N-aminopyrroledione-hydrazonoketene-pyrazolium oxide-pyrazolone rearrangements and pyrazolone tautomerism

Flash vacuum thermolysis (FVT) of 1-(dimethylamino)pyrrole-2,3-diones 5 causes extrusion of CO with formation of transient hydrazonoketenes 7. The transient ketenes 7 are observable in the form of weak bands at 2130 (7a) or 2115 cm(-1) (7b) in the Ar matrix IR spectra resulting from either FVT or photolysis of either 5 or 1,1- dimethylpyrazolium-5- oxides 8, and these absorptions are in excellent agreement with B3LYP/6-31G* frequency calculations. Under FVT conditions the ketenes 7 cyclize to pyrazolium oxides 8, which undergo 1,4-migration of a methyl group to yield 1,4-dimethyl-3-phenylpyrazole-5(4H)-one 9a and 1,4,4-trimethyl-3-phenylpyrazole-5(4H)-one 9b. All three tautomers of 9a have been characterized, viz. the CH form 9a (most stable form in the gas phase, the solid state and solvents of low polarity), the OH form 9a' (metastable solid at room temperature) and the NH form 9a (stable in aprotic dipolar solvents). The isomeric 1,4-dimethyl-5-phenylpyrazole-3(2H)-one 12 tautomerizes to the 3-hydroxypyrazole 12'. The crystal structure of the hydrochloride 14 of 9a'/9a is reported, representing the first structurally characterised example of a protonated 5-hydroxypyrazole.

Model-based analysis of anaerobic acetate uptake by a mixed culture of polyphosphate-accumulating and glycogen-accumulating organisms

An increasing number of studies shows that the glycogen-accumulating organisms (GAOs) can survive and may indeed proliferate under the alternating anaerobic/aerobic conditions found in EBPR systems, thus forming a strong competitor of the polyphosphate-accumulating organisms (PAOs). Understanding their behaviors in a mixed PAO and GAO culture under various operational conditions is essential for developing operating strategies that disadvantage the growth of this group of unwanted organisms. A model-based data analysis method is developed in this paper for the study of the anaerobic PAO and GAO activities in a mixed PAO and GAO culture. The method primarily makes use of the hydrogen ion production rate and the carbon dioxide transfer rate resulting from the acetate uptake processes by PAOs and GAOs, measured with a recently developed titration and off-gas analysis (TOGA) sensor. The method is demonstrated using the data from a laboratory-scale sequencing batch reactor (SBR) operated under alternating anaerobic and aerobic conditions. The data analysis using the proposed method strongly indicates a coexistence of PAOs and GAOs in the system, which was independently confirmed by fluorescent in situ hybridization (FISH) measurement. The model-based analysis also allowed the identification of the respective acetate uptake rates by PAOs and GAOs, along with a number of kinetic and stoichiometric parameters involved in the PAO and GAO models. The excellent fit between the model predictions and the experimental data not involved in parameter identification shows that the parameter values found are reliable and accurate. It also demonstrates that the current anaerobic PAO and GAO models are able to accurately characterize the PAO/GAO mixed culture obtained in this study. This is of major importance as no pure culture of either PAOs or GAOs has been reported to date, and hence the current PAO and GAO models were developed for the interpretation of experimental results of mixed cultures. The proposed method is readily applicable for detailed investigations of the competition between PAOs and GAOs in enriched cultures. However, the fermentation of organic substrates carried out by ordinary heterotrophs needs to be accounted for when the method is applied to the study of PAO and GAO competition in full-scale sludges. (C) 2003 Wiley Periodicals, Inc.

Water sorption into poly[(2-hydroxyethyl methacrylate)-co-(1-vinyl-2-pyrrolidone]at 310 K

Poly(2-hydroxyethyl methacrylate) and copolymers of 2-hydroxyethyl methacrylate (HEMA) and 1-vinyl-2-pyrrolidone (VP) in the form of cylindrical samples (approximate to8mm x 20mm) have been prepared and the sorption of water into these cylinders has been studied by the mass-uptake methods and by magnetic-resonance imaging. The equilibrium water contents for the cylinders were found to vary systematically with the copolymer composition. Diffusion of water into the cylinders was found to follow Fickian behaviour for cylinders with high HEMA contents, with the diffusion coefficients obtained from mass-uptake studies dependent on the copolymer composition, varying from 1.7 x 10(-11) m(2) s(-1) for poly(HEMA) to 2.0 x 10(-11) m(2) s(-1) for poly(HEMA-co-VP) with a composition of 1:1. However, NMR-imaging studies showed that, while the profiles of the water diffusion fronts for cylinders with high HEMA contents were Fickian, that for the 1:1 copolymer was not and indicated that the mechanism was Case III. The polymers which were rich in VP were characterized by a water-sorption process which follows Case-III behaviour. (C) 2003 Society of Chemical Industry.

