Synthesis, characterization and redox behaviour of benzoyldiazenido- and oxorhenium complexes bearing N,N- and S,S-type ligands

The reactions of [ReCl2{eta(2)-N2C(O)Ph}(PPh3)(2)](1) with 2-aminopyrimidine (H(2)Npyrm), 2,2'-bipyridine (bpy) and tetraethylthiuram disulfide (tds), in MeOH upon reflux, lead to the new eta(1)-(benzoyldiazenido)-rhenium(III) complexes [ReCl{eta(1)-N2C(O)Ph}(HNpyrm)(PPh3)(2)](2)and [ReCl2{eta(1)-N2C(O)Ph}(bpy)(PPh3)] (3), and the known oxo(diethyldithiocarbamato)dirhenium(v)complex [Re2O2(mu O){Et2NC(S)S}(4)](4), respectively. The Et2NC(S)S ligands in 4 result from S-S bond rupture of tds molecules. The obtained compounds have been characterized by IR, H-1, P-31{H-1} and C-13{H-1} NMR spectroscopies, FAB(+)-MS, elemental and single-crystal X-ray diffraction (for 2 and 4)analyses. Complex 2 represents the first structurally characterized Re compound derived from 2-aminopyrimidine. Besides, the redox behaviour of 2-4 in CH2Cl2 solution has been studied by cyclic voltammetry, and the Lever electrochemical ligand parameter (E-L)has been estimated, for the first time, for HNpyrm. The electrochemical results are discussed in terms of electronic properties of the Re centres and the ligands.

Bodas de sangue: um exemplo prático de crioulização cénica

O presente relatório pretende fazer uma descrição do processo de crioulização cénica – adaptação teatral ao contexto crioulo de Cabo Verde – da peça de Federico Garcia Lorca, Bodas de Sangue, cuja estreia teve lugar na última edição do Festival Internacional de Teatro do Mindelo – Mindelact 2011. O texto inclui uma componente conceptual, onde se procura explicar e enquadrar o conceito sócio-antropológico de crioulização à arte cénica. Neste sentido, são apresentados alguns exemplos concretos da sua aplicação no terreno, numa prática que vem sendo desenvolvida desde os anos noventa do século XX até à presente data, no âmbito do trabalho com o Grupo de Teatro do Centro Cultural Português – IC do Pólo do Mindelo, em Cabo Verde. Após essa introdução teórica e histórica, damos conta dos elementos preponderantes ao longo da crioulização cénica da peça, começando com a adaptação dramatúrgica, que implicou um enquadramento histórico, social, linguístico e cultural diferente do da peça original. Damos conta da investigação realizada no âmbito das tradições ligadas ao casamento no arquipélago caboverdiano, nomeadamente no campo social, tradicional e musical, que serviram de base para a elaboração do texto dramático final. Por fim, inserimos uma descrição dos resultados obtidos com a montagem cénica no que diz respeito às opções de encenação, figurinos, adereços, iluminação, banda sonora e recepção do público na noite da estreia, fazendo uma ligação final entre esses mesmos resultados e o conceito de crioulização cénica explanado no capítulo inicial.

Cuidados de saúde primários: as regras do jogo

Enquadramento – A reforma dos Cuidados de Saúde Primários (CSP) é um facto irreversível. Uma “onda” de reforma percorre igualmente grande parte dos países ocidentais exigindo uma reflexão sobre o processo. Objetivo – Descrever a reforma em curso nos CSP e identificar os potenciais factores de sucesso e insucesso dos serviços públicos de cuidados de saúde primários. Metodologia – Análise crítica da literatura. Resultados e conclusões – A eficiência, eficácia e equidade de acesso aos cuidados de saúde são insuficientes. Mudanças organizacionais estão a ser operadas alterando as relações e a cooperação inter‑profissional e inter‑organizacional. É evidente a tensão que existe entre as partes envolvidas. Novas formas organizacionais estão a ser criadas para garantir a viabilidade das reformas e equilíbrio dos sistemas. O novo modelo organizacional, se pretender garantir a sustentabilidade e a viabilidade dos cuidados primários, deverá assentar num equilíbrio de gestão de recursos e numa estratégia de saúde para todos que não significa saúde para tudo. ABSTRACT: Background – Primary Health Care (PHC) reform is a fact in several countries and is happening also in Portugal demanding a reflection on the process. Aim – To describe the PHC reform and to identify the factors of success or potential failure in PHC public services. Methods – Critical appraisal of the literature. Results and Conclusions – The efficiency, efficacy and access to health care are insufficient. Organizational changes are taking place altering inter‑professional and inter‑organizational cooperation and relationship. Tension among the parts involved is evident. New organizational models are being created to secure the sustainability of the reforms and the systems. The new models should provide a balanced management of the available resources, in a strategy of health for all that doesn’t mean health for everything.

The solvation and redox behaviour of mixed ligand COPPER(II) complexes of acetylacetonate and aromatic dimines in ionic liquids

The behavior of two cationic copper complexes of acetylacetonate and 2,2'-bipyridine or 1,10-phenanthroline, [Cu(acac)(bipy)]Cl (1) and [Cu(acac)(phen)]Cl (2), in organic solvents and ionic liquids, was studied by spectroscopic and electrochemical techniques. Both complexes showed solvatochromism in ionic liquids although no correlation with solvent parameters could be obtained. By EPR spectroscopy rhombic spectra with well-resolved superhyperfine structure were obtained in most ionic liquids. The spin Hamiltonian parameters suggest a square pyramidal geometry with coordination of the ionic liquid anion. The redox properties of the complexes were investigated by cyclic voltammetry at a Pt electrode (d = 1 mm) in bmimBF(4) and bmimNTf(2) ionic liquids. Both complexes 1 and 2 are electrochemically reduced in these ionic media at more negative potentials than when using organic solvents. This is in agreement with the EPR characterization, which shows lower A(z) and higher g(z) values for the complexes dissolved in ionic liquids, than in organic solvents, due to higher electron density at the copper center. The anion basicity order obtained by EPR is NTf2-, N(CN)(2)(-), MeSO4- and Me2PO4-, which agrees with previous determinations. (C) 2013 Elsevier B.V. All rights reserved.

Study of the interactions in a three-way crossed classification model

Crossed classification models are applied in many investigations taking in consideration the existence of interaction between all factors or, in alternative, excluding all interactions, and in this case only the effects and the error term are considered. In this work we use commutative Jordan algebras in the study of the algebraic structure of these designs and we use them to obtain similar designs where only some of the interactions are considered. We finish presenting the expressions of the variance componentes estimators.

Catalytic activity of a benzoyl hydrazone based dimeric dicopper(II) complex in catechol and alcohol oxidation reactions

The benzoyl hydrazone based dimeric dicopper(II) complex [Cu2(R)(CH3O)(NO3)]2(CH3O)2 (R-Cu2+), recently reported by us, catalyzes the aerobic oxidation of catechols (catechol (S1), 3,5- itertiarybutylcatechol (S2) and 3-nitrocatechol (S3)) to the corresponding quinones (catecholase like activity), as shown by UV–Vis absorption spectroscopy in methanol/HEPES buffer (pH 8.2) medium at 25 C. The highest activity is observed for the substituted catechol (S2) with the electron donor tertiary butyl group, resulting in a turnover frequency (TOF) value of 1.13 103 h1. The complex R-Cu2+ also exhibits a good catalytic activity in the oxidation (without added solvent) of 1-phenylethanol to acetophenone by But OOH under low power (10 W) microwave (MW) irradiation. 2014 Elsevier B.V. All rights reserved.