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.

Discrete cyanide-bridged mixed-valence Co/Fe complexes: Outer-sphere redox behaviour

The outer-sphere redox behaviour of a series of [LnCoIII-NCFeII(CN)(5)](-) (L-n = n-membered pentadentate aza-macrocycle) complexes have been studied as a function of pH and oxidising agent. All the dinuclear complexes show a double protonation process at pH approximate to 2 that produces a shift in their UV/Vis spectra. Oxidation of the different non-protonated and diprotonated complexes has been carried out with peroxodisulfate, and of the non-protonated complexes also with trisoxalatocobaltate(III). The results are in agreement with predictions from the Marcus theory. The oxidation of [Fe(phen)(3)](3+) and [IrCl6](2-) is too fast to be measured, although for the latter the transient observation of the process has been achieved at pH = 0. The study of the kinetics of the outer-sphere redox process, with the S2O82- and [Co(ox)(3)](3-) oxidants, has been carried out as a function of pH, temperature, and pressure. As a whole, the values found for the activation volumes, entropies, and enthalpies are in the following margins, for the diprotonated and non-protonated dinuclear complexes, respectively: DeltaV(not equal) from 11 to 13 and 15 to 20 cm(3) mol(-1); DeltaS(not equal) from 110 to 30 and -60 to -90 J K-1 mol(-1); DeltaH(not equal) from 115 to 80 and 50 to 65 kJ.mol(-1). The thermal activation parameters are clearly dominated by the electrostriction occurring on outer-sphere precursor formation, while the trends found for the values of the volume of activation indicate an important degree of tuning due to the charge distribution during the electron transfer process. The special arrangement on the amine ligands in the isomer trans[(L14CoNCFeII)-N-III(CN)(5)](-) accounts for important differences in solvent-assisted hydrogen bonding occurring within the outer-sphere redox process, as has been established in redox reactions of similar compounds. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).

Evidence and information for health policy: a decade of change

Over the past decade or so, there has been increasing demand for greater clarity about the major causes of disease and injury, how these differentially affect populations, and how they are changing. In part, this demand has been motivated by resource constraints and a realisation that better health is possible with more informed allocation of resources. At the same time, there has been a change in the way population health and its determinants are quantified, with a much closer integration of the quantitative population sciences (such as epidemiology, demography and health economics) to strengthen and broaden the evidence base for healthcare policy.

A reestrutura????o da carreira de especialista em pol??ticas p??blicas e gest??o governamental e seu impacto na reforma administrativa de 1995

As reformas administrativas brasileiras sempre foram uma forma de tentar aprimorar a gest??o p??blica em nosso pa??s, mas ?? verdade tamb??m que in??meras vezes elas foram usadas como plataforma eleitoral ou ret??rica em esbo??os de programas de Governo. Podemos considerar como a primeira dessas reformas a realizada na d??cada de 1930 pelo Governo de Get??lio Vargas que reduziu bastante as pr??ticas patrimonialistas de gerir o Estado. Posteriormente tivemos, sem muito sucesso, a tentativa de reforma implantada atrav??s edi????o do Decreto-Lei 200 de 1967, durante os governos militares. Com a redemocratiza????o, tentou-se uma reforma no Governo Sarney, da qual resultou como pontos positivos a cria????o da Escola Nacional de Administra????o P??blica e a cria????o da Carreira de Especialista em Pol??ticas P??blicas e Gest??o Governamental (EPPGG). No Governo Collor tentou-se fazer nova reforma administrativa, que n??o logrou ??xito. J?? no Governo Fernando Henrique Cardoso, o Ministro Bresser Pereira foi respons??vel, a partir de 1995, por implementar uma nova e grande reforma administrativa no Brasil. Um dos objetivos dessa Reforma era o fortalecimento do N??cleo Estrat??gico do Estado; para realizar essa tarefa, Bresser Pereira optou por fortalecer as carreiras do chamado Ciclo de Gest??o do Estado, nesse processo ela realizou uma grande reestrutura????o da carreira de EPPGG. Essa reestrutura????o trouxe para o N??cleo Estrat??gico do Estado um corpo de servidores bem treinados e sintonizados com as propostas de gest??o previstas na Reforma. Esses profissionais tiveram uma participa????o marcante nas mudan??as ocorridas na gest??o da Administra????o P??blica durante os dois Governos de Fernando Henrique, participando de v??rios projetos e ocupando v??rios Cargos de Dire????o em todos os n??veis na Administra????o P??blica. O trabalho de sucesso desses profissionais continuou nos dois mandatos seguintes do Presidente Lula. Na constru????o dessa pesquisa foram utilizados v??rios estudos, livros, artigos e entrevistas que levaram ?? conclus??o que a reestrutura????o da Carreira de EPPGG foi um instrumento eficaz para que a Reforma Administrativa de 1995 tivesse sucesso no objetivo de fortalecer o N??cleo Estrat??gico do Estado.