Comparative study of the radiation-induced grafting of styrene onto poly(tetrafluoroethylene-co-perfluoropropylvinyl ether) and polypropylene substrates. I: Kinetics and structural investigation

A comparative study has been made of the radiation grafting of styrene onto poly(tetrafluoroethylene-co-perfluoropropyl vinyl ether) (PFA) and polypropylene (PP) substrates, using the simultaneous irradiation method. Effects of grafting conditions such as monomer concentrations, type of solvent, dose rate and irradiation dose on the grafting yield were investigated. Under the same grafting conditions it was found that a higher degree of grafting of styrene was obtained using a mixture of dichloromethane/methanol solvents for PFA and methanol for PP and the degree of grafting was higher in PP than in PFA at all doses. However, the micro-Raman spectroscopy analysis of the graft revealed that, for the same degree of grafting, the penetration depth of the grafted polystyrene into the substrate was higher in PFA than in PP substrates. In both polymers the crystallinity was hardly affected by the grafting process and the degree of crystallinity decreased slightly with grafting dose. The dependence of the initial rate of grafting on the dose rate and the monomer concentration was found to be 0.6 and 1.4 order for PFA and 0.15 and 2.2 for PP, respectively. The degree of grafting increased with increasing radiation dose in both polymers. However, the grafting yield decreased with an increase in the dose rate. The increase in the overall grafting yield for PFA and PP was accompanied by a proportional increase in the penetration depth of the graft into the substrates. (C) 2003 Society of Chemical Industry.

Radical formation on gamma-radiolysis of poly [(methacrylic acid)-co-acrylonitri

The radicals formed on gamma-radiolysis of a series of copolymers of methacrylic acid and acrylonitrile have been investigated by ESR spectroscopy. This series of copolymers spanned the full composition range and the study was carried out at 77 K and ambient temperature. The radicals formed in the copolymers at 77 and 303 K were found to be similar to those found in the two homopolymers, but in the intermediate composition range the presence of acrylonitrile propagation radicals was also detected. These radicals were not observed to be formed in significant quantities on the radiolysis of polyacrylonitrile. They are believed to result from a scission of the main chain at methacrylic acid/acrylonitrile diad sequences following loss of the methacrylic acid carboxyl group. At 77 K, the copolymers with high methacrylic acid contents were found to be more sensitive to radical formation than the methacrylic acid homopolymer, but this enhanced sensitivity was not evident at ambient temperature, where the G-values for radical formation for the copolymers were slightly less than the values for the homopolymers. (C) 2003 Society of Chemical Industry.

A síntese do aduto binuclear [Fe(CNBut)(CO)4(HgSO4 )]

The binuclear [Fe(CNBut)(CO)4(HgSO4 )] adduct was obtained in the reaction of HgSO4 with [Fe(CNBut)(CO)4] in methanol. This adduct, without a similar in the homoleptic pentacarbonyliron, was characterized by analytical and spectroscopic data. Further Mössbauer and molar conductivity studies have confirmed it's adduct nature.

O treinamento da operação osteoplástica usando o seio frontal do cão

O acesso ao seio frontal usando a técnica do retalho osteoplástico está indicada em lesões que não podem ser abordadas pela via endonasal. O aprendizado da técnica pode ser realizado em cães, mas a delimitação do seio do cão, de forma como se faz no homem, não é facilmente realizável. OBJETIVO: Apresentar um método de localização e delimitação do seio frontal do cão que permita reproduzir a técnica osteoplástica. FORMA DE ESTUDO: Técnica cirúrgica em animal. MATERIAL E MÉTODO: Em cães traçaram-se duas linhas retas, uma delas ao longo da linha média da região frontal, outra passando pela pupila, inclinada 45º em direção à linha anterior. No ponto de intersecção, mede-se um ou um centímetro e meio para frente e um centímetro para trás. A partir destas medidas desenha-se um retângulo incompleto que delineia os limites aproximados do seio frontal. RESULTADOS: O procedimento foi realizado 12 vezes com a participação de médicos residentes. O seio frontal foi aberto facilmente em todos os animais, reproduzindo a técnica osteoplástica sem erros de localização do seio. CONCLUSÃO: O método de localização e de limitação do seio frontal do cão mostrou-se útil no ensino da técnica osteoplástica de acesso por ser reproduzível de forma realística.

