Apropriação de conteúdos do conhecimento explícito da língua por alunos do 2.º ano do 1.º ciclo do ensino básico

Relatório de Estágio apresentado à Escola Superior de Educação de Lisboa para obtenção de grau de mestre em Ensino do 1.º e 2.º Ciclo do Ensino Básico

Complexes of copper(II) with 3-(ortho-substituted phenylhydrazo)pentane-2,4-diones: syntheses,properties and catalytic activity for cyclohexane oxidation

Reactions of copper(II) with 3-phenylhydrazopentane-2,4-diones X-2-C6H4-NHN = C{C(= O)CH3}(2) bearing a substituent in the ortho-position [X = OH (H2L1) 1, AsO3H2 (H3L2) 2, Cl (HL3) 3, SO3H (H2L4) 4, COOCH3 (HL5) 5, COOH (H2L6) 6, NO2 (HL7) 7 or H (HL8) 8] lead to a variety of complexes including the monomeric [CuL4(H2O)(2)]center dot H2O 10, [CuL4(H2O)(2)] 11 and [Cu(HL4)(2)(H2O)(4)] 12, the dimeric [Cu-2(H2O)(2)(mu-HL2)(2)] 9 and the polymeric [Cu(mu-L-6)](n)] 13 ones, often bearing two fused six-membered metallacycles. Complexes 10-12 can interconvert, depending on pH and temperature, whereas the Cu(II) reactions with 4 in the presence of cyanoguanidine or imidazole (im) afford the monomeric compound [Cu(H2O)(4){NCNC(NH2)(2)}(2)](HL4)(2)center dot 6H(2)O 14 and the heteroligand polymer [Cu(mu-L-4)(im)](n) 15, respectively. The compounds were characterized by single crystal X-ray diffraction (complexes), electrochemical and thermogravimetric studies, as well as elemental analysis, IR, H-1 and C-13 NMR spectroscopies (diones) and ESI-MS. The effects of the substituents in 1-8 on the HOMO-LUMO gap and the relative stability of the model compounds [Cu(OH)(L-8)(H2O)]center dot H2O, [Cu(L-1)(H2O)(2)]center dot H2O and [Cu(L-4)(H2O)(2)]center dot H2O are discussed on the basis of DFT calculations that show the stabilization follows the order: two fused 6-membered > two fused 6-membered/5-membered > one 6-membered metallacycles. Complexes 9, 10, 12 and 13 act as catalyst precursors for the peroxidative oxidation (with H2O2) of cyclohexane to cyclohexanol and cyclohexanone, in MeCN/H2O (total yields of ca. 20% with TONs up to 566), under mild conditions.

Prática de ensino supervisionado no 1.º e 2.º ciclo do ensino básico: o TEA como estratégia de implicação do aluno no seu processo de ensino aprendizagem

Relatório Final apresentado à Escola Superior de Educação de Lisboa para obtenção do grau de mestre em Ensino do 1º e do 2º Ciclo de Ensino Básico

Halogen-bonded tris (2,4-Bis(trichloromethyl)-1,3,5,triazapentadienato)-M(III) [M = Mn, Fe, Co] complexes and their catalytic activity in the peroxidative oxidation of 1-phenylethanol to acetophenone

One-pot template condensation of CCl3C=N with ammonia on a metal source [MnCl2 center dot 4H(2)O, FeCl3 center dot 6H(2)O or Co(CH3COO)(2)center dot 4H(2)O] in DMSO led to the formation of tris(2,4-bis(trichloromethyl)-1,3,5-triazapentadienato)-M(III) complexes, [M(NH=C(CCl3)NC(CCl3)=-NH}(3)]center dot n(CH3)(2)SO [M = Mn, n = 1 (1); M = Fe, n = 2 (2); M = Co, n = 2 (3)1, which were characterized using elemental analysis, and IR, ESI-MS and single-crystal X-ray analysis. The role of inter- and intramolecular non-covalent halogen and hydrogen bonds in the synthesis of 1-3 is discussed. It is shown that the crystal ionic radii of the metal ions [68.5 (Co) < 69 (Fe) < 72 (Mn), pm] are related to the corresponding Cl center dot center dot center dot Cl distances [3.178 (3) > 3.155 (2) > 3.133 (1) Al. Compounds 1-3 and the related di(triazapentadienato)-Cu(v) complex [Cu(NH=C(CCl3)NC(CCl3)=NH}2]center dot 2(CH3)(2)SO (4) act as catalyst precursors for the additive-free microwave (MW) assisted homogeneous oxidation of 1-phenylethanol with tert-butylhydroperoxide (TBHP), leading to the formation of acetophenone with yields up to 99% and TONs up to 5.0 x 10(3) after 1 h of low power (10 W) MW irradiation.