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.

Desenvolvimento de metodologia para determinação de Co, Cr, Fe, Mn, Ni, Se e V em amostras de água produzida da indústria do petróleo através da técnica ICP OES utilizando digestão por micro-ondas

O descarte ou reutilização da água produzida da indústria do petróleo é difícil por causa dos impactos ambientais causados devido à presença de alta salinidade e componentes tóxicos, ou pelo risco de obstrução nas colunas de produção devido à formação de incrustações que causam redução na produção de petróleo e enormes perdas no processo de extração. Assim, o conhecimento da composição química da água produzida é muito importante. O método proposto por este trabalho visa a determinação de elementos traço (Co, Cr, Fe, Mn, Ni, Se e V) em amostras de água produzida de petróleo por espectrometria de emissão óptica com plasma indutivamente acoplado (ICP OES) utilizando a digestão ácida assistida por micro-ondas para o preparo das amostras (15 g de amostra e 2 mL de HNO3 concentrado). A curva analítica construída em HNO3 2% v v-1 foi adotada para o método após verificar que não é necessário o uso de salinidade para equiparação de matriz. Para o elemento Ni, não há necessidade do uso de padrão interno, para os elementos Co, Cr, Fe, Mn e V os melhores resultados foram obtidos usando Sc como padrão interno. Para o elemento Se é recomendado o uso de Y como padrão interno. Os limites de detecção obtidos foram Co 0,67, Cr 1,2, Fe 2,3, Mn 0,49, Ni 1,9, Se 3,7 e V 5,5 μg L-1; e os limites de quantificação foram Co 2,2, Cr 4,0, Fe 7,7, Mn 1,6, Ni 6,5, Se 12,4 e V 18,3 μg L-1. A exatidão do procedimento foi verificada através de testes de recuperação em dois níveis de concentração (40 e 80 μg L-1) e análise dos materiais certificados de referência de água estuarina SLEW-2 e de água do mar NASS-5. Bons valores de recuperação foram obtidos e não houve diferença significativa (95% de confiança) entre os resultados obtidos e os valores certificados dos materiais de referência.

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.

The influence of nationalism in Mercosur and in South America: can the regional integration project survive?

The article discusses if nationalism is getting in the way of regional integration through a Brazilian prism due to Brazil’s pivotal role in regional integration in Mercosur and South America.

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.

