Synthesis, Antimicrobial and Antiproliferative Activity of Novel Silver(I) Tris(pyrazolyl)methanesulfonateand 1,3,5-Triaza-7-phosphadamantane Complexes

Five new silver(I) complexes of formulas [Ag(Tpms)] (1), [Ag(Tpms)-(PPh3)] (2), [Ag(Tpms)(PCy3)] (3), [Ag(PTA)][BF4] (4), and [Ag(Tpms)(PTA)] (5) {Tpms = tris(pyrazol-1-yl)methanesulfonate, PPh3 = triphenylphosphane, PCy3 = tricyclohexylphosphane, PTA = 1,3,5-triaza-7-phosphaadamantane) have been synthesized and fully characterized by elemental analyses, H-1, C-13, and P-31 NMR, electrospray ionization mass spectrometry (ESI-MS), and IR spectroscopic techniques. The single crystal X-ray diffraction study of 3 shows the Tpms ligand acting in the N-3-facially coordinating mode, while in 2 and 5 a N2O-coordination is found, with the SO3 group bonded to silver and a pendant free pyrazolyl ring. Features of the tilting in the coordinated pyrazolyl rings in these cases suggest that this inequivalence is related with the cone angles of the phosphanes. A detailed study of antimycobacterial and antiproliferative properties of all compounds has been carried out. They were screened for their in vitro antimicrobial activities against the standard strains Enterococcus faecalis (ATCC 29922), Staphylococcus aureus (ATCC 25923), Streptococcus pneumoniae (ATCC 49619), Streptococcus pyogenes (SF37), Streptococcus sanguinis (SK36), Streptococcus mutans (UA1S9), Escherichia coli (ATCC 25922), and the fungus Candida albicans (ATCC 24443). Complexes 1-5 have been found to display effective antimicrobial activity against the series of bacteria and fungi, and some of them are potential candidates for antiseptic or disinfectant drugs. Interaction of Ag complexes with deoxyribonucleic acid (DNA) has been studied by fluorescence spectroscopic techniques, using ethidium bromide (EB) as a fluorescence probe of DNA. The decrease in the fluorescence of DNA EB system on addition of Ag complexes shows that the fluorescence quenching of DNA EB complex occurs and compound 3 is particularly active. Complexes 1-5 exhibit pronounced antiproliferative activity against human malignant melanoma (A375) with an activity often higher than that of AgNO3, which has been used as a control, following the same order of activity inhibition on DNA, i.e., 3 > 2 > 1 > 5 > AgNO3 >> 4.

A her��ldica e a emblem��tica da Guarda Nacional Republicana I

RESUMO: Ensaia-se o estudo da evolu����o da her��ldica e emblem��tica da Guarda Nacional Republicana. Trata-se da primeira tentativa de abordagem da mat��ria em apre��o, privilegiando-se e an��lise em termos art��sticos, ou seja a experimenta����o est��tica das armas.

O Balanced Scorecard como instrumento de gest��o estrat��gica: sua aplicabilidade no Instituto Superior de Gest��o Financeira da Seguran��a Social, I.P.

Pretende-se com esta disserta����o efectuar um estudo dos conceitos associados ao sistema Balanced Scorecard e como este agrupa e articula os v��rios indicadores financeiros e n��o financeiros em quatro perspectivas, a sua aplicabilidade em grandes ou pequenas organiza����es, qualquer que seja o seu ��mbito de actua����o, privada ou p��blica, com ou sem fins lucrativos e a sua import��ncia para a gest��o estrat��gica. De facto, as mudan��as tecnol��gicas, socioculturais e econ��micas que se t��m verificado nas ��ltimas d��cadas, t��m impelido as organiza����es a adaptarem-se a um novo mundo global e competitivo. Assim, desde 1990 que t��m surgido diversos conte��dos bibliogr��ficos e divulga����es em confer��ncias dando ��nfase �� efic��cia da sua adop����o, com reflexos vis��veis na gest��o das empresas e organiza����es do sector p��blico que optam pela implementa����o deste instrumento que articula a estrat��gia com a gest��o. A ader��ncia �� realidade atrav��s de um Estudo de Caso aplicado �� implementa����o do Balanced Scorecard no Instituto de Gest��o Financeira da Seguran��a Social, I. P. ir�� dar uma forte consist��ncia ao desenvolvimento te��rico a efectuar na primeira parte da disserta����o.

