Synthesis, characterization, electrochemical behavior and in vitro protein tyrosine kinase inhibitory activity of the cymene-halogenobenzohydroxamato [Ru(eta(6)-cymene)(bha)Cl] complexes

The ruthenium(II)-cymene complexes [Ru(eta(6)-cymene)(bha)Cl] with substituted halogenobenzohydroxamato (bha) ligands (substituents = 4-F, 4-Cl, 4-Br, 2,4-F-2, 3,4-F-2, 2,5-F-2, 2,6-F-2) have been synthesized and characterized by elemental analysis, IR, H-1 NMR, C-13 NMR, cyclic voltammetry and controlled-potential electrolysis, and density functional theory (DFT) studies. The compositions of their frontier molecular orbitals (MOs) were established by DFT calculations, and the oxidation and reduction potentials are shown to follow the orders of the estimated vertical ionization potential and electron affinity, respectively. The electrochemical E-L Lever parameter is estimated for the first time for the various bha ligands, which can thus be ordered according to their electron-donor character. All complexes exhibit very strong protein tyrosine kinase (PTK) inhibitory activity, even much higher than that of genistein, the clinically used PTK inhibitory drug. The complex containing the 2,4-difluorobenzohydroxamato ligand is the most active one, and the dependences of the PTK activity of the complexes and of their redox potentials on the ring substituents are discussed. (C) 2012 Elsevier B.V. All rights reserved.

Sistema múltiplo de apoio à decisão para a programação de sistemas do tipo Job-Shop

Mestrado em Engenharia Electrotécnica e de Computadores

Melhoria do processo de fabrico de esterilizadores

Mestrado em Engenharia Mecânica. Gestão de Processos e Operações.

Padrão de ativação de músculos do core abdominal e tilt pélvico no teste de extensão da anca, em indivíduos com e sem dor lombo- pélvica

Introdução: Os padrões de movimento podem sofrer alterações por atraso no timing de ativação e/ou modificações na sequência de recrutamento muscular, predispondo o indivíduo a disfunções, nomeadamente a dor lombo-pélvica. Objetivo: Investigar o timing e o padrão de ativação de músculos do core abdominal, durante o movimento de extensão da anca, do membro dominante, em indivíduos com e sem dor lombo- pélvica crónica inespecífica. Pretende-se, também, pesquisar a existência do padrão de ativação considerado “normal“ e verificar a relação entre o padrão de ativação e o tilt pélvico, em ambos os indivíduos. Métodos: Estudo transversal, com 64 estudantes universitários, divididos em dois grupos: 31 sem e 33 com dor lombo-pélvica. Através de eletromiografia de superfície foi recolhida a atividade muscular dos Eretores da Espinha ipsilateral e contralateral, Glúteo Máximo e Bicípite Femoral ipsilaterais. Foi analisado o timing de ativação muscular e as respetivas ordens de ativação. Adicionalmente foi medido o tilt pélvico. Resultados: O grupo com dor lombo-pélvica apresentou um atraso significativo no timing de ativação dos músculos Glúteo Máximo ipsilateral (t=-3,171;p=0,002) e Bicípite Femoral ipsilateral (t=-2,092;p=0,041), em comparação com o grupo sem dor. Verificou-se uma associação significativa entre as 5 ordens de ativação mais frequentes e a presença de dor lombo-pélvica (xf2=11,54;p=0,015). A ordem de ativação "normal" – Glúteo Máximo ipsilateral>Bicípite Femoral ipsilateral>Eretor da Espinha contralateral>Eretor da Espinha ipsilateral – não foi utilizada. Verificou-se que o Bicípite Femoral ipsilateral foi maioritariamente o primeiro a ativar-se e o Glúteo Máximo ipsilateral o último em ambos os grupos. Verificou-se um tilt pélvico significativamente superior nos indivíduos que ativam primeiro o Bicípite Femoral ipsilateral nos grupos com (U=51;p=0,001) e sem dor (U=41p=0,001). Conclusão: Os indivíduos com dor lombo-pélvica apresentaram um atraso no timing de ativação dos músculos do core abdominal. Os resultados parecem refutar a ordem de ativação "normal" que tem sido proposta. Não foi possível apoiar nem contestar a teoria de que um atraso na ativação do Glúteo Máximo está associado com dor lombo-pélvica.

