O que diferencia os desiguais na federação brasileira?: políticas públicas e ação coletiva no semi-árido da Paraíba

O presente estudo analisa a desigualdade entre os municípios brasileiros com enfoque nas políticas públicas descentralizadas e as mudanças institucionais após a Constituição de 1988. Para isso faz-se uma discussão do federalismo brasileiro e da cooperação intergovernamental, imprescindível para implementação de políticas com responsabilidades compartilhadas entre os entes federativos. A situação e o resultado destas políticas são ilustrados e complementados a partir da análise de quatro cidades no semi-árido paraibano que apresentam diferentes resultados nas variáveis analisadas, sendo elas o Programa Bolsa Família, as políticas governamentais de saúde e educação, a capacidade governamental (política e burocrática) e o associativismo. Por meio do aprofundamento nos casos procura-se também identificar as raízes institucionais da pobreza e desigualdade na região e argumentar sobre a importância de iniciativas empreendidas no sentido de aprimorar a cooperação entre as esferas de governo e de criar incentivos que catalisem as iniciativas associativas tanto governamentais quanto da sociedade civil.

Novo formalismo semi-empírico para cálculos químico-quânticos

Realizou-se a dedução de um formalismo básico, útil para o desenvolvimento de novas implementações semi-empíricas, partindo de primeiros princípios. A abordagem utilizada é inspirada nos métodos da família HAM, e visa possibilitar o desenvolvimento de uma implementação semi-empírica de última geração que não esteja sujeita às di culdades que ocorrem com métodos da família ZDO. São apresentadas as expressões para a energia total e para os elementos da matriz de Fock segundo este formalismo básico. O emprego de expoentes variáveis nas funções de base (orbitais atômicos) é proposto e modelado com esquemas tipo HAM/3, HAM/4 e polinomial, tomando-se como referência resultados obtidos por cálculo ab initio. Além disso, uma contribuição para produção de conjuntos de dados de referência por cálculo ab initio é fornecida. Esta contribuição permite que sejam produzidos resultados de alto nível para energias eletrônicas a um custo computacional moderado, por meio da extrapola- ção da energia de correlação eletrônica em cálculos com bases correlation consistent de Dunning.

Integração semi-Lagrangeana num modelo oceano-atmosfera e ajuste geostrófico no domínio tempo

Este trabalho visa o uso da função de Green de valor inicial no ajuste geostrófico e do método Semi-Lagrangeano na integração de um modelo acoplado oceano-atmosfera descrito pelas equações de águas rasas. O ajuste geostrófico é considerado atravées de perturbações na pressão e do vento. No caso de sistemas sem rotação, é discutida a relação da equação hidrostática com ondas longas não-dispersivas. Com rotação, a conservação da vorticidade potencial permite escolher a elevação correspondente a um estado de equilíbrio geostrófico. O sistema de equações de águas rasas é desacoplado em equações de Klein