O PLH – o contexto familiar, motivacional e cultural dos alunos lusodescendentes

A relação entre língua e identidade e, o reforço do vínculo afetivo dos alunos com as suas raízes, é um dos objetivos principais do ensino português no estrangeiro (EPE). Neste contexto, a língua portuguesa (LP) não é a língua dominante para os nossos alunos, mas, sim uma língua de herança, com a qual os alunos mantêm uma relação de afetividade e de pertença. Para podermos identificar e caracterizar, esta relação de afetividade e pertença com a LP, e o contexto em que decorre a aprendizagem, recorremos a uma entrevista realizada aos encarregados de educação (EE) / pais dos nossos alunos

O Ensino do Português no Estrangeiro – O resgate de uma língua. Contributo para a identificação da identidade lingüística e cultural de alunos lusodescendentes

Este trabalho de investigação insere-se na realidade do ensino do português no estrangeiro (EPE), na Alemanha, onde somos professora e propõe-se a refletir sobre qual o estatuto que a língua portuguesa (LP), assume para os nossos alunos lusodescendentes, da segunda e terceira geração de imigrantes, procurando saber se o processo de ensino e aprendizagem (E/A) adotado vai ao encontro dos perfis e dos desejos do público-alvo dos cursos de língua e cultura portuguesas (LCP) do EPE. Assim, com esta tese intitulada “O Ensino do Português no Estrangeiro – O resgate de uma língua de Herança – Contributo para a identificação da identidade linguística e cultural de alunos lusodescendentes”, é nossa intenção apurar (i) quem são estes alunos lusodescendentes e caracterizar a sua identidade linguística, motivacional e cultural; (ii) que dimensão assume a LCP que é aprendida pelos alunos lusodescendentes e (iii) perceber se a organização e a estrutura do modelo de E/A do EPE são adequados ao perfil e às expectativas destes alunos

Os projectos comenius 1 nas escolas do Concelho de Silves: Contributo para a avaliação dos impactos percepcionados pelos professores-coordenadores, nas diferentes dimensões do processo educativo

Este estudo teve como principal objectivo ser um contributo para a compreensão e identificação dos impactos importantes que os Projectos Europeus, na área da Educação, no âmbito da sub-acção Comenius 1 - Parcerias entre Escolas, do Programa Sócrates, tiveram e têm na comunidade educativa do concelho de Silves. O estudo parte, assim, da seguinte questão de investigação: Quais são os impactos percepcionados pelos professores coordenadores dos projectos Comenius 1 nas diferentes dimensões do processo educativo? Neste sentido, estabeleceram-se as seguintes questões secundárias: • Como se construíram e implementaram estes Projectos nas Escolas? • De que forma é que estes Projectos foram integrados no desenho curricular da escola? • Quais foram as maiores dificuldades sentidas pelos responsáveis pelos Projectos na implementação dos mesmos? Através de uma metodologia qualitativa, foram realizadas entrevistas semi­estruturadas a cinco professores de escolas diferentes do Concelho de Silves e recorreu-se à análise documental e de testemunhos. Os resultados parecem indicar que a implementação deste tipo de projectos nas escolas deixa impactos em todos os intervenientes (na Escola, no Conselho Executivo, nos Professores da escola e das escolas parceiras, no Pessoal não Docente, na Comunidade Envolvente, na Família, no responsável pelo Projecto e nos alunos) e que, muitas vezes, esses impactos só se verificam a longo prazo. Verificamos também que a implementação destes projectos segue três princípios essenciais: a planificação, a realização e a avaliação sendo que as escolas tentam integrar os projectos no seu Projecto Educativo. As maiores dificuldades sentidas verificaram-se a nível da organização da escola, da carga burocrática inerente ao projecto e do pouco envolvimento e participação de alguns professores. Sugere-se que a Escola aposte cada vez mais na implementação deste tipo de projectos, pois estes podem contribuir para uma Escola mais democrática, mais flexível, com mais qualidade, mais motivadora e mais Europeia. ABSTRACT; The aim of this study was to understand and to identify the biggest impacts that the Community's education-related action programmes "Socrates" (namely Comenius 1) have in the School policy. So, the central question of this research was to find out, from the coordinators points of view, which were the most important impacts of the Comenius projects. This central question led to the formulation of the following three questions: a) How were the Comenius projects implemented at school? b) How were the Comenius projects integrated in school organisation and structure? c) Which were the difficulties coordinators had to face in order to organize and implement a Comenius project? Using a qualitative methodology, semi-structured interviews were held with five teachers from different schools in the region of Silves. The following instruments were used during the research: analysis of documents and interviews. The results of the research revealed that the Comenius projects have impacts (although they take a lot of time to be felt) on School, on School heads, on other teachers, on School staff, on the region, on parents, on coordinators and on pupils. They also revealed that the preparation, the activities and the evaluation are important moments to implement Comenius project and that all the projects are included in the School policy. The biggest difficulties had to do with the school organization, with the coordination work and with the lack of motivation and of participation of some colleagues. It is suggested that schools should implement more Comenius projects, because they can lead to a more democratic, flexible, motivating and European School