Colloidal dipolar interactions in 2D smectic-C films

We use a two-dimensional (2D) elastic free energy to calculate the effective interaction between two circular disks immersed in smectic-C films. For strong homeotropic anchoring, the distortion of the director field caused by the disks generates topological defects that induce an effective interaction between the disks. We use finite elements, with adaptive meshing, to minimize the 2D elastic free energy. The method is shown to be accurate and efficient for inhomogeneities on the length scales set by the disks and the defects, that differ by up to 3 orders of magnitude. We compute the effective interaction between two disk-defect pairs in a simple (linear) configuration. For large disk separations, D, the elastic free energy scales as similar to D-2, confirming the dipolar character of the long-range effective interaction. For small D the energy exhibits a pronounced minimum. The lowest energy corresponds to a symmetrical configuration of the disk-defect pairs, with the inner defect at the mid-point between the disks. The disks are separated by a distance that, is twice the distance of the outer defect from the nearest disk. The latter is identical to the equilibrium distance of a defect nucleated by an isolated disk.

Vertex component analysis: a fast algorithm to unmix hyperspectral data

Given a set of mixed spectral (multispectral or hyperspectral) vectors, linear spectral mixture analysis, or linear unmixing, aims at estimating the number of reference substances, also called endmembers, their spectral signatures, and their abundance fractions. This paper presents a new method for unsupervised endmember extraction from hyperspectral data, termed vertex component analysis (VCA). The algorithm exploits two facts: (1) the endmembers are the vertices of a simplex and (2) the affine transformation of a simplex is also a simplex. In a series of experiments using simulated and real data, the VCA algorithm competes with state-of-the-art methods, with a computational complexity between one and two orders of magnitude lower than the best available method.

Hélices e Espirais em Micro e Nanofibras Celulósicas

A celulose é o polímero renovável mais abundante do mundo. É conhecido pela sua excelente biocompatibilidade, propriedades térmicas e mecânicas. A celulose assim como os polipéptideos e o ADN, pertence a uma família de moléculas orgânicas que dão origem à formação de fases líquidas cristalinas (LCs) colestéricas. A Passiflora Edulis, tal como outras plantas trepadeiras, possui longas e flexíveis gavinhas que permitem à planta encontrar um suporte para se fixar. As gavinhas podem assumir a forma de espirais ou de hélices consoante sejam sustentadas por apenas uma ou por ambas as extremidades. As hélices apresentam muitas vezes duas porções helicoidais, uma esquerda e outra direita, separadas por um segmento recto denominado perversão. Este comportamento é consequência da curvatura intrínseca das gavinhas produzidas pela planta trepadeira. O mesmo comportamento pode ser observado em micro e nanofibras celulósicas fabricadas a partir de soluções líquido-cristalinas, numa escala três a quatro ordens de grandeza inferior à das gavinhas. Este facto sugere que o modelo físico utilizado tenha invariância de escala. Neste trabalho é feito o estudo de fibras e jactos que imitam as estruturas helicoidais apresentadas pelas gavinhas das plantas trepadeiras. As fibras e jactos são produzidos a partir de soluções líquidas cristalinas celulósicas. De modo a determinar as características morfológicas e estruturais, que contribuem para a curvatura das fibras, foram utilizadas técnicas de imagem por ressonância magnética (MRI), microscopia óptica com luz polarisada (MOP), microscopia electrónica de varrimento (SEM) e microscopia de força atómica (AFM) . A variação da forma das estruturas helicoidais com a temperatura parece ser relevante para o fabrico de membranas não tecidas para aplicação em sensores termo-mecânicos.

