Coordination Chemistry of the (eta(6)-p-Cymene)ruthenium(II) Fragment with Bis-, Tris-, andTetrakis(pyrazol-1-yl)borate Ligands: Synthesis, Structural, Electrochemical, and CatalyticDiastereoselective Nitroaldol Reaction Studies

Novel [Ru(eta(6)-p-cymene)(kappa(2)-L)X] and [Ru(eta(6)-p-cymene)(kappa(3)-L)]X center dot nH(2)O complexes (L = bis-, tris-, or tetrakis-pyrazolylborate; X = Cl, N-3, PF6, or CF3SO3) are prepared by treatment of [Ru(eta(6)-p-cymene)Cl-2](2) with poly-(pyrazolyl)borate derivatives [M(L)] (L in general; in detail L = Ph(2)Bp = diphenylbis-(pyrazol-1-yl)borate; L = Tp = hydrotris(pyrazol-1-yl)borate; L = pzTp = tetrakis(pyrazol-1-yl)borate; L = Tp(4Bo) = hydrotris(indazol-1-yl)borate, L = T-p4Bo,T-5Me = (5-methylindazol-1-yl)borate; L = Tp(Bn,4Ph) = hydrotris(3-benzyl-4-phenylpyrazol-1-yl)borate; M = Na, K, or TI) and characterized by analytical and spectral data (IR, ESIMS, H-1 and C-13 NMR). The structures of [Ru(eta(6)-p-cymene)(Ph(2)Bp)Cl] (1) and [Ru(eta(6)-p-cymene)(Tp)Cl] (3) have been established by single-crystal X-ray diffraction analysis. Electrochemical studies allowed comparing the electron-donor characters of Tp and related ligands and estimating the corresponding values of the Lever E-L ligand parameter. The complexes [Ru(eta(6)-p-cymene)-(kappa(2)-L)X] and [Ru(eta(6)-p-cymene)(kappa(3)-L)]X center dot nH(2)O act as catalyst precursors for the diastereoselective nitroaldol reaction of benzaldehyde and nitroethane to the corresponding beta-nitroalkanol (up to 82% yield, at room temperature) with diastereoselectivity toward the formation of the threo isomer.

O Balanced Scorecard como instrumento de gestão estratégica: sua aplicabilidade no Instituto Superior de Gestão Financeira da Segurança Social, I.P.

Pretende-se com esta dissertação efectuar um estudo dos conceitos associados ao sistema Balanced Scorecard e como este agrupa e articula os vários indicadores financeiros e não financeiros em quatro perspectivas, a sua aplicabilidade em grandes ou pequenas organizações, qualquer que seja o seu âmbito de actuação, privada ou pública, com ou sem fins lucrativos e a sua importância para a gestão estratégica. De facto, as mudanças tecnológicas, socioculturais e económicas que se têm verificado nas últimas décadas, têm impelido as organizações a adaptarem-se a um novo mundo global e competitivo. Assim, desde 1990 que têm surgido diversos conteúdos bibliográficos e divulgações em conferências dando ênfase à eficácia da sua adopção, com reflexos visíveis na gestão das empresas e organizações do sector público que optam pela implementação deste instrumento que articula a estratégia com a gestão. A aderência à realidade através de um Estudo de Caso aplicado à implementação do Balanced Scorecard no Instituto de Gestão Financeira da Segurança Social, I. P. irá dar uma forte consistência ao desenvolvimento teórico a efectuar na primeira parte da dissertação.

Modeling Allee Effect from Beta(p, 2) Densities

In this work we develop and investigate generalized populational growth models, adjusted from Beta(p, 2) densities, with Allee effect. The use of a positive parameter leads the presented generalization, which yields some more flexible models with variable extinction rates. An Allee limit is incorporated so that the models under study have strong Allee effect.

a-SiH p-i-n structures with extreme i-layer thickness

We present measurements and numerical simulation of a-Si:H p-i-n detectors with a wide range of intrinsic layer thickness between 2 and 10 pm. Such a large active layer thickness is required in applications like elementary particle detectors or X-ray detectors. For large thickness and depending on the applied bias, we observe a sharp peak in the spectral response in the red region near 700 nm. Simulation results obtained with the program ASCA are in agreement with the measurement and permit the explanation of the experimental data. In thick samples holes recombine or are trapped before reaching the contacts, and the conduction mechanism is fully electron dominated. As a consequence, the peak position in the spectral response is located near the optical band gap of the a-Si:H i-layer. (C) 2009 Elsevier B.V. All rights reserved.

