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.

Synthesis of new Fe(II) and Ru(II) eta(5)-monocyclopentadienyl compounds showing significant second order NLO properties

A series of new ruthenium(II) complexes of the general formula [Ru(eta(5)-C5H5)(PP)(L)][PF6] (PP = DPPE or 2PPh(3), L = 4-butoxybenzonitrile or N-(3-cyanophenyl)formamide) and the binuclear iron(II) complex [Fe(eta(5)-C5H5)(PP)(mu-L)(PP)(eta(5)-C5H5)Fe][PF6](2) (L = (E)-2-(3-(4-nitrophenyl)allylidene)malononitrile, that has been also newly synthesized) have been prepared and studied to evaluate their potential in the second harmonic generation property. All the new compounds were fully characterized by NMR, IR and UV-Vis spectroscopies and their electrochemistry behaviour was studied by cyclic voltammetry. Quadratic hyperpolarizabilities (beta) of three of the complexes have been determined by hyper-Rayleigh scattering (HRS) measurements at fundamental wavelength of 1500 nm and the calculated static beta(0) values are found to fall in the range 65-212 x 10(-30) esu. Compound presenting beta(0) = 212 x 10(-30) esu has revealed to be 1.2 times more efficient than urea standard in the second harmonic generation (SHG) property, measured in the solid state by Kurtz powder technique, using a Nd:YAG laser (1064 nm). (C) 2013 Elsevier B.V. All rights reserved.

Biological activity and cellular uptake of [Ru(eta(5)-C5H5)(PPh3)(Me(2)bpy)][CF3SO3] complex

Anticancer activity of the new [Ru(eta(5)-C5H5)(PPh3)(Me(2)bpy)][CF3SO3] (Me(2)bpy = 4,4'-dimethyl-2,2'-bipyridine) complex was evaluated in vitro against several human cancer cell lines, namely A2780, A2780CisR, HT29, MCF7, MDAMB231 and PC3. Remarkably, the IC50 values, placed in the nanomolar and sub-micromolar range, largely exceeded the activity of cisplatin. Binding to human serum albumin, either HSA (human serum albumin) or HSA(faf) (fatty acid-free human serum albumin) does not affect the complex activity. Fluorescence studies revealed that the present ruthenium complex strongly quench the intrinsic fluorescence of albumin. Cell death by the [Ru(eta(5)-C5H5)(PPh3)(Me(2)bpy)][CF3SO3] complex was reduced in the presence of endocytosis modulators and at low temperature, suggesting an energy-dependent mechanism consistent with endocytosis. On the whole, the biological activity evaluated herein suggests that the complex could be a promising anticancer agent. (C) 2013 Elsevier Inc. All rights reserved.

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.

The Tetrahymena chaperonin subunit CCT eta gene is coexpressed with CCT gamma gene during cilia biogenesis and cell sexual reproduction

We report here the cloning and the characterization of the T. pyriformis CCT eta gene (TpCCT eta) and also a partial sequence of the corresponding T. thermophila gene (TtCCT eta). The TpCCt eta gene encodes a protein sharing a 60.3% identity with the mouse CCT eta. We have studied the expression of these genes in Tetrahymena exponentially growing cells, cells regenerating their cilia for different periods and during different stages of the cell sexual reproduction. These genes have similar patterns of expression to those of the previously identified TpCCt gamma gene. Indeed, the Tetrahymena CCT eta and CCT gamma genes are up-regulated at 60-120 min of cilia recovery, and in conjugation when vegetative growth was resumed and cell division took place. Our results seem to indicate that both CCT subunits play an important role in the biogenesis of the newly synthesized cilia of Tetrahymena and during its cell division.

Blistering of W-Ta composites at different irradiation energies

Pure tungsten and tantalum plates and tungsten-tantalum composites produced via mechanical alloying and spark plasma sintering were bombarded with He+ and D+ energetic ion beams and deuterium plasmas. The aim of this experiment is to study the effects caused by individual helium and deuterium exposures and to evidence that the modifications induced in the composites at different irradiation energies could be followed by irradiating the pristine constituent elements under the same experimental conditions, which is relevant considering the development of tailored composites for fusion applications. Higher D retentions, especially in tungsten, and superficial blistering are observed in both components after helium exposure. The blistering is magnified in the tantalum phase of composites due to its higher ductility and to water vapour production under deuterium irradiation. At lower irradiation energies the induced effects are minor. After plasma exposure, the presence of tantalum does not increase the D content in the composites. (C) 2013 Elsevier B.V. All rights reserved.

