999 resultados para Põld, Peeter: Valitud tööd. 1
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Solubilities of red 153, (3-[[4-[[5,6(or 6,7)-dichloro-2-benzothiazolyl]azo]phenyl]ethylamino]propanenitrile), an azo compound, and disperse blue1 (1,4,5,8-tetraaminoantraquinone) in supercritical carbon dioxide (SC CO(2)) were measured at T = (333.2 to 393.2) K over the pressure range (12.0 to 40.0) MPa by a flow type apparatus. The solubility of red 153 (0.985. 10(-6) to 37.2. 10(-6)) in the overall region of measurements is found to be significantly higher than that of disperse blue 1 (1.12.10(-7) to 4.89.10(-7)). The solubility behavior of disperse red 153 follows the general solubility trend displayed by disperse dyes with a crossover pressure at about 20 MPa. On the other hand, blue 1, which is a disperse anthraquinone dye, exhibits unexpected behavior not recorded previously there is no crossover pressure at the temperature and pressure ranges studied, and the dye's solubility at T = 333.2 K practically does not increase with pressure. To the best of our knowledge, there are no previous measurements of blue 1 solubility in SC CO(2) reported in the literature. The experimental data were correlated by using the Soave Redlich Kwong equation of state (EoS) with the one-fluid van der Waals mixing rule, and an acceptable correlation of the solubility data for both dyes was obtained.
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The organotin(IV) compounds [Me2Sn(L)(2)] (1), [Et(2)sn(L)(2)] (2), [(Bu2Sn)-Bu-n(L)(2)] (3), [(n)Oct(2)Sn(L)(2)] (4), [Ph2Sn(L)(2)] (5), and [PhOSnL](6) (6) have been synthesized from the reactions of 1-(4-chlorophenyl)-1-cyclopentanecarboxylic acid (HL) with the corresponding diorganotin(IV) oxide or dichloride. They were characterized by IR and multinuclear NMR spectroscopies, elemental analysis, cyclic voltammetry, and, for 2, 3, 4 and 6, single crystal X-ray diffraction analysis. While 1-5 are mononuclear diorganotin (IV) compounds, the X-ray diffraction of 6 discloses a hexameric drumlike structure with a prismatic Sn6O6 core. All these complexes undergo irreversible reductions and were screened for their in vitro antitumor activities toward HL-60, BGC-823, Bel-7402, and KB human cancer cell lines. Within the mononuclear compounds, the most active ones (3, 5) are easiest to reduce (least cathodic reduction potentials), while the least active ones (1, 4) are the most difficult to reduce. Structural rearrangements (i.e., Sn-O bond cleavages and trans-to-cis isomerization) induced by reduction, which eventually can favor the bioactivity, are disclosed by theoretical/electrochemical studies.
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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.
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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.
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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.
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Dissertação apresentada à Escola Superior de Educação de Lisboa para obtenção de grau de mestre em Ciências da Educação, especialização Supervisão em Educação
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Dissertação Apresentada à Escola Superior de Educação de Lisboa para obtenção de grau de mestre em Ciências da Educação - Especialidade Supervisão em Educação
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Dissertação apresentada à Escola Superior de Educação de Lisboa para obtenção de grau de mestre em Ciências da Educação, especialidade Educação Especial – Problemas Cognitivos e Multideficiência
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Projeto de Intervenção apresentado à Escola Superior de Educação de Lisboa para obtenção de grau de mestre em Ciências da Educação - Especialidade Educação Especial
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Dissertação apresentada à Escola Superior de Educação de Lisboa para obtenção de grau de mestre em Ciências da Educação, especialidade em Educação Artística -Teatro na Educação
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Dissertação apresentada à Escola Superior de Educação de Lisboa para obtenção de grau de mestre em Ciências da Educação, Especialidade em Educação Artística – Teatro na Educação
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Mestrado em Intervenção Sócio-Organizacional na Saúde. Área de especialização: Políticas de Administração e Gestão dos Serviços de Saúde.
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Power systems are planed and operated according to the optimization of the available resources. Traditionally these tasks were mostly undertaken in a centralized way which is no longer adequate in a competitive environment. Demand response can play a very relevant role in this context but adequate tools to negotiate this kind of resources are required. This paper presents an approach to deal with these issues, by using a multi-agent simulator able to model demand side players and simulate their strategic behavior. The paper includes an illustrative case study that considers an incident situation. The distribution company is able to reduce load curtailment due to load flexibility contracts previously established with demand side players.
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Presently power system operation produces huge volumes of data that is still treated in a very limited way. Knowledge discovery and machine learning can make use of these data resulting in relevant knowledge with very positive impact. In the context of competitive electricity markets these data is of even higher value making clear the trend to make data mining techniques application in power systems more relevant. This paper presents two cases based on real data, showing the importance of the use of data mining for supporting demand response and for supporting player strategic behavior.
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Power systems operation in a liberalized environment requires that market players have access to adequate decision support tool, allowing them to consider all the business opportunities and take strategic decisions. Ancillary services represent a good negotiation opportunity that must be considered by market players. For this, decision support tools must include ancillary market simulation. This paper deals with ancillary services negotiation in electricity markets. The proposed concepts and methodologies are implemented in MASCEM, a multi-agent based electricity market simulator. A test case concerning the dispatch of ancillary services using two different methods (Linear Programming and Genetic Algorithm approaches) is included in the paper.