Composition and antioxidant activity of thymus vulgaris volatiles: comparison between supercritical fluid extraction and hydrodistillation

Supercritical fluid extraction (SEE) of the volatile oil from Thymus vulgaris L. aerial flowering parts was performed under different conditions of pressure, temperature, mean particle size and CO2 flow rate and the correspondent yield and composition were compared with those of the essential oil isolated by hydrodistillation (HD). Both the oils were analyzed by GC and GC-MS and 52 components were identified. The main volatile components obtained were p-cymene (10.0-42.6% for SFE and 28.9-34.8% for HD), gamma-terpinene (0.8-6.9% for SFE and 5.1-7.0% for HD), linalool (2.3-5.3% for SFE and 2.8-3.1% for HD), thymol (19.5-40.8% for SFE and 35.4-41.6% for HD), and carvacrol (1.4-3.1% for SFE and 2.6-3.1% for HD). The main difference was found to be the relative percentage of thymoquinone (not found in the essential oil) and carvacryl methyl ether (1.0-1.2% for HD versus t-0.4 for SFE) which can explain the higher antioxidant activity, assessed by Rancimat test, of the SFE volatiles when compared with HD. Thymoquinone is considered a strong antioxidant compound.

Molybdenum Complexes Bearing the Tris(1-pyrazolyl)methanesulfonate Ligand: Synthesis, Characterization and Electrochemical Behaviour

The tris(1-pyrazolyl)methanesulfonate lithium salt Li(Tpms) [Tpms = SO3C(pz)(3)-] reacts with [Mo(CO)(6)] in NCMe heated at reflux to yield Li[Mo(Tpms)(CO)(3)] (1), which, upon crystallization from thf, forms the coordination polymer [Mo(Tpms)(CO)(2)(mu-CO)Li(thf)(2)](n) (2). Reaction of 1 with I-2, HBF4 or AgBF4 yields [Mo(Tpms)I(CO)(3)] (3), (Mo(Tpms)-H(CO)(3)] (5) or (Mo(Tpms)O-2](2)(mu-O) (7), respectively. The high-oxidation-state dinuclear complexes [{Mo(Tpms)O(mu-O)}(2)] (4) and [{Mo(tpms)OCl)(2)](mu-O) (6) are formed upon exposure to air of solutions of 3 and 5, respectively. Compounds 1-7, which appear to be the first tris(pyrazolyl)methanesulfonate complexes of molybdenum to be reported, were characterized by IR, H-1 and C-13 NMR spectroscopy, ESI-MS, elemental analysis, cyclic voltammetry and, in the cases of Li(Tpms) and compounds 2, 4.2CH(3)CN, 6.6CHCl(3) and 7, by X-ray diffraction analyses. Li(Tpms) forms a 1D polymeric structure (i.e., [Li(tpms)](n)} with Tpms as a tetradentate N2O2 chelating ligand that bridges two Li cations with distorted tetrahedral coordination. Compound 2 is a 1D coordination polymer in which Tpms acts as a bridging tetradentate N3O ligand and each Li(thf)(2)(+) moiety is coordinated by one bridging CO ligand and by the sulfonyl group of a contiguous monomeric unit. In 4, 6 and 7, the Tpms ligand is a tridentate chelator either in the NNO (in 4) or in the NNN (in 6 and 7) fashion. Complexes 1, 3 and 5 exhibit, by cyclic voltammetry, a single-electron oxidation at oxidation potential values that indicate that the Tpms ligand has an electron-donor character weaker than that of cyclopentadienyl.