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

A Hexanuclear Mixed-Valence Oxovanadium(IV,V) Complex as a Highly Efficient Alkane Oxidation Catalyst

The new hexanuclear mixed-valence vanadium complex [V3O3(OEt)(ashz)(2)(mu-OEt)](2) (1) with an N,O-donor ligand is reported. It acts as a highly efficient catalyst toward alkane oxidations by aqueous H2O2. Remarkably, high turnover numbers up to 25000 with product yields of up to 27% (based on alkane) stand for one of the most active systems for such reactions

Fe(III) complexes in cyclohexane oxidation: comparison of catalytic activities under different energy stimuli

In this study, the mononuclear Fe(III) complex [Fe(HL)(NO3)(H2O)2]NO3 (1) derived from N0 -acetylpyrazine-2-carbohydrazide (H2L) was synthesized and characterized by several physicochemical methods, e.g., elemental analysis, infrared (IR) spectroscopy, electrospray ionization mass spectrometry (ESI-MS), and single crystal X-ray diffraction analysis. The catalytic performances of 1 and the previously reported complexes [Fe(HL)Cl2] (2) and [Fe(HL)Cl(µ-OMe)]2 (3) towards the peroxidative oxidation of cyclohexane under three different energy stimuli (microwave irradiation, ultrasound, and conventional heating) were compared. 1-3 displayed homogeneous catalytic activity, leading to the formation of cyclohexanol and cyclohexanone as final products, with a high selectivity for the alcohol (up to 95%). Complex 1 exhibited the highest catalytic activity, with a total product yield of 38% (cyclohexanol + cyclohexanone) under optimized microwave-assisted conditions.info:eu-repo/semantics/publishedVersio