How to mimic the shapes of plant tendrils on the nano and microscale: spirals and helices of electrospun liquid crystalline cellulose derivatives

We show that suspended nano and microfibres electrospun from liquid crystalline cellulosic solutions will curl into spirals if they are supported at just one end, or, if they are supported at both ends, will twist into a helix of one handedness over half of its length and of the opposite handedness over the other half, the two halves being connected by a short straight section. This latter phenomenon, known as perversion, is a consequence of the intrinsic curvature of the fibres and of a topological conservation law. Furthermore, agreement between theory and experiment can only be achieved if account is taken of the intrinsic torsion of the fibres. Precisely the same behaviour is known to be exhibited by the tendrils of climbing plants such as Passiflora edulis, albeit on a lengthscale of millimetres, i.e., three to four orders of magnitude larger than in our fibres. This suggests that the same basic, coarse-grained physical model is applicable across a range of lengthscales.

Estratégias de implementação de plataformas de e-maintenance na indústria: desenvolvimento de uma aplicação para um sistema logístico de viaturas

Mestrado em Engenharia Electrotécnica – Sistemas Eléctricos de Energia

The Interactions between clients and providers of services related to marketing activities

The purpose of this paper is to analyze the business interactions involved in the purchase of services related to marketing activities. We build on the literature about business services classifications and the interaction between clients and providers of business services. An empirical study is conducted by means of a survey questionnaire. Data were collected from a sample of 80 buying firms of services related to marketing activities who agreed to cooperate and represent medium and large Portuguese’s firms. The results show that the buying of services related to marketing activities involves both the client and the provider in the interaction process. This paper contributes to understanding the interaction process of buying services related to marketing activities in terms of the parties involved, product/service exchange, financial and information exchange. Providers of services related to marketing activities can expect stable and preferred relationships if they can offer a good price and quality of service, meet the agreed deadlines and respond quickly to client orders. On the client’s side, the relevance, the characteristics and the wide diversity of services related to marketing activities requires a good understanding and management of the interaction portfolio with providers.

Fractional dynamics and MDS visualization of earthquake phenomena

This paper analyses earthquake data in the perspective of dynamical systems and fractional calculus (FC). This new standpoint uses Multidimensional Scaling (MDS) as a powerful clustering and visualization tool. FC extends the concepts of integrals and derivatives to non-integer and complex orders. MDS is a technique that produces spatial or geometric representations of complex objects, such that those objects that are perceived to be similar in some sense are placed on the MDS maps forming clusters. In this study, over three million seismic occurrences, covering the period from January 1, 1904 up to March 14, 2012 are analysed. The events are characterized by their magnitude and spatiotemporal distributions and are divided into fifty groups, according to the Flinn–Engdahl (F–E) seismic regions of Earth. Several correlation indices are proposed to quantify the similarities among regions. MDS maps are proven as an intuitive and useful visual representation of the complex relationships that are present among seismic events, which may not be perceived on traditional geographic maps. Therefore, MDS constitutes a valid alternative to classic visualization tools for understanding the global behaviour of earthquakes.

Accounting for the dissociating properties of organic chemicals in LCIA: an uncertainty analysis applied to micropollutants in the assessment of freshwater ecotoxicity

In life cycle impact assessment (LCIA) models, the sorption of the ionic fraction of dissociating organic chemicals is not adequately modeled because conventional non-polar partitioning models are applied. Therefore, high uncertainties are expected when modeling the mobility, as well as the bioavailability for uptake by exposed biota and degradation, of dissociating organic chemicals. Alternative regressions that account for the ionized fraction of a molecule to estimate fate parameters were applied to the USEtox model. The most sensitive model parameters in the estimation of ecotoxicological characterization factors (CFs) of micropollutants were evaluated by Monte Carlo analysis in both the default USEtox model and the alternative approach. Negligible differences of CFs values and 95% confidence limits between the two approaches were estimated for direct emissions to the freshwater compartment; however the default USEtox model overestimates CFs and the 95% confidence limits of basic compounds up to three orders and four orders of magnitude, respectively, relatively to the alternative approach for emissions to the agricultural soil compartment. For three emission scenarios, LCIA results show that the default USEtox model overestimates freshwater ecotoxicity impacts for the emission scenarios to agricultural soil by one order of magnitude, and larger confidence limits were estimated, relatively to the alternative approach.