Acompanhamento da reabilitação estrutural da ETA de Morgavel

Relatório de Estágio para obtenção do grau de Mestre em Engenharia Civil na Área de Especialização de Edificações

Mono(Eta(5)-cyclopentadienyl)metal(II) complexes with thienyl acetylide chromophores: synthesis, electrochemical studies, and first hyperpolarizabilities

A series of mono(eta(5)-cyclopentadienyl)metal-(II) complexes with nitro-substituted thienyl acetylide ligands of general formula [M(eta(5)-C5H5)(L)(C C{C4H2S}(n)NO2)] (M = Fe, L = kappa(2)-DPPE, n = 1,2; M = Ru, L = kappa(2)-DPPE, 2 PPh3, n = 1, 2; M = Ni, L = PPh3, n = 1, 2) has been synthesized and fully characterized by NMR, FT-IR, and UV-Vis spectroscopy. The electrochemical behavior of the complexes was explored by cyclic voltammetry. Quadratic hyperpolarizabilities (beta) of the complexes have been determined by hyper-Rayleigh scattering (HRS) measurements at 1500 nm. The effect of donor abilities of different organometallic fragments on the quadratic hyperpolarizabilities was studied and correlated with spectroscopic and electrochemical data. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations were employed to get a better understanding of the second-order nonlinear optical properties in these complexes. In this series, the complexity of the push pull systems is revealed; even so, several trends in the second-order hyperpolarizability can still be recognized. In particular, the overall data seem to indicate that the existence of other electronic transitions in addition to the main MLCT clearly controls the effectiveness of the organometallic donor ability on the second-order NLO properties of these push pull systems.

Estudo da problemática da presença de alumínio na linha de tratamento de água para consumo humano, na ETA da Póvoa

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para a obtenção do grau de Mestre em Engenharia do Ambiente, perfil Engenharia Sanitária

Angioplastia Coronária no Enfarte Agudo do Miocárdio: Impacto do Timing da Revascularização na Alternância da Onda Ta