União Européia, reformas institucionais e déficit democrático: uma análise a partir do mecanismo de co-decisão

O artigo discute o processo decisório europeu a partir de um mapeamento do sistema de co-decisão adotado pelo triângulo institucional da União Européia (UE). Na primeira parte, há uma explicação acerca do funcionamento do sistema decisório europeu, privilegiando as instituições que definem as regras do jogo e a forma como a tomada de decisão é praticada; na segunda parte, são expostos os dados coletados sobre a aplicabilidade da co-decisão durante os anos de 1999 a 2006, cruzando os principais temas e a sua freqüência por fase de decisão.

Molybdenum mixed with glyphosate and alone via foliar spray in no-tillage common bean grown on corn stover

The effect of molybdenum (Mo) on common bean grown in desiccated corn stover in a no-tillage system was evaluated under two application modes: Mo mixed with the desiccant glyphosate and Mo direct spray to the bean leaves. The treatments (four replicates) were assigned to a completely randomized block design in a split-plot arrangement with the application of Mo (0, 100, 200, 400 and 800 g ha-1) mixed with glyphosate in the main plots and Mo foliar spray (0 and 100 g ha-1) in the sub-plots. The field experiments were carried out in 2009 and 2010 in the municipality of Coimbra, Minas Gerais State, with the common bean cultivar Ouro Vermelho. Mo mixed with glyphosate had neither an effect on common bean yield nor on the Mo and N contents in leaves, however it increased the Mo and N contents in seeds. Application of Mo via foliar spray increased Mo content in leaves and Mo and N contents in seeds. The reapplication of molybdenum with glyphosate for desiccation in subsequent crops caused a cumulative effect of Mo content in bean seeds.

O hemograma no cão e contribuição para a sua caracterização no cão da Serra da Estrela, variedade de pêlo comprido

O hemograma é dos exames mais frequentemente solicitados na prática clínica. Está indicado sempre que se suspeite de doença, para ajudar no diagnóstico, monitorizar a sua evolução e resposta à terapêutica. Os valores hematológicos devem ser, idealmente, comparados com intervalos de referência específicos para determinada população, no entanto, estes estão caracterizados para poucas raças de cães. Os objectivos da presente dissertação, para além de rever a bibliografia relativa ao hemograma no cão saudável, foram contribuir para a caracterização do hemograma no Cão da Serra da Estrela de Pêlo Comprido, propondo um intervalo de valores de referência específico para esta raça. Os valores hematológicos foram determinados, numa amostra de 37 Cães Serra da Estrela adultos, inteiros e clinicamente saudáveis, utilizando o analisador automático «IDEXX Lasercyte®» e avaliação dos esfregaços sanguíneos. Para cada parâmetro foi determinada a normalidade, média, desvio padrão e intervalo de referência utilizando o percentil 2,5 e 97,5%. Propôs-se um conjunto de intervalos de referência hematológicos e reportou-se que, para a amostra estudada, o hematócrito e volume corpuscular médio tendem a estar elevados, enquanto que a concentração de hemoglobina corpuscular média e plaquetas tendem a estar diminuídas.Os resultados sugerem a eventual existência de particularidades do hemograma na raça estudada, pelo que maior investigação deve ser efectuada.

Accountability and co-production of information and control: social observatories and their relationship with government agencies

Abstract:Through the development of a proposal to categorize accountability into four stages - classical, cross-sectional, systemic, and diffused -, this article aims to identify characteristics of co-production of information and socio-political control of public administration in the work of Brazilian social observatories in relationship with government control agencies. The study analyses data from 20 social observatories and, particularly, three experiences of co-production of information and control, based on a systemic perspective on accountability and a model with four categories: Political and cultural; valuing; systemic-organizational, and production. The conclusions summarize characteristics of these practices, specific phases in the accountability processes, as well as the potentialities and challenges of co-production of information and control, which not only influences, but it is also influenced by the accountability system.