Relações públicas no sector da saúde e do bem-estar: estratégia de r.p. para o posionamento de uma cadeia de spas de hotel

A área da saúde e do bem-estar em Portugal, é um segmento em clara expansão. Dadas as suas características geográficas, estranha-se, contudo, a falta de equipamentos no campo da talassoterapia bem como a dispersidade da oferta no sector do turismo de saúde. Respondendo a uma necessidade sentida pelo grupo Hotéis Real, este trabalho de projecto pode definir-se como o desenvolvimento de uma estratégia de construção e expressão de um novo serviço de spas para esta cadeia hoteleira, numa perspectiva de comunicação corporate. Para tal, o projecto estrutura-se assente numa revisão de literatura que analisa as principais temáticas e questões tanto da área da saúde e do bem-estar, como do sector do turismo.

O Balanced Scorecard como instrumento de gestão estratégica: sua aplicabilidade no Instituto de Gestão Financeira da Segurança Social, I.P.

Mestrado em Contabilidade e Gestão das Instituições Financeiras

Particle agglomeration study in rf silane plasmas: In situ study by polarization-sensitive laser light scattering

To determine self-consistently the time evolution of particle size and their number density in situ multi-angle polarization-sensitive laser light scattering was used. Cross-polarization intensities (incident and scattered light intensities with opposite polarization) measured at 135 degrees and ex situ transmission electronic microscopy analysis demonstrate the existence of nonspherical agglomerates during the early phase of agglomeration. Later in the particle time development both techniques reveal spherical particles again. The presence of strong cross-polarization intensities is accompanied by low-frequency instabilities detected on the scattered light intensities and plasma emission. It is found that the particle radius and particle number density during the agglomeration phase can be well described by the Brownian free molecule coagulation model. Application of this neutral particle coagulation model is justified by calculation of the particle charge whereby it is shown that particles of a few tens of nanometer can be considered as neutral under our experimental conditions. The measured particle dispersion can be well described by a Brownian free molecule coagulation model including a log-normal particle size distribution. (C) 1996 American Institute of Physics.

Chiroptical and emissive properties of a calix[4]arene-containing chiral poly (P-phenylene ethynylene) with enantioselective recognition ability

Supramolecular chirality was achieved in solutions and thin films of a calixarene-containing chiral aryleneethynylene copolymer. The observed chiroptical activity, which is primarily allied with the formation of aggregates of high molecular weight polymer chains, is the result of a combination of intrachain and interchain effects. The former arises by the adoption of an induced helix-sense by the polymer main-chain while the latter comes from the exciton coupling of aromatic backbone transitions. The co-existence of bulky bis-calixKlarene units and chiral side-chains on the polymer skeleton prevents efficient pi-stacking of neighbouring chains, keeping the chiral assembly highly emissive. In contrast, for a model polymer lacking calixarene moieties, the chiroptical activity is dominated by strong interchain exciton couplings as a result of more favourable packing of polymer chains, leading to a marked decrease of photoluminescence in the aggregate state. The enantiomeric recognition abilities of both polymers towards (R)- and (S)-alpha-methylbenzylamine were examined. It was found that a significant enantiodiscrimination is exhibited by the calixarene-based polymer in the aggregate state.

Cultura da (in) segurança nos contextos de trabalho em enfermagem: o caso do Hospital do Espírito Santo de Évora - E.P.E.

Mestrado em Intervenção Sócio-Organizacional na Saúde - Área de especialização: Políticas de Administração e Gestão de Serviços de Saúde

Insights into the mechanims underlyng the antiproliferative potential of a Co(II) coordination compound bearing 1,10-Phenanthroline-5,6-Dione: DNA and protein interaction studies

The very high antiproliferative activity of [Co(Cl)(H2O)(phendione)(2)][BF4] (phendione is 1,10-phenanthroline-5,6-dione) against three human tumor cell lines (half-maximal inhibitory concentration below 1 mu M) and its slight selectivity for the colorectal tumor cell line compared with healthy human fibroblasts led us to explore the mechanisms of action underlying this promising antitumor potential. As previously shown by our group, this complex induces cell cycle arrest in S phase and subsequent cell death by apoptosis and it also reduces the expression of proteins typically upregulated in tumors. In the present work, we demonstrate that [Co(Cl)(phendione)(2)(H2O)][BF4] (1) does not reduce the viability of nontumorigenic breast epithelial cells by more than 85 % at 1 mu M, (2) promotes the upregulation of proapoptotic Bax and cell-cycle-related p21, and (3) induces release of lactate dehydrogenase, which is partially reversed by ursodeoxycholic acid. DNA interaction studies were performed to uncover the genotoxicity of the complex and demonstrate that even though it displays K (b) (+/- A standard error of the mean) of (3.48 +/- A 0.03) x 10(5) M-1 and is able to produce double-strand breaks in a concentration-dependent manner, it does not exert any clastogenic effect ex vivo, ruling out DNA as a major cellular target for the complex. Steady-state and time-resolved fluorescence spectroscopy studies are indicative of a strong and specific interaction of the complex with human serum albumin, involving one binding site, at a distance of approximately 1.5 nm for the Trp214 indole side chain with log K (b) similar to 4.7, thus suggesting that this complex can be efficiently transported by albumin in the blood plasma.