Encontra-se bem estabelecido que, na abordagem terapêutica do enfarte agudo do miocárdio (EAM), a trombólise e a angioplastia coronária percutânea (ACTP) permitem diminuir a mortalidade e melhorar o prognóstico, sendo esse benefício tanto maior quanto menor o tempo decorrido entre o evento isquémico e o procedimento terapêutico. No entanto, não está ainda estabelecido qual o impacto que o atraso da implementação dessas terapêuticas tem no desenvolvimento de taquidisritmias ventriculares e por consequência no resultado da alternância da onda T(TWA), que representa um método reconhecido para avaliação da vulnerabilidade ventricular às referidas arritmias. Objectivo: Analisar os resultados da TWA por microvoltagem numa população submetida a ACTP na sequência de EAM e avaliar a influência do timing de revascularização miocárdica nos resultados da TWA. Métodos: Estudámos 79 doentes (67 do sexo masculino; 57 ± 11 anos) consecutivos, admitidos por EAM e sujeitos a revascularização miocárdica por ACTP durante o internamento. A TWA foi avaliada utilizando um aparelho da HeartTwave System (Cambridge Heart, Inc., Bedford, Massachusetts) nos 30 dias pós-EAM. Durante a realização de uma prova de esforço em tapete rolante com protocolo manual, com o objectivo de elevar a frequência cardíaca até aos 110 batimentos por minuto, realizou-se o registo electrocardiográfico através da aplicação de sete eléctrodos standard e outros sete eléctrodos sensores de alta-resolução, especialmente concebidos para redução do «ruído», dispostos segundo as derivações ortogonais de Frank(X,Y, Z). A TWA foi considerada positiva quando se verificou a presença de alternância da onda T de magnitude ³ 1,9 μV de forma consistente e mantida (> 1 minuto), com início para frequências cardíacas < 110 batimentos/minuto ou quando esta alternância se verificou em doentes em repouso. Foi considerada negativa quando se conseguiu obter dados sem artefactos durante pelo menos um minuto, com frequências > 105 batimentos/minuto, sem atingir critério de positividade e indeterminada se não podia ser classificada como positiva ou negativa. Foram excluídos doentes com EAM ou revascularização miocárdica (cirúrgica ou percutânea) prévios, os que apresentavam insuficiência cardíaca congestiva, com fibrilhação auricular, > 10 extrassístoles por minuto, pacemaker definitivo, bradicárdia < 40 bpm, complexos QRS com duração > 130 ms ou sob terapêutica anti-arrítmica. Considerámos como marcador de risco para a ocorrência de eventos arrítmicos ventriculares malignos a presença de TWA positiva ou indeterminada. (TWA «nãonegativa»). Os resultados da TWA foram comparados entre o grupo de doentes submetidos a ACTP nas primeiras 24 horas pós-EAM (Grupo A; n = 45) e o grupo de doentes submetidos a ACTP > 24 horas pós-EAM. (Grupo B; n = 34) Resultados: A TWA foi positiva em 16 doentes (20,2%) e negativa em 56 (70,9%). Em 7 casos (8,9%), o resultado do teste foi considerado indeterminado. A TWA foi «não-negativa» em 29,1% da população. No grupo A a TWA foi “não-negativa” em 9 doentes (20 %) (6 com TWA positiva e três com TWA indeterminada) e negativa em 36 doentes (80 %) e no grupo B foi «não-negativa» em 14 doentes (41%) (10 com TWA positiva e quatro com TWA indeterminada) e negativa em 20 (59 %) (p < 0,05). Não se encontraram diferenças entre os dois grupos no que respeita à fracção de ejecção ventricular esquerda. No seguimento até aos 60 dias após a alta hospitalar não foram documentados eventos arrítmicos ventriculares, síncopes ou óbito. Foram reinternados cinco doentes (7 %) por recorrênciade angor. Conclusões: Numa população de sobreviventes de EAM encontrámos uma prevalência de TWA não negativa de 29 %, apesar da revascularização miocárdica com ACTP. A ACTP, quando efectuada nas primeiras 24 horas após o início do EAM, reduz de forma significativa o número de doentes com TWA não negativa,sugerindo que esta intervenção precoce poderá baixar o risco arrítmico destes doentes e influenciar favoravelmente o prognóstico pós-EAM. O impacto da morte súbita na mortalidade pós-EAM justifica estudos prospectivos de maiores dimensões

Decision-making process in radiology: the magnetic resonance example in the TA context

Based on the report for “Project IV” unit of the PhD programme on Technology Assessment (Doctoral Conference) at Universidade Nova de Lisboa (December 2011). This thesis research has the supervision of António Moniz (FCT-UNL and ITAS-KIT) and Michael Decker (Karlsruhe Institute of Technology-ITAS). Other members of the thesis committee are Carlos Alberto da Silva (University of Évora), José Maria de Albuquerque (Institute of Welding and Quality), Lotte Steuten (University of Twente), Mário Forjaz Secca (FCT-UNL) and Nelson Chibeles Martins (FCT-UNL).

Renewable energy systems the theme for the PACITA summer school on TA, Liège, Belgium, 25 28 June 2012

The summer school “Renewable Energy Systems: Role and Use of Parliamentary Technology Assessment” was the first European Summer School with a pure focus on technology assessment. The aim of the three-day long summer school of the European project Parliaments and Civil Society in Technology Assessment (PACITA) was to create awareness of the potential of technology groups in Europe. Therefore, the summer school involved keynotes, practical exercises, mutual reflection, cutting edge training and networking to deal with the theme of renewable energy systems out of the perspective of Technology Assessment (TA), to meet transition objectives or to critically assess energy technologies.

Cuando las ciudades se transforman en paisajes: representación, fragmentación e idealización del espacio urbano

El texto considera que el espacio de la ciudad es representado hoy a partir de los mecanismos de construcción cultural del paisaje. Se concluye que estos tienen por consecuencia una fragmentación y una idealización/estilización del territorio. Al mismo tiempo que afirman el deleite estético y la idealización de la vida, los mecanismos referidos fomentan el abandono de una mirada crítica y global sobre la ciudad.