Precursors’ order effect on the properties of sulfurized Cu2ZnSnS4 thin films

A dc magnetron sputtering-based method to grow high-quality Cu2ZnSnS4 (CZTS) thin films, to be used as an absorber layer in solar cells, is being developed. This method combines dc sputtering of metallic precursors with sulfurization in S vapour and with post-growth KCN treatment for removal of possible undesired Cu2−xS phases. In this work, we report the results of a study of the effects of changing the precursors’ deposition order on the final CZTS films’ morphological and structural properties. The effect of KCN treatment on the optical properties was also analysed through diffuse reflectance measurements. Morphological, compositional and structural analyses of the various stages of the growth have been performed using stylus profilometry, SEM/EDS analysis, XRD and Raman Spectroscopy. Diffuse reflectance studies have been done in order to estimate the band gap energy of the CZTS films. We tested two different deposition orders for the copper precursor, namely Mo/Zn/Cu/Sn and Mo/Zn/Sn/Cu. The stylus profilometry analysis shows high average surface roughness in the ranges 300–550 nm and 230–250 nm before and after KCN treatment, respectively. All XRD spectra show preferential growth orientation along (1 1 2) at 28.45◦. Raman spectroscopy shows main peaks at 338 cm−1 and 287 cm−1 which are attributed to Cu2ZnSnS4. These measurements also confirm the effectiveness of KCN treatment in removing Cu2−xS phases. From the analysis of the diffuse reflectance measurements the band gap energy for both precursors’ sequences is estimated to be close to 1.43 eV. The KCN-treated films show a better defined absorption edge; however, the band gap values are not significantly affected. Hot point probe measurements confirmed that CZTS had p-type semiconductor behaviour and C–V analysis was used to estimate the majority carrier density giving a value of 3.3 × 1018 cm−3.

Evaluating the duration of message transactions in broadcast wired/wireless fieldbus networks

Determining the response time of message transactions is one of the major concerns in the design of any distributed computer-controlled system. Such response time is mainly dependent on the medium access delay, the message length and the transmission delay. While the medium access delay in fieldbus networks has been thoroughly studied in the last few years, the transmission delay has been almost ignored as it is considered that it can be neglected when compared to the length of the message itself. Nevertheless, this assumption is no longer valid when considering the case of hybrid wired/wireless fieldbus networks, where the transmission delay through a series of different mediums can be several orders of magnitude longer than the length of the message itself. In this paper, we show how to compute the duration of message transactions in hybrid wired/wireless fieldbus networks. This duration is mainly dependent on the duration of the request and response frames and on the number and type of physical mediums that the frames must cross between initiator and responder. A case study of a hybrid wired/wireless fieldbus network is also presented, where it becomes clear the interest of the proposed approach

Smart-HOP: a reliable handoff mechanism for mobile wireless sensor networks

Handoff processes, the events where mobile nodes select the best access point available to transfer data, have been well studied in cellular and WiFi networks. However, wireless sensor networks (WSN) pose a new set of challenges due to their simple low-power radio transceivers and constrained resources. This paper proposes smart-HOP, a handoff mechanism tailored for mobile WSN applications. This work provides two important contributions. First, it demonstrates the intrinsic relationship between handoffs and the transitional region. The evaluation shows that handoffs perform the best when operating in the transitional region, as opposed to operating in the more reliable connected region. Second, the results reveal that a proper fine tuning of the parameters, in the transitional region, can reduce handoff delays by two orders of magnitude, from seconds to tens of milliseconds.