Bioconversion of D-glucose into D-glucosone by Glucose 2-oxidase from Coriolus versicolor at Moderate Pressures

Glucose 2-oxidase (pyranose oxidase, pyranose: oxygen-2-oxidoreductase, EC 1.1.3.10) from Coriolus versicolor catalyses the oxidation of D-glucose at carbon 2 in the presence of molecular O(2) producing D-glucosone (2-keto-glucose and D-arabino-2-hexosulose) and H(2)O(2). It was used to convert D-glucose into D-glucosone at moderate pressures (i.e. up to 150 bar) with compressed air in a modified commercial batch reactor. Several parameters affecting biocatalysis at moderate pressures were investigated as follows: pressure, [enzyme], [glucose], pH, temperature, nature of fluid and the presence of catalase. Glucose 2-oxidase was purified by immobilized metal affinity chromatography on epoxy-activated Sepharose 6B-IDA-Cu(II) column at pH 6.0. The rate of bioconversion of D-glucose increased with the pressure since an increase in the pressure with compressed air resulted in higher rates of conversion. On the other hand, the presence of catalase increased the rate of reaction which strongly suggests that H(2)O(2) acted as inhibitor for this reaction. The rate of bioconversion of D-glucose by glucose 2-oxidase in the presence of either nitrogen or supercritical CO(2) at 110 bar was very low compared with the use of compressed air at the same pressure. The optimum temperature (55 degrees C) and pH (5.0) of D-glucose bioconversion as well as kinetic parameters for this enzyme were determined under moderate pressure. The activation energy (E(a)) was 32.08 kJmol(-1) and kinetic parameters (V(max), K(m), K(cat) and K(cat)/K(m)) for this bioconversion were 8.8 Umg(-1) protein, 2.95 mM, 30.81 s(-1) and 10,444.06 s(-1)M(-1), respectively. The biomass of C. versicolor as well as the cell-free extract containing glucose 2-oxidase activity were also useful for bioconversion of D-glucose at moderate pressures. The enzyme was apparently stable at moderate pressures since such pressures did not affect significantly the enzyme activity.

Bioconversion of D-glucose into D-glucosone by immobilized glucose 2-oxidase from Coriolus versicolorat moderate pressures

The immobilized glucose 2-oxidase (pyranose oxidase, pyranose:oxygen-2-oxidoreductase, EC 1.1.3.10) from Coriolus versicolor was used to convert D-glucose into D-glucosone at moderate pressures, up to 150 bar, with compressed air in a modified commercial batch reactor. Several parameters affecting biocatalysis at moderate pressures were investigated as follows: pressure, different forms of immobilized biocatalysts, glucose concentration, pH, temperature and the presence of catalase. Glucose 2-oxidase (GOX2) was purified by immobilized metal affinity chromatography on epoxy-activated Sepharose 6B-IDA-Cu(II) column at pH 6.0. Purified enzyme and catalase were immobilized into a polyethersulfone (PES) membrane in the presence of glutaraldehyde and gelatin. Enhancement of the bioconversion of D-glucose was done by the pressure since an increase in the pressure with compressed air increases the conversion rates. The optimum temperature and pH for bioconversion of D-glucose were found to be 62 degrees C and pH 6.0, respectively and the activation energy (E(a)) was 28.01 kJ mol(-1). The apparent kinetic constants (V(max)' K(m)', K(cat)' and K(cat)/K(m)') for this bioconversion were 2.27 U mg(-1) protein, 11.15 mM, 8.33 s(-1) and 747.38 s(-1) M(-1), respectively. The immobilized biomass of C. versicolor as well as crude extract containing GOX2 activity were also useful for bioconversion of D-glucose at 65 bar with a yield of 69.9 +/- 3.8% and 91.3 +/- 1.2%, respectively. The immobilized enzyme was apparently stable for several months without any significant loss of enzyme activity. On the other hand, this immobilized enzyme was also stable at moderate pressures, since such pressures did not affect significantly the enzyme activity. (C) 2010 Elsevier Ltd. All rights reserved.