Trends in properties of para-substituted 3-(phenylhydrazo)pentane-2,4-diones

Trends between the Hammett's sigma(p) and related normal sigma(n)(p), inductive sigma(I), resonance sigma(R), negative sigma(-)(p) and positive sigma(+)(p) polar conjugation and Taft's sigma(o)(p) substituent constants and the N-H center dot center dot center dot O distance, delta(N-H) NMR chemical shift, oxidation potential (E-p/2(ox), measured in this study by cyclic voltammetry (CV)) and thermodynamic parameters (pK, Delta G(0), Delta H-0 and Delta S-0) of the dissociation process of unsubstituted 3-(phenylhydrazo)pentane-2,4-dione (HL1) and its para-substituted chloro (HL2), carboxy (HL3), fluoro (HL4) and nitro (HL5) derivatives were recognized. The best fits were found for sigma(p) and/or sigma(-)(p) in the cases of d(N center dot center dot center dot O), delta(N-H) and E-p/2(ox), showing the importance of resonance and conjugation effects in such properties, whereas for the above thermodynamic properties the inductive effects (sigma(I)) are dominant. HL2 exists in the hydrazo form in DMSO solution and in the solid state and contains an intramolecular H-bond with the N center dot center dot center dot O distance of 2.588(3)angstrom. It was also established that the dissociation process of HL1-5 is non-spontaneous, endothermic and entropically unfavourable, and that the increase in the inductive effect (sigma(I)) of para-substitutents (-H < -Cl < -COOH < -F < -NO2) leads to the corresponding growth of the N center dot center dot center dot O distance and decrease of the pK and of the changes of Gibbs free energy, of enthalpy and of entropy for the HL1-5 acid dissociation process. The electrochemical behaviour of HL1-5 was interpreted using theoretical calculations at the DFT/HF hybrid level, namely in terms of HOMO and LUMO compositions, and of reactivities induced by anodic and cathodic electron-transfers. Copyright (C) 2010 John Wiley & Sons, Ltd

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

Synthesis and Coordination Chemistry of a New N-4-Polydentate Class of Pyridyl-Functionalized Scorpionate Ligands: Complexes of Fe-II, Zn-II, V-IV, Pd-II and Use for Heterobimetallic Systems

The new potentially N-4-multidentate pyridyl-functionalized scorpionates 4-((tris-2,2,2-(pyrazol-1-ypethoxy)methyl)pyridine (TpmPy, (1)) and 4-((tris-2,2,2-(3-phenylpyrazol-1-yl)ethoxy)methyl)pyridine (TpmPy(Ph), (2)) have been synthesized and their coordination behavior toward Fe-II, Ni-II, Zn-II, Cu-II, Pd-II, and V-III centers has been studied. Reaction of (1) with Fe(BF4)(2)center dot 6H(2)O yields [Fe(TpmPy)(2)](BF4)(2) (3), that, in the solid state, shows the sandwich structure with trihapto ligand coordination via the pyrazolyl arms, and is completely low spin (LS) until 400 K. Reactions of 2 equiv of (1) or (2) with Zn-II or Ni-II chlorides give the corresponding metal complexes with general formula [MCl2(TpmPy*)(2)] (M = Zn, Ni; TpmPy* = TpmPy, TpmPy(Ph)) (4-7) where the ligand is able to coordinate through either the pyrazolyl rings (in case of [Ni(TpmPy)(2)Cl-2 (5)) or the pyridyl-side (for [ZnCl2(TpmPy)(2)] (4), [ZnCl2(TpmPy(Ph))(2)] (6) and [NiCl2(TpmPy(Ph))(2)] (7)). The reaction of (1) with VCl3 gives [VOCl2(TpmPy)] (8) that shows the N-3-pyrazolyl coordination-mode. Moreover, (1) and react with cis-[PdCl2(CH3CN)(2)] to give the disubstituted complexes [PdCl2(TprnPy)(2)] (9) and [PdCl2(TpmPy(Ph))(2)] (10), respectively, bearing the scorpionate coordinated via the pyridyl group. Compounds (9) and (10) react with Fe(BF4)(2) to give the heterobimetallic Pd/Fe systems [PdCl2(mu-TpmPy)(2)-Fe](BF4)(2) (11) and [PdCl2(mu-TpmPy(Ph))(2)Fe-2(H2O)(6)]BF4)(4) (13), respectively. Compound (11) can also be formed from reaction of (3) with cis-[PdCl2(CH3CN)(2)], while reaction of (3) with Cu(NO3)(2).2.5H(2)O generates [Fe(mu-TpmPy)(2)-Cu(NO3)(2)](BF4)(2) (12), confirming the multidentate ability of the new chelating ligands. The X-ray diffraction analyses of compounds (1), (3), (4), (5), and (9) are also reported