A percepção dos profissionais de saúde sobre o trabalho em equipa no contexto do Hospital do Espírito Santo de Évora, E.P.E.

Mestrado em Intervenção Sócio-Organizacional na Saúde - Área de especialização: Políticas de Administração e Gestão de Serviços de Saúde

Substituted P-Phenylene Ethynylene trimers as fluorescent sensors for nitroaromatic explosives

New sensory materials based on p-phenylene ethynylene trimers integrating calix[4]arene receptors (CALIX-PET) and tert-butylphenol (TBP-PET) moieties have been synthesized and their sensitivity and selectivity for the detection of nitroaromatic compounds (NACs) such as nitrobenzene (NB), 2,4-dinitrotoluene (2,4-DNT), 2,4,6-trinitrotoluene (TNT) and picric acid (PA) investigated in fluid phase and solid-state. It was found that both fluorophores displayed high sensitivities toward NACs detection in solution as evaluated by the Stern-Volmer formalism. For all the tested explosives, the ratio of fluorescence intensities (F-0/F) is a linear function of the quencher concentration only after appropriate correction of fluorescence quenching data for inner-filter effects. The quenching efficiencies for CALIX-PET and TBP-PET follow the order PA >> TNT > DNT > NB, which correlate well with the quenchers electron affinities as evaluated from their LUMOs energies thereby suggesting a photoinduced electron transfer as the dominant mechanism of fluorescence quenching. The selectivity of these sensors was checked against exemplar interferents possessing differentiated electronic properties (benzoic acid, 2,4-dichlorophenol and benzoquinone) and reduced quenching activity was detected. The quenching efficiencies and response times of the two fluorophores in the solid-state toward NB, 2,4-DNT and TNT vapors were evaluated through steady-state fluorescence quenching experiments with the materials dispersed in polymeric matrices or as neat films. The most significant fluorescence quenching responses were achieved for drop-casted films of TBP-PET upon exposure to nitroaromatics.

Generalized models from Beta(p,2) densities with strong allee effect: dynamical approach

A dynamical approach to study the behaviour of generalized populational growth models from Bets(p, 2) densities, with strong Allee effect, is presented. The dynamical analysis of the respective unimodal maps is performed using symbolic dynamics techniques. The complexity of the correspondent discrete dynamical systems is measured in terms of topological entropy. Different populational dynamics regimes are obtained when the intrinsic growth rates are modified: extinction, bistability, chaotic semistability and essential extinction.

Deep structure of crust and mantle beneath Iberia and Western Mediterranean from P and S Receiver functions and SKS Waveforms

We have conducted a P and S receiver functions [PRFs and SRFs] analysis for 19 seismic stations on the Iberia and western Mediterranean. In the transition zone [TZ] the PRFs analysis reveals a band [from Gibraltar to Balearic] increased by 10-20 km relative to the standard 250 km. The TZ thickness variations are strongly correlated with the P660s times in PRFs. We interpret the variable depth of the 660-km discontinuity as an effect of subduction. Over the anomalous TZ we found a reduced velocity zone in the upper mantle. Joint inversion of PRFs and SRFs reveals a subcrustal high S velocity lid and an underlying LVZ. A reduction of the S velocity in the LVZ is less than 10%. The Gutenberg discontinuity is located at 65±5 km, but in several models sampling the Mediterranean, the lid is missing or its thickness is reduced to ~30 km. In the Gibraltar and North Africa this boundary is located at ~100 km. The lid Vp/Vs beneath Betics is reduced relative to the standard 1.8. Another evidence of the Vp/Vs anomaly is provided by S410p phase late arrivals in the SRFs. The azimuthal anisotropy analysis with a new technology was conducted at 5 stations and at 2 groups of stations. The fast direction in the uppermost mantle layer is ~90º in Iberian Massif. In Balearic is in the azimuth of ~120º. At a depth of ~60 km the direction becomes 90º. Anisotropy in the upper layer can be interpreted as frozen, whereas anisotropy in the lower layer is active, corresponding to the present-day or recent flow. The effect of the asthenosphere in the SKS splitting is much larger than the effect of the subcrustal lithosphere.