Synthesis and structural characterization of iron complexes with 2,2,2-tris(1-pyrazolyl)ethanol ligands: Application in the peroxidative oxidation of cyclohexane under mild conditions

The reactions of FeCl2 center dot 2H(2)O and 2,2,2-tris(1-pyrazolyl) ethanol HOCH2C(pz)(3) (1) (pz = pyrazolyl) afford [Fe{HOCH2C(pz)(3)}(2)][FeCl4]Cl (2), [Fe{HOCH2C(pz)(3)}(2)](2)[Fe2OCl6](Cl)(2)center dot 4H(2)O (3 center dot 4H(2)O), [Fe{HOCH2C(pz)(3)}(2)] [FeCl{HOCH2C(pz)(3)}(H2O)(2)](2)(Cl)(4) (4) or [Fe{HOCH2C(pz)(3)}(2)]Cl-2 (5), depending on the experimental conditions. Compounds 1-5 were isolated as air-stable crystalline solids and fully characterized, including (1-4) by single-crystal X-ray diffraction analyses. The latter technique revealed strong intermolecular H-bonds involving the OH group of the scorpionate 2 and 3 giving rise to 1D chains which, in 3, are further expanded to a 2D network with intercalated infinite and almost plane chains of H-interacting water molecules. In 4, intermolecular pi center dot center dot center dot pi interactions involving the pyrazolyl rings are relevant. Complexes 2-5 display a high solubility in water (S-25 degrees C ca. 10-12 mg mL(-1)), a favourable feature towards their application as catalysts (or catalyst precursors) for the peroxidative oxidation of cyclo-hexane to cyclohexanol and cyclohexanone, with aqueous H2O2/MeCN, at room temperature (TON values up to ca. 385). (C) 2011 Elsevier B. V. All rights reserved.

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.

Formação contínua e supervisão pedagógica: o impacto do Programa Nacional do Ensino do Português no desenvolvimento profissional de professores do 1º Ciclo do Ensino Básico

Este estudo pretende descrever e compreender o processo formativo dos professores do 1º ciclo do Ensino Básico, no contexto do Programa Nacional de Ensino do Português (PNEP), as suas dimensões mais relevantes e como é percecionada a supervisão nesse processo de formação contínua. A metodologia adotada nesta investigação foi de natureza qualitativa e baseou-se num conjunto de entrevistas semi-diretivas realizadas a formandos que frequentaram o PNEP entre 2008/2010. Dos resultados obtidos foi possível verificar o impacto positivo que esta modalidade de formação contínua teve no desenvolvimento profissional dos professores preparando-os para a implementação do novo programa de português e permitindo-lhes desmistificar o papel do supervisor através da participação numa experiência de supervisão. O trabalho colaborativo entre professores emergiu durante este processo formativo fomentando a construção de saber em colaboração. A prática pedagógica dos professores apresentou mudanças que pretenderam repercutir-se no aproveitamento dos alunos na área da língua portuguesa. - Abstract This study aims to comprehend and describe the formative process and practice of teachers in Basic education (1st Cycle), in the context of the National Programme for the Teaching of Portuguese Language (PNEP), its most relevant dimensions, the factors which affected it and how supervision was perceived by the teachers involved. A qualitative approach was used, based on semi-directed interviews done to teachers that attended the PNEP, from 2008 to 2010. The impact of this type of continuing training on teachers‟ professional development was positive. They felt prepared for the implementation of the new Portuguese Language Programme. They also demystified the role of the supervisor through the participation in an experience of supervision. The teachers‟ collaborative work emerged during this formative process, promoting the construction of knowledge among teachers. Added to this, teachers‟ pedagogical practice also improved reflected on the students‟ proficiency in the Portuguese language.

Perspetivas dos professores do 1º ciclo sobre a supervisão no processo de avaliação de desempenho e os seus efeitos no desenvolvimento profissional

Dissertação apresentada à Escola Superior de Educação de Lisboa para obtenção de grau de mestre em Ciências da Educação, especialização Supervisão em Educação

O fim de um ciclo? A coconstrução da articulação curricular entre o 1.º e o 2.º Ciclos do Ensino Básico

Dissertação Apresentada à Escola Superior de Educação de Lisboa para obtenção de grau de mestre em Ciências da Educação - Especialidade Supervisão em Educação