Atas do I Encontro de Mestrados em Educa����o da Escola Superior de Educa����o de Lisboa

Os artigos reunidos neste volume de atas pretendem tornar acess��veis, a um p��blico mais vasto e diversificado, a confer��ncia plen��ria, proferida por Clara Rolo, e as comunica����es realizadas pelos participantes no I Encontro dos Mestrados em Educa����o da ESELx (I EME), que decorreu na Escola Superior de Educa����o de Lisboa, no dia 12 de janeiro de 2013. O Encontro foi dinamizado pela Comiss��o Coordenadora de Mestrados P��s-profissionaliza����o, inst��ncia do Conselho T��cnico-Cient��fico, em colabora����o com o Centro Interdisciplinar de Estudos Educacionais ��� CIED, em que se inscrevem os projetos e programas de investiga����o desenvolvidos na ESELx. Prevendo-se que venha a ter, futuramente, uma periodicidade bianual, o Encontro dos Mestrados em Educa����o da ESELx tem como objetivos centrais divulgar a investiga����o produzida no ��mbito dos v��rios Mestrados P��s-Profissionaliza����o existentes na ESELx, e simultaneamente, constituir-se como um f��rum de discuss��o, n��o s�� dos resultados obtidos, mas tamb��m das diversas abordagens metodol��gicas adotadas.

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.

Sequencing of a 17.6 kb segment on the right arm of yeast chromosome VII reveals 12 ORFs, including CCT, ADE3 and TR-I genes, homologues of the yeast PMT and EF1G genes, of the human and bacterial electron-transferring flavoproteins (beta-chain) and of the Escherichia coli phosphoserine phosphohydrolase, and five new ORFs.

A 17.6 kb DNA fragment from the right arm of chromosome VII of Saccharomyces cerevisiae has been sequenced and analysed. The sequence contains twelve open reading frames (ORFs) longer than 100 amino acids. Three genes had already been cloned and sequenced: CCT, ADE3 and TR-I. Two ORFs are similar to other yeast genes: G7722 with the YAL023 (PMT2) and PMT1 genes, encoding two integral membrane proteins, and G7727 with the first half of the genes encoding elongation factors 1gamma, TEF3 and TEF4. Two other ORFs, G7742 and G7744, are most probably yeast orthologues of the human and Paracoccus denitrificans electron-transferring flavoproteins (beta chain) and of the Escherichia coli phosphoserine phosphohydrolase. The five remaining identified ORFs do not show detectable homology with other protein sequences deposited in data banks. The sequence has been deposited in the EMBL data library under Accession Number Z49133.

O Balanced Scorecard como instrumento de gest��o estrat��gica: sua aplicabilidade no Instituto de Gest��o Financeira da Seguran��a Social, I.P.

Mestrado em Contabilidade e Gest��o das Institui����es Financeiras

Atas do VI Encontro do CIED ��� I Encontro Internacional em estudos educacionais. avalia����o: desafios e riscos

Esta publica����o cont��m as comunica����es apresentadas no VI Encontro do CIED ��� I Encontro Internacional em Estudos Educacionais. Avalia����o: Desafios e Riscos, nos dias 15 e 16 de novembro de 2013, na Escola Superior de Educa����o de Lisboa, Instituto Polit��cnico de Lisboa, organizado pelo CIED, com o apoio da Escola Superior de Educa����o de Lisboa.

Jornalismo pol��tico e censura na I Guerra ��� uma vis��o comparativa entre os jornais O Mundo e A Lucta

���Se os governantes soubessem a curiosidade que desperta a censura, se pudessem ler as perguntas feitas aos jornais censurados, se avaliassem bem os efeitos da cria����o deste novo fruto proibido, mandariam para as profundezas do inferno a lei da censura preventiva���, escrevia Jo��o Barbosa, a 1 de Maio de 1917, no di��rio A Lucta. A materializa����o da censura nas p��ginas dos jornais di��rios, por via de intrusivos espa��os em branco, de configura����o vari��vel, n��o deixou de constituir uma nova forma de enunciar o ���problema��� pol��tico. Na nossa an��lise sobre a censura aos jornais A Lucta e o O Mundo, durante a I Guerra Mundial, procuraremos ultrapassar a vis��o excessivamente redutora dos jornais como sendo meros transmissores de mensagens de um emissor para um recetor, aceitando a proposta de M. Schudson:��� que o poder dos m��dia est�� n��o apenas (e nem sequer primariamente) no seu poder de declarar as coisas como sendo verdadeiras mas no poder de fornecer as formas nas quais as declara����es aparecem���. A pr��tica de censura constitui elemento determinante na reconfigura����o do campo pol��tico republicano.

Tris(2-Ethylhexyl) trimellitate (TOTM) a potential reference fluid for high viscosity. Part I: viscosity measurements at temperatures from (303 to 373)K and pressures up to 65MPa, using a novel vibrating-wire instrument

No literature data above atmospheric pressure could be found for the viscosity of TOTIVI. As a consequence, the present viscosity results could only be compared upon extrapolation of the vibrating wire data to 0.1 MPa. Independent viscosity measurements were performed, at atmospheric pressure, using an Ubbelohde capillary in order to compare with the vibrating wire results, extrapolated by means of the above mentioned correlation. The two data sets agree within +/- 1%, which is commensurate with the mutual uncertainty of the experimental methods. Comparisons of the literature data obtained at atmospheric pressure with the present extrapolated vibrating-wire viscosity measurements have shown an agreement within +/- 2% for temperatures up to 339 K and within +/- 3.3% for temperatures up to 368 K. (C) 2014 Elsevier B.V. All rights reserved.