Frequência e distribuição de Helicobacter spp. na mucosa gástrica de cães

A associação das helicobacterias com doença gástrica em humanos e em alguns animais domésticos e selvagens sugere a participação dessas na patogênese da gastrite em cães. Neste artigo procurou-se verificar a presença de Helicobacter spp. na mucosa gástrica de cães e avaliar sua associação com os achados macro e microscópicos, considerando a idade. Coletaram-se amostras das regiões cárdica, fúndica, do corpo e pilórica dos estômagos de 60 cães para a realização de exame histopatológico, utilizando-se as colorações pela hematoxilina-eosina (HE) e carbolfucsina (CF). Tais exames revelaram Helicobacter spp. em 96,7% dos animais, sendo observados infiltrados inflamatórios, predominantemente mononucleares (100%), hiperplasia de nódulos linfoides (98,3%), erosões/ulcerações (6,7%), hemorragia (5%) e hiperemia (95%) em amostras coradas por HE. Não houve correlação da infecção por helicobacter spp. com a idade do animal e da idade com alterações inflamatórias na presença da bactéria. As amostras das regiões do corpo e pilórica apresentaram maior presença de bactérias a histopatologia (CF) (ambos 95%), em seguida vindo as regiões fúndica (91,7%) e cárdica (56,7%). Houve correlação do número de Helicobacter spp. com o de células inflamatórias e nódulos linfoides nessas regiões, sugerindo que as bactérias encontradas na mucosa gástrica dos cães poderiam ser responsáveis pelas alterações que caracterizam a gastrite.

Certification and integration of management systems: the experience of Portuguese small and medium enterprises

The purpose of this study was to characterize the situation of Portuguese Small and Medium Enterprises (SMEs) concerning the certification of their Quality Management Systems (QMS), Environmental Management Systems (EMS) and Occupational Health and Safety Management Systems (OHSMS), in their individually form, to identify benefits, drawbacks and difficulties associated with the certification process and to characterize the level of integration that has been achieved. This research was based on a survey carried out by the research team; it was administered to 46 Portuguese SMEs. Our sample comprised 20 firms (43%) from the Trade/Services activity sector, 17 (37%) from the Industrial sector, 5 (11%) from the Electricity/Telecommunications sector and 4 (9%) from the Construction area. All SMEs surveyed were certified according to the ISO 9001 (100%), a quarter of firms were certified according to the ISO 14001 (26.1%) and a few certified by OHSAS 18001 (15.2%). We undertook a multivariate cluster analysis, which enabled grouping variables into homogeneous groups or one or more common characteristics of the SMEs participating in the study. Results show that the main benefits that Portuguese SMEs have gained from the referred certifications have been, among others, an improvement of both their internal organization and external image. We also present the main difficulties in achieving certification. Overall, 7 of the Portuguese SMEs examined indicated that the main benefits of the IMS implementation management included costs reduction, increased employee training and easier compliance of legislation. The respective drawbacks and difficulties are also presented. Finally, we presented the main integrated items in the certified Portuguese SMEs we examined.

The role of coordination analysis in software integration projects

What sort of component coordination strategies emerge in a software integration process? How can such strategies be discovered and further analysed? How close are they to the coordination component of the envisaged architectural model which was supposed to guide the integration process? This paper introduces a framework in which such questions can be discussed and illustrates its use by describing part of a real case-study. The approach is based on a methodology which enables semi-automatic discovery of coordination patterns from source code, combining generalized slicing techniques and graph manipulation

Certification and integration of environment with quality and safety – a path to sustained success

According to Wright [1] certification of products and processes began during the 1960’s in the manufacturing industry, as a tool to control and assure the quality/conformity of products and services provided by suppliers to customers/consumers. Thus, the series of ISO 9000 was published first time, in 1987 and it was been created with a flexible character, to be reviewed periodically. Later, were published others normative references, which highlight the ISO 14001 in 1996 and OHSAS 18001 in 1999. This was also, the natural sequence of the certification processes in the organizations, i.e., began with the certification of quality management systems (QMS) followed by the environmental management systems (EMS) and after for the Occupational Health and Safety Management System (OHSMS). Hence, a high percentage of organizations with an EMS, in accordance with the ISO 14001, had also implemented, a certified QMS, in accordance with ISO 9001. At first the implementation of a QMS was particularly relevant in high demanding activity sectors, like the automotive and aeronautical industries, but it has rapidly extended to every activity sector, becoming a common requisite of any company worldwide and a factor of competitiveness and survival. Due to the increasingly demanding environmental legislation in developed countries, companies nowadays are required to seriously take into consideration not only environmental aspects associated to the production chain itself, but also to the life cycle of their products.