Preparação e análise estrutural de complexos de samário

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química e Biológica - Ramo de Bioprocessos

Constructing and Using Multimodal Narratives to Research in Science Education: Contributions Based on Practical Classroom

This study deals with the problem of how to collect genuine and useful data about science classroom practices, and preserving the complex and holistic nature of teaching and learning. Additionally, we were looking for an instrument that would allow comparability and verifiability for teaching and research purposes. Given the multimodality of teaching and learning processes, we developed the multimodal narrative (MN), which describes what happens during a task and incorporates data such as examples of students’ work.

Acessibilidade à atenção básica a famílias negras em bairro popular de Salvador, Brasil

OBJETIVO: Analisar a acessibilidade de famílias negras de bairro popular aos serviços de atenção básica à saúde. MÉTODOS: Estudo etnográfico, ancorado na antropologia de base interpretativa, realizado com 18 famílias selecionadas de um bairro popular de Salvador, BA, no período de dois anos. Os critérios de inclusão foram residência no bairro e autoclassificação como negros. A análise se baseou na antropologia interpretativa e considerou as categorias: autorreferência étnico-racial; experiências de discriminação nos serviços; percepção sobre acessibilidade na atenção básica; e barreiras de acessibilidade. RESULTADOS E DISCUSSÃO: Identificaram-se os seguintes aspectos: a) identidade étnico-racial e saúde: percepção dos usuários de que as barreiras organizacionais e de acesso se devem a um amplo contexto social que produz cidadãos "de primeira e de segunda categorias", mais do que a um racismo institucional; b) acessibilidade no Sistema Único de Saúde (SUS): acesso problemático, permeado pela demora no atendimento, falta de compromisso dos profissionais de saúde, omissão dos gestores no controle e correção dessas situações; c) acessibilidade na atenção básica: visão sobre o contexto mais geral do SUS e apoio na descrição dos entrevistados sobre o acesso aos serviços de atenção básica. CONCLUSÕES: Há barreiras de acessibilidade econômicas, organizacionais e culturais que se interpõem entre a oferta de serviços e o atendimento efetivo e oportuno das necessidades da população estudada.

Fatores maternos e neonatais associados ao mecônio no líquido amniótico em um centro de parto normal

OBJETIVO: Analisar a frequência e os fatores maternos e neonatais associados ao mecônio no líquido amniótico no parto. MÉTODOS: Estudo transversal com 2.441 nascimentos em um centro de parto normal hospitalar em São Paulo, SP, em março e abril de 2005. A associação entre mecônio no líquido amniótico e as variáveis independentes (idade materna, paridade, ter ou não cesariana prévia, idade gestacional, antecedentes obstétricos, uso de ocitocina no trabalho de parto, dilatação cervical na admissão, tipo do parto atual, peso do RN, índice de Apgar de 1º e 5º minutos de vida) foi expressa como razão de prevalência. RESULTADOS: Verificou-se mecônio no líquido amniótico em 11,9% dos partos; 68,2% desses foram normais e 38,8%, cesarianas. O mecônio esteve associado a: primiparidade (RP = 1,49; IC95% 1,29;1,73), idade gestacional ≥ 41 semanas (RP = 5,05; IC95% 1,93;13,25), ocitocina no parto (RP = 1,83, IC95% 1,60;2,10), cesariana (RP = 2,65; IC95% 2,17;3,24) e índice de Apgar < 7 no 5º minuto (RP = 2,96, IC95% 2,94;2,99). A mortalidade neonatal foi 1,6/1.000 nascidos vivos; mecônio no líquido amniótico foi encontrado em 50% das mortes neonatais e associado a maiores taxas de partos cirúrgicos. CONCLUSÕES: Emprego de ocitocina, piores condições do recém-nascido logo após o parto e aumento de taxas de cesariana foram fatores associados ao mecônio. A utilização rotineira de ocitocina no intraparto poderia ser revista por sua associação com mecônio no líquido amniótico.

A Biotecnologia na esfera pública

Este trabalho foca o envolvimento de cidadãos ligados à agricultura, à I&D agronómica e ao meio rural em assuntos de inovação na agricultura,tomando como caso de estudo ‘a biotecnologia na agricultura’ designada por agrobiotecnologia ou biotecnologia verde, na qual se incluem os organismos geneticamente modificados (‘OGM’) ou transgénicos. O seu uso na agricultura tem gerado desacordo entre os seus adeptos e os seus opositores, incluindo-se nestes dois grupos diversos actores. Pelo facto de à sua inerente complexidade técnico- científica acrescer uma vasta gama de implicações sócio- políticoeconómicas, este assunto tem sido objecto de estudos reveladores da existência de diversos modos de cobertura mediática e de mecanismos de regulação que vão a par de diferentes padrões de percepções públicas. Esta teia de complexidade poderá ter influído nas políticas do sector agrícola, que evidenciou maior apoio, a nível comunitário e nacional, à agricultura biológica. A persistência, por mais de uma década, da polarização sobre este assunto, que mobilizou, entre outros actores, alguns cientistas, associada ao facto de existirem diferentes percepções de risco e benefício ligadas a várias aplicações, não só em diferentes países e culturas, mas também entre os indivíduos de um dado país, e nestes indivíduos em momentos e contextos diferentes, indiciam que a abordagem deste assunto em termos estritamente científicos e que exclui as preocupações existentes tenderá a perpetuar a polarização e a estagnação. No seguimento da Comissão Europeia ter reconhecido a importância da comunicação da investigação, da abertura e do contacto dos investigadores com a sociedade (CE, COM 2004- 250) pressupõe-se que os cidadãos são actores com os quais se pode trocar argumentos relevantes sobre este assunto e que os cidadãos minimamente esclarecidos possuem capacidade de articular ideias sobre implicações sociais da biotecnologia na agricultura. A análise da percepção de actores envolvidos neste assunto permite identificar áreas de conflito que requerem particular atenção na construção de políticas públicas mais eficientes e fundamentadas. Para tal, neste trabalho, mediante metodologias participativas foram analisadas as percepções dos actores chave envolvidos, tendo-se chegado a resultados que, relativamente à Informação e Comunicação realçaram ‘o fraco esclarecimento público existente em Portugal sobre OGM’ e ‘a necessidade de revitalizar a extensão rural’’, e no que se refere à mediação entre Ciência e Política, foi realçada à ineficácia dos políticos na actualização de conhecimentos sobre o tema’. Do mapeamento de preocupações efectuado, realçam-se a ‘desigual partilha de benefícios e riscos’; ‘a sobreposição de critérios económicos a abordagens cautelosas’ e ‘a eventual perda de valor de fileiras/produtos agrícolas com cariz tradicional forte (fileira vitícola) caso nelas(es) se incorporassem tecnologias de modificação genética’. O envolvimento neste assunto de jovens do ensino profissional agrícola, num projecto piloto educativo, e de agricultores, cientistas e outros actores ligados ao sector agrícola, em processos participativos de tipo focus grupos, permite uma partilha de informação e uma clarificação das suas preocupações, de potencial utilidade ao delinear de futuras linhas de I&D e políticas neste âmbito, sobretudo quando a nível nacional é inexistente uma estratégia clara para a biotecnologia na agricultura, constituindo estas iniciativas de envolvimento dos cidadãos um contributo para o desenvolvimento de capital social neste âmbito.

Variações do repertório clássico nas aulas de Técnica de Dança Clássica do 4º e do 5º ano da Escola de Dança Ana Mangerição

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

Impact of a training course on the quality of malaria diagnosis by microscopy in Angola

Background: In Angola, malaria is an endemic disease having a major impact on the economy. The WHO recommends testing for all suspected malaria cases, to avoid the presumptive treatment of this disease. In malaria endemic regions laboratory technicians must be very comfortable with microscopy, the golden standard for malaria diagnosis, to avoid the incorrect diagnosis. The improper use of medication promotes drug resistance and undesirable side effects. The present study aims to assess the impact of a three-day refresher course on the knowledge of technicians, quality of blood smears preparation and accuracy of microscopy malaria diagnosis, using qPCR as reference method. Methods: This study was implemented in laboratories from three hospitals in different provinces of Angola: Bengo, Benguela and Luanda. In each laboratory samples were collected before and after the training course (slide with thin and thick blood smears, a dried blood spot and a form). The impact of the intervention was evaluated through a written test, the quality of slide preparation and the performance of microscopy. Results: It was found a significant increase on the written test median score, from 52.5% to 65.0%. A total of 973 slides were analysed to evaluate the quality of thick and thin blood smears. Considering all laboratories there was a significant increase in quality of thick and thin blood smears. To determine the performance of microscopy using qPCR as the reference method we used 1,028 samples. Benguela presented the highest values for specificity, 92.9% and 98.8% pre and post-course, respectively and for sensitivity the best pre-course was Benguela (75.9%) and post-course Luanda (75.0%). However, no significant increase in sensitivity and specificity after the training course was registered in any laboratory analysed. Discussion: The findings of this study support the need of continuous refresher training for microscopists and other laboratory staff. The laboratories should have a quality control programme to supervise the diagnosis and also to assess the periodicity of new training. However, other variables needed to be considered to have a correct malaria diagnosis, such as adequate equipment and reagents for staining and visualization, good working conditions, motivated and qualified personnel.

Healthcare-associated infections: challenges to public health in Brazil

This study presents a critical evaluation of the scientific literature related to this subject, aiming to assess the policies and administrative issues regarding the prevention and magnitude of healthcare-associated infections and discuss the challenges for their prevention in Brazil. The topics discussed included historical and administrative issues, challenges imposed by the characteristics of the healthcare system and the territorial dimension, laboratorial support limitations, costs, institutional culture, professional qualification, and patient engagement. It is urgent to hold a nationwide discussion among government representatives, institutions, and healthcare workers and users to overcome these challenges.

Dinuclear Mn (II,II) complexes: magnetic properties and microwave assisted oxidation of alcohols

A series of six new mixed-ligand dinuclear Mn(II, II) complexes of three different hydrazone Schiff bases (H3L1, H3L2 and H3L3), derived from condensation of the aromatic acid hydrazides benzohydrazide, 2-aminobenzohydrazide or 2-hydroxybenzohydrazide, with 2,3-dihydroxy benzaldehyde, respectively, is reported. Reactions of Mn(NO3)(2) center dot 4H(2)O with the H3L1-3 compounds, in the presence of pyridine (1 : 1 : 1 mole ratio), in methanol at room temperature, yield [Mn(H2L1)(py)(H2O)](2)(NO3)(2) center dot 2H(2)O (1 center dot 2H(2)O), [Mn(H2L2)(py)(CH3OH)](2)(NO3)(2) center dot 4H(2)O (2 center dot 4H(2)O) and [Mn(H2L3)(py)(H2O)](2)(NO3)(2) (3) respectively, whereas the use of excess pyridine yields complexes with two axially coordinated pyridine molecules at each Mn(II) centre, viz. [Mn(H2L1)(py)(2)] 2(NO3)(2) center dot H2O (4 center dot H2O), [Mn(H2L2)(py) H-O (6 center dot 2CH(3)OH), respectively. In all the complexes, the (H2L1-3)-ligand coordinates in the keto form. Complexes 1 center dot 2H(2)O, 2 center dot 4H(2)O, 4 center dot H2O, 5 center dot 2H(2)O and 6 center dot 2CH(3)OH are characterized by single crystal X-ray diffraction analysis. The complexes 1, 2 and 6, having different coordination environments, have been selected for variable temperature magnetic susceptibility measurements to examine the nature of magnetic interaction between magnetically coupled Mn(II) centres and also for exploration of the catalytic activity towards microwave assisted oxidation of alcohols. A yield of 81% (acetophenone) is obtained using a maximum of 0.4% molar ratio of catalyst relative to the substrate in the presence of TEMPO and in aqueous basic solution, under mild conditions.

Mu-Chlorido-Bridged Dimanganese(II) complexes of the schiff base derived from [2+2] condensation of 2,6-diformyl-4-methylphenol and 1,3-bis(3-aminopropyl)tetramethyldisloxane: structure, magnetismo, electrochemical behaviour, and catalytic oxidation of secondary alcohols

The reaction of 2,6-diformyl-4-methylphenol with 1,3-bis(3-aminopropyl)tetramethyldisiloxane in the presence of MnCl2 in a 1:1:2 molar ratio in methanol afforded a dinuclear -chlorido-bridged manganese(II) complex of the macrocyclic [2+2] condensation product (H2L), namely, [Mn2Cl2(H2L)(HL)]Cl center dot 3H(2)O (1). The latter afforded a new compound, namely, [Mn2Cl2(H2L)(2)][MnCl4]center dot 4CH(3)CN center dot 0.5CHCl(3 center dot)0.4H(2)O (2), after recrystallisation from 1:1 CHCl3/CH3CN. The co-existence of the free and complexed azomethine groups, phenolato donors, mu-chlorido bridges, and the disiloxane unit were well evidenced by ESI mass spectrometry and FTIR spectroscopy and confirmed by X-ray crystallography. The magnetic measurements revealed an antiferromagnetic interaction between the two high-spin (S = 5/2, g = 2) manganese(II) ions through the mu-chlorido bridging ligands. The electrochemical behaviour of 1 and 2 has been studied, and details of their redox properties are reported. Both compounds act as catalysts or catalyst precursors in the solvent-free low-power microwave-assisted oxidation of selected secondary alcohols, for example, 1-phenylethanol, cyclohexanol, 2- and 3-octanol, to the corresponding ketones in the absence of solvent. The highest yield of 72% was achieved for 1-phenylethanol by using a maximum of 1% molar ratio of catalyst relative to substrate.

New RuII(arene) complexes with halogen-substituted bis- and tris(pyrazol-1-YL)borate ligands

[RuCl(arene)(-Cl)](2) dimers were treated in a 1:2 molar ratio with sodium or thallium salts of bis- and tris(pyrazolyl)borate ligands [Na(BpBr3)], [Tl(TpBr3)], and [Tl(Tp(iPr,4Br))]. Mononuclear neutral complexes [RuCl(arene)((2)-BpBr3)] (1: arene=p-cymene (cym); 2: arene=hexamethylbenzene (hmb); 3: arene=benzene (bz)), [RuCl(arene)((2)-TpBr3)] (4: arene=cym; 6: arene=bz), and [RuCl(arene)((2)-Tp(iPr,4Br))] (7: arene=cym, 8: arene=hmb, 9: arene=bz) have been always obtained with the exception of the ionic [Ru-2(hmb)(2)(-Cl)(3)][TpBr3] (5), which formed independently of the ratio of reactants and reaction conditions employed. The ionic [Ru(CH3OH)(cym)((2)-BpBr3)][X] (10: X=PF6, 12: X=O3SCF3) and the neutral [Ru(O2CCF3)(cym)((2)-BpBr3)] (11) have been obtained by a metathesis reaction with corresponding silver salts. All complexes 1-12 have been characterized by analytical and spectroscopic data (IR, ESI-MS, H-1 and (CNMR)-C-13 spectroscopy). The structures of the thallium and calcium derivatives of ligand TpBr3, [Tl(TpBr3)] and [Ca(dmso)(6)][TpBr3](2)2DMSO, of the complexes 1, 4, 5, 6, 11, and of the decomposition product [RuCl(cym)(Hpz(iPr,4Br))(2)][Cl] (7) have been confirmed by using single-crystal X-ray diffraction. Electrochemical studies showed that 1-9 and 11 undergo a single-electron (RuRuIII)-Ru-II oxidation at a potential, measured by cyclic voltammetry, which allows comparison of the electron-donor characters of the bis- and tris(pyrazol-1-yl)borate and arene ligands, and to estimate, for the first time, the values of the Lever E-L ligand parameter for BpBr3, TpBr3, and Tp(iPr,4Br). Theoretical calculations at the DFT level indicated that both oxidation and reduction of the Ru complexes under study are mostly metal-centered with some involvement of the chloride ligand in the former case, and also demonstrated that the experimental isolation of the (3)-binuclear complex 5 (instead of the mononuclear 5) is accounted for by the low thermodynamic stability of the latter species due to steric reasons.

Evaluating the use of in-store measures in retail food stores and restaurants in Brazil

ABSTRACTOBJECTIVE To assess inter-rater reliability, test-retest reliability, and construct validity of retail food store, open-air food market, and restaurant observation tools adapted to the Brazilian urban context.METHODS This study is part of a cross-sectional observation survey conducted in 13 districts across the city of Sao Paulo, Brazil in 2010-2011. Food store and restaurant observational tools were developed based on previously available tools, and then tested it. They included measures on the availability, variety, quality, pricing, and promotion of fruits and vegetables and ultra-processed foods. We used Kappa statistics and intra-class correlation coefficients to assess inter-rater and test-retest reliabilities in samples of 142 restaurants, 97 retail food stores (including open-air food markets), and of 62 restaurants and 45 retail food stores (including open-air food markets), respectively. Construct validity as the tool’s abilities to discriminate based on store types and different income contexts were assessed in the entire sample: 305 retail food stores, 8 fruits and vegetable markets, and 472 restaurants.RESULTS Inter-rater and test-retest reliability were generally high, with most Kappa values greater than 0.70 (range 0.49-1.00). Both tools discriminated between store types and neighborhoods with different median income. Fruits and vegetables were more likely to be found in middle to higher-income neighborhoods, while soda, fruit-flavored drink mixes, cookies, and chips were cheaper and more likely to be found in lower-income neighborhoods.CONCLUSIONS The measures were reliable and able to reveal significant differences across store types and different contexts. Although some items may require revision, results suggest that the tools may be used to reliably measure the food stores and restaurant food environment in urban settings of middle-income countries. Such studies can help .inform health promotion interventions and policies in these contexts.

Synthesis and characterization of COPPER(II) 4´-phenyl-terpyridine compounds and catalytic application for aerobic oxidation of benzylic alcohols

The reactions between 4'-phenyl-terpyridine (L) and nitrate, acetate or chloride Cu(II) salts led to the formation of [Cu(NO3)(2)L] (1), [Cu(OCOCH3)(2)L]center dot CH2Cl2 (2 center dot CH2Cl2)and [CuCl2L]center dot[Cu(Cl)(mu-Cl)L](2) (3), respectively. Upon dissolving 1 in mixtures of DMSO-MeOH or EtOH-DMF the compounds [Cu(H2O){OS(CH3)(2)}L]-(NO3)(2) (4) and [Cu(HO)(CH3CH2OH)L](NO3) (5) were obtained, in this order. Reaction of 3 with AgSO3CF3 led to [CuCl(OSO2CF3)L] (6). The compounds were characterized by ESI-MS, IR, elemental analysis, electrochemical techniques and, for 2-6, also by single crystal X-ray diffraction. They undergo, by cyclic voltammetry, two single-electron irreversible reductions assigned to Cu(II) -> Cu(I)and Cu(I) -> Cu(0) and, for those of the same structural type, the reduction potential appears to correlate with the summation of the values of the Lever electrochemical EL ligand parameter, which is reported for the first time for copper complexes. Complexes 1-6 in combination with TEMPO (2,2,6,6-tetramethylpiperidinyl-1-oxyl radical) can exhibit a high catalytic activity, under mild conditions and in alkaline aqueous solution, for the aerobic oxidation of benzylic alcohols. Molar yields up to 94% (based on the alcohol) with TON values up to 320 were achieved after 22 h.

Tetranuclear COPPER(II) complexes with macrocyclic and open-chain disiloxane ligands as catalyst precursors for hydrocarboxylation and oxidation of alkanes and 1-phenylethanol

Two new tetranuclear complexes [Cu-4(mu-O)(L-1)-Cl-4] and [Cu-4(mu(4)-O)(L-2)(2)Cl-4] (2), where H2L1 is a macrocyclic ligand resulting from [2+2] condensation of 2,6-diformy1-4-methylphanol (DFF) and 1,3-bis(aminopropy1)tetramethyldisiloxane, and HL2 is a 1:2 condensation product: of DFF with trimethylsilyl p-aminobenzoate, have been prepared. The structures of the products were established by Xray diffraction. The complexes have been characterised by FTIR, UV/Vis spectroscopy, ES1 mass-spectrometry and magnetic susceptibility measurements. The latter revealed that the letrftriuclear complexes can be descr bed as two ferromagnetically coupled dinuclear units, in which the two copper(II) ions interact antiferromacinetically. The ccimpi.iunds act as homogeneous catalyst precursors for a number of single-pot reactions, including (I) hydrocarbaxylation, with CO, H2O and K2S2O8, of a variety of linear and cyclic (n = 5-8) alkanes into the corresponding Cn+1 carboxylic acids, (ii) peroxidative oxidation of cyclohexane, and (iii) solvent-free microwave-assisted oxidation of 1-phenyletha.nol.

µ-Chlorido-bridged dimanganese(II) complexes of the schiff base derived from [2+2] condensation of 2,6-diformyl-4-methylphenol and 1,3-bis(3-aminopropyl)tetramethyldisiloxane: structure, magnetismo, electrochemical behaviour, and catalytic oxidation of secondary alcohols

The reaction of 2,6-diformyl-4-methylphenol with 1,3-bis(3-aminopropyl)tetramethyldisiloxane in the presence of MnCl2 in a 1:1:2 molar ratio in methanol afforded a dinuclear -chlorido-bridged manganese(II) complex of the macrocyclic [2+2] condensation product (H2L), namely, [Mn2Cl2(H2L)(HL)]Cl center dot 3H(2)O (1). The latter afforded a new compound, namely, [Mn2Cl2(H2L)(2)][MnCl4]center dot 4CH(3)CN center dot 0.5CHCl(3 center dot)0.4H(2)O (2), after recrystallisation from 1:1 CHCl3/CH3CN. The co-existence of the free and complexed azomethine groups, phenolato donors, mu-chlorido bridges, and the disiloxane unit were well evidenced by ESI mass spectrometry and FTIR spectroscopy and confirmed by X-ray crystallography. The magnetic measurements revealed an antiferromagnetic interaction between the two high-spin (S = 5/2, g = 2) manganese(II) ions through the mu-chlorido bridging ligands. The electrochemical behaviour of 1 and 2 has been studied, and details of their redox properties are reported. Both compounds act as catalysts or catalyst precursors in the solvent-free low-power microwave-assisted oxidation of selected secondary alcohols, for example, 1-phenylethanol, cyclohexanol, 2- and 3-octanol, to the corresponding ketones in the absence of solvent. The highest yield of 72% was achieved for 1-phenylethanol by using a maximum of 1% molar ratio of catalyst relative to substrate.