Reactivity of bulky tris(Phenylpyrazolyl) methanesulfonate copper(I) complexes towards small unsaturated molecules

Reaction of the tris(3-phenylpyrazolyl)methane sulfonate species (Tpms(Ph))Li with the copper(I) complex [Cu(MeCN)(4)][PF6] affords [Cu(Tpms(Ph))(MeCN)] 1. The latter, upon reaction with equimolar amounts of cyclohexyl-(CyNC) or 2,6-dimethylphenyl (XylNC) isocyanides, or excess CO, furnishes the corresponding Cu(I)complexes [Cu(Tpms(Ph))(CNR)] (R = Cy 2, Xyl 3) or [Cu(Tpms(Ph))(CO)] 4. The ligated isocyanide in 2 or 3 (or the acetonitrile ligand in 1)is displaced by 3-iminoisoindolin-1-one to afford 5, the first copper(I) complex containing an 3-iminoisoindolin-1-one ligand. The ligated acetonitrile in 1 undergoes nucleophilic attack by methylamine to give the amidine complex [Cu(Tpms(Ph)){MeC(NH)NHMe}] 6, whereas only the starting materials were recovered from the attempted corresponding reactions of 2 and 3 with methylamine. Complexes 1 or 6 form the trinuclear hydroxo-copper(II)species [(mu-Cu){Cu(mu-OH) (2)(Tpms(Ph))}(2)] 7 upon air oxidation in moist methanol. In all the complexes the scorpionate ligand facially caps the metal in the N,N,O-coordination mode.

Liquid crystal beads constrained on thin cellulosic fibers: Electric field induced microrotors and N-I transition

We directly visualize the response of nematic liquid crystal drops of toroidal topology threaded in cellulosic fibers, suspended in air, to an AC electric field and at different temperatures over the N-I transition. This new liquid crystal system can exhibit non-trivial point defects, which can be energetically unstable against expanding into ring defects depending on the fiber constraining geometries. The director anchoring tangentially near the fiber surface and homeotropically at the air interface makes a hybrid shell distribution that in turn causes a ring disclination line around the main axis of the fiber at the center of the droplet. Upon application of an electric field, E, the disclination ring first expands and moves along the fiber main axis, followed by the appearance of a stable "spherical particle" object orbiting around the fiber at the center of the liquid crystal drop. The rotation speed of this particle was found to vary linearly with the applied voltage. This constrained liquid crystal geometry seems to meet the essential requirements in which soliton-like deformations can develop and exhibit stable orbiting in three dimensions upon application of an external electric field. On changing the temperature the system remains stable and allows the study of the defect evolution near the nematic-isotropic transition, showing qualitatively different behaviour on cooling and heating processes. The necklaces of such liquid crystal drops constitute excellent systems for the study of topological defects and their evolution and open new perspectives for application in microelectronics and photonics.

Deep crustal structure across a young passive margin from wide-angle and reflection seismic data (The Sardinia Experiment) - I. Gulf of Lion's margin

The conjugate margins system of the Gulf of Lion and West Sardinia (GLWS) represents a unique natural laboratory for addressing fundamental questions about rifting due to its landlocked situation, its youth, its thick sedimentary layers, including prominent palaeo-marker such as the MSC event, and the amount of available data and multidisciplinary studies. The main goals of the SARDINIA experiment, were to (i) investigate the deep structure of the entire system within the two conjugate margins: the Gulf of Lion and West Sardinia, (ii) characterize the nature of the crust, and (iii) define the geometry of the basin and provide important constrains on its genesis. This paper presents the results of P-wave velocity modelling on three coincident near-vertical reflection multi-channel seismic (MCS) and wide-angle seismic profiles acquired in the Gulf of Lion, to a depth of 35 km. A companion paper [part II Afilhado et al., 2015] addresses the results of two other SARDINIA profiles located on the oriental conjugate West Sardinian margin. Forward wide-angle modelling of both data sets confirms that the margin is characterised by three distinct domains following the onshore unthinned, 33 km-thick continental crust domain: Domain I is bounded by two necking zones, where the crust thins respectively from 30 to 20 and from 20 to 7 km over a width of about 170 km; the outermost necking is imprinted by the well-known T-reflector at its crustal base; Domain II is characterised by a 7 km-thick crust with anomalous velocities ranging from 6 to 7.5 km/s; it represents the transition between the thinned continental crust (Domain I) and a very thin (only 4-5 km) "atypical" oceanic crust (Domain III). In Domain II, the hypothesis of the presence of exhumed mantle is falsified by our results: this domain may likely consist of a thin exhumed lower continental crust overlying a heterogeneous, intruded lower layer. Moreover, despite the difference in their magnetic signatures, Domains II and III present the very similar seismic velocities profiles, and we discuss the possibility of a connection between these two different domains.

Estrat��gias informativas de um jornal h��brido: o caso do ���I��� nos media portugueses

Disserta����o apresentada �� Escola Superior de Comunica����o Social como parte dos requisitos para obten����o de grau de mestre em Audiovisual e Multim��dia.