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.

On the solubility of three disperse anthraquinone dyes in supercritical carbon dioxide: new experimental data and correlation

Solubility measurements of quinizarin. (1,4-dihydroxyanthraquinone), disperse red 9 (1-(methylamino) anthraquinone), and disperse blue 14 (1,4-bis(methylamino)anthraquinone) in supercritical carbon dioxide (SC CO2) were carried out in a flow type apparatus, at a temperature range from (333.2 to 393.2) K and at pressures from (12.0 to 40.0) MPa. Mole fraction solubility of the three dyes decreases in the order quinizarin (2.9 x 10(-6) to 2.9.10(-4)), red 9 (1.4 x 10(-6) to 3.2 x 10(-4)), and blue 14 (7.8 x 10(-8) to 2.2 x 10(-5)). Four semiempirical density based models were used to correlatethe solubility of the dyes in the SC CO2. From the correlation results, the total heat of reaction, heat of vaporization plus the heat of solvation of the solute, were calculated and compared with the results presented in the literature. The solubilities of the three dyes were correlated also applying the Soave-Redlich-Kwong cubic equation of state (SRK CEoS) with classical mixing rules, and the physical properties required for the modeling were estimated and reported.

Microscopic Theory of Anchoring Transitions at the Surfaces of Pure Liquid-Crystals and their Mixtures .1. The Fowler Approximation

We have generalized earlier work on anchoring of nematic liquid crystals by Sullivan, and Sluckin and Poniewierski, in order to study transitions which may occur in binary mixtures of nematic liquid crystals as a function of composition. Microscopic expressions have been obtained for the anchoring energy of (i) a liquid crystal in contact with a solid aligning surface; (ii) a liquid crystal in contact with an immiscible isotropic medium; (iii) a liquid crystal mixture in contact with a solid aligning surface. For (iii), possible phase diagrams of anchoring angle versus dopant concentration have been calculated using a simple liquid crystal model. These exhibit some interesting features including re-entrant conical anchoring, for what are believed to be realistic values of the molecular parameters. A way of relaxing the most drastic approximation implicit in the above approach is also briefly discussed.

A metáfora e a imagem : estratégias pedagógicas no processo de ensino-aprendizagem na aula de Técnica de Dança Moderna com os alunos dos 2º e 3º anos do ensino vocacional na Academia de Dança Contemporânea de Setúbal

Relatório Final de Estágio apresentado à Escola Superior de Dança, com vista à obtenção do grau de Mestre emMetodologias do Ensino da Dança.

Strabismus, visual acuity, and uncorrected refractive error in Portuguese children aged 6 to 11 years

Introduction: Visual anomalies that affect school-age children represent an important public health problem. Data on the prevalence are lacking in Portugal but is needed for planning vision services. This study was conducted to determine the prevalence of strabismus, decreased visual acuity, and uncorrected refractive error in Portuguese children aged 6 to 11 years. Methods and materials: A cross-sectional study was carried out on a sample of 672 school-age children (7.69 ± 1.19 years). Children received an orthoptic assessment (visual acuity, ocular alignment, and ocular movements) and non-cycloplegic autorefraction. Results: After orthoptic assessment, 13.8% of children were considered abnormal (n = 93). Manifest strabismus was found in 4% of the children. Rates of esotropia (2.1%) were slightly higher than exotropia (1.8%). Strabismus rates were not statistically significant different per sex (p = 0.681) and grade (p = 0.228). Decreased visual acuity at distance was present in 11.3% of children. Visual acuity ≤20/66 (0.5 logMAR) was found in 1.3% of the children. We also found that 10.3% of children had an uncorrected refractive error. Conclusions: Strabismus affects a small proportion of the Portuguese school-age children. Decreased visual acuity and uncorrected refractive error affected a significant proportion of school-age children. New policies need to be developed to address this public health problem.