamento dos problemas; - Identificação de potenciais causas; - Formulação de ações de propostas de melhoria na gestão da empresa; - Programação das ações e avaliação de resultados alcançados; A estrutura definida nesta dissertação após a sua introdução no capítulo 1 centra-se no capítulo 2 na apresentação da empresa AMC, com a descrição dos problemas levantados atendendo às vertentes mais críticas. Seguidamente, no capítulo 3, com ferramentas de análise de problemas, serão encontradas as causas raiz destes problemas. Posteriormente no capítulo seguinte serão criados planos de ações para a resolução das causas. No capítulo 4 as ações serão implementadas e avaliadas para garantir a sua eficácia e eficiência. Por fim, no capítulo 5 são descritas as conclusões e os desenvolvimentos futuros enquadráveis com a melhoria contínua da AMC. Como conclusão, este trabalho, mostra que várias propostas de melhoria implementadas trouxeram ganhos efetivos para a empresa e que futuras propostas são potencialmente válidas num futuro próximo. Esta dissertação com ligação direta à AMC tem igualmente dados que podem ser extrapolados e adaptados a outras empresas do mesmo setor. O objetivo principal deste estudo é a análise e o levantamento dos problemas com a utilização de ferramentas tais como: Benchmarking, Diagrama causa-efeito, ciclo PDCA, análise de SWOT e indicadores operativos da oficina.

Interoperability frameworks for competencies and learning outcomes: databases vs ontologies

The changes introduced into the European Higher Education Area (EHEA) by the Bologna Process, together with renewed pedagogical and methodological practices, have created a new teaching-learning paradigm: Student-Centred Learning. In addition, the last few years have been characterized by the application of Information Technologies, especially the Semantic Web, not only to the teaching-learning process, but also to administrative processes within learning institutions. On one hand, the aim of this study was to present a model for identifying and classifying Competencies and Learning Outcomes and, on the other hand, the computer applications of the information management model were developed, namely a relational Database and an Ontology.

Tech-based Innovations in pedagogical practices: the case of ISCAP

TICEduca. III Congresso Internacional TIC e Educação. 14 a 16 Novembro, Lisboa

The European Project Semester at ISEP: the challenge of educating global engineers

Current engineering education challenges require approaches that promote scientific, technical, design and complementary skills while fostering autonomy, innovation and responsibility. The European Project Semester (EPS) at Instituto Superior de Engenharia do Porto (ISEP) (EPS@ISEP) is a one semester project-based learning programme (30 European Credit Transfer Units (ECTU)) for engineering students from diverse scientific backgrounds and nationalities that intends to address these goals. The students, organised in multidisciplinary and multicultural teams, are challenged to solve real multidisciplinary problems during one semester. The EPS package, although on project development (20 ECTU), includes a series of complementary seminars aimed at fostering soft, project-related and engineering transversal skills (10 ECTU). Hence, the students enrolled in this programme improve their transversal skills and learn, together and with the team of supervisors, subjects distinct from their core training. This paper presents the structure, implementation and results of the EPS@ISEP that was created in 2011 to apply the best engineering practices and promote internationalisation and engineering education innovation at ISEP.

Radioactivity levels of 238U and 232Th decay series and related dose rates in the surroundings of a coal power plant using high resolution g-spectrometry

Gamma radiations measurements were carried out in the vicinity of a coal-fired power plant located in the southwest coastline of Portugal. Two different gamma detectors were used to assess the environmental radiation within a circular area of 20 km centred in the coal plant: a scintillometer (SPP2 NF, Saphymo) and a high purity germanium detector (HPGe, Canberra). Fifty urban and suburban measurements locations were established within the defined area and two measurements campaigns were carried out. The results of the total gamma radiation ranged from 20.83 to 98.33 counts per second (c.p.s.) for both measurement campaigns and outdoor doses rates ranged from 77.65 to 366.51 Gy/h. Natural emitting nuclides from the U-238 and Th-232 decay series were identified as well as the natural emitting nuclide K-40. The radionuclide concentration from the uranium and thorium series determined by gamma spectrometry ranged from 0.93 to 73.68 Bq/kg, while for K-40 the concentration ranged from 84.14 to 904.38 Bq/kg. The obtained results were used primarily to define the variability in measured environmental radiation and to determine the coal plant’s influence in the measured radiation levels. The highest values were measured at two locations near the power plant and at locations between the distance of 6 and 20 km away from the stacks, mainly in the prevailing wind direction. The results showed an increase or at least an influence from the coal-fired plant operations, both qualitatively and quantitatively.

Vertex component analysis: a geometric-based approach to unmix hyperspectral data

Hyperspectral remote sensing exploits the electromagnetic scattering patterns of the different materials at specific wavelengths [2, 3]. Hyperspectral sensors have been developed to sample the scattered portion of the electromagnetic spectrum extending from the visible region through the near-infrared and mid-infrared, in hundreds of narrow contiguous bands [4, 5]. The number and variety of potential civilian and military applications of hyperspectral remote sensing is enormous [6, 7]. Very often, the resolution cell corresponding to a single pixel in an image contains several substances (endmembers) [4]. In this situation, the scattered energy is a mixing of the endmember spectra. A challenging task underlying many hyperspectral imagery applications is then decomposing a mixed pixel into a collection of reflectance spectra, called endmember signatures, and the corresponding abundance fractions [8–10]. Depending on the mixing scales at each pixel, the observed mixture is either linear or nonlinear [11, 12]. Linear mixing model holds approximately when the mixing scale is macroscopic [13] and there is negligible interaction among distinct endmembers [3, 14]. If, however, the mixing scale is microscopic (or intimate mixtures) [15, 16] and the incident solar radiation is scattered by the scene through multiple bounces involving several endmembers [17], the linear model is no longer accurate. Linear spectral unmixing has been intensively researched in the last years [9, 10, 12, 18–21]. It considers that a mixed pixel is a linear combination of endmember signatures weighted by the correspondent abundance fractions. Under this model, and assuming that the number of substances and their reflectance spectra are known, hyperspectral unmixing is a linear problem for which many solutions have been proposed (e.g., maximum likelihood estimation [8], spectral signature matching [22], spectral angle mapper [23], subspace projection methods [24,25], and constrained least squares [26]). In most cases, the number of substances and their reflectances are not known and, then, hyperspectral unmixing falls into the class of blind source separation problems [27]. Independent component analysis (ICA) has recently been proposed as a tool to blindly unmix hyperspectral data [28–31]. ICA is based on the assumption of mutually independent sources (abundance fractions), which is not the case of hyperspectral data, since the sum of abundance fractions is constant, implying statistical dependence among them. This dependence compromises ICA applicability to hyperspectral images as shown in Refs. [21, 32]. In fact, ICA finds the endmember signatures by multiplying the spectral vectors with an unmixing matrix, which minimizes the mutual information among sources. If sources are independent, ICA provides the correct unmixing, since the minimum of the mutual information is obtained only when sources are independent. This is no longer true for dependent abundance fractions. Nevertheless, some endmembers may be approximately unmixed. These aspects are addressed in Ref. [33]. Under the linear mixing model, the observations from a scene are in a simplex whose vertices correspond to the endmembers. Several approaches [34–36] have exploited this geometric feature of hyperspectral mixtures [35]. Minimum volume transform (MVT) algorithm [36] determines the simplex of minimum volume containing the data. The method presented in Ref. [37] is also of MVT type but, by introducing the notion of bundles, it takes into account the endmember variability usually present in hyperspectral mixtures. The MVT type approaches are complex from the computational point of view. Usually, these algorithms find in the first place the convex hull defined by the observed data and then fit a minimum volume simplex to it. For example, the gift wrapping algorithm [38] computes the convex hull of n data points in a d-dimensional space with a computational complexity of O(nbd=2cþ1), where bxc is the highest integer lower or equal than x and n is the number of samples. The complexity of the method presented in Ref. [37] is even higher, since the temperature of the simulated annealing algorithm used shall follow a log( ) law [39] to assure convergence (in probability) to the desired solution. Aiming at a lower computational complexity, some algorithms such as the pixel purity index (PPI) [35] and the N-FINDR [40] still find the minimum volume simplex containing the data cloud, but they assume the presence of at least one pure pixel of each endmember in the data. This is a strong requisite that may not hold in some data sets. In any case, these algorithms find the set of most pure pixels in the data. PPI algorithm uses the minimum noise fraction (MNF) [41] as a preprocessing step to reduce dimensionality and to improve the signal-to-noise ratio (SNR). The algorithm then projects every spectral vector onto skewers (large number of random vectors) [35, 42,43]. The points corresponding to extremes, for each skewer direction, are stored. A cumulative account records the number of times each pixel (i.e., a given spectral vector) is found to be an extreme. The pixels with the highest scores are the purest ones. N-FINDR algorithm [40] is based on the fact that in p spectral dimensions, the p-volume defined by a simplex formed by the purest pixels is larger than any other volume defined by any other combination of pixels. This algorithm finds the set of pixels defining the largest volume by inflating a simplex inside the data. ORA SIS [44, 45] is a hyperspectral framework developed by the U.S. Naval Research Laboratory consisting of several algorithms organized in six modules: exemplar selector, adaptative learner, demixer, knowledge base or spectral library, and spatial postrocessor. The first step consists in flat-fielding the spectra. Next, the exemplar selection module is used to select spectral vectors that best represent the smaller convex cone containing the data. The other pixels are rejected when the spectral angle distance (SAD) is less than a given thresh old. The procedure finds the basis for a subspace of a lower dimension using a modified Gram–Schmidt orthogonalizati on. The selected vectors are then projected onto this subspace and a simplex is found by an MV T pro cess. ORA SIS is oriented to real-time target detection from uncrewed air vehicles using hyperspectral data [46]. In this chapter we develop a new algorithm to unmix linear mixtures of endmember spectra. First, the algorithm determines the number of endmembers and the signal subspace using a newly developed concept [47, 48]. Second, the algorithm extracts the most pure pixels present in the data. Unlike other methods, this algorithm is completely automatic and unsupervised. To estimate the number of endmembers and the signal subspace in hyperspectral linear mixtures, the proposed scheme begins by estimating sign al and noise correlation matrices. The latter is based on multiple regression theory. The signal subspace is then identified by selectin g the set of signal eigenvalue s that best represents the data, in the least-square sense [48,49 ], we note, however, that VCA works with projected and with unprojected data. The extraction of the end members exploits two facts: (1) the endmembers are the vertices of a simplex and (2) the affine transformation of a simplex is also a simplex. As PPI and N-FIND R algorithms, VCA also assumes the presence of pure pixels in the data. The algorithm iteratively projects data on to a direction orthogonal to the subspace spanned by the endmembers already determined. The new end member signature corresponds to the extreme of the projection. The algorithm iterates until all end members are exhausted. VCA performs much better than PPI and better than or comparable to N-FI NDR; yet it has a computational complexity between on e and two orders of magnitude lower than N-FINDR. The chapter is structure d as follows. Section 19.2 describes the fundamentals of the proposed method. Section 19.3 and Section 19.4 evaluate the proposed algorithm using simulated and real data, respectively. Section 19.5 presents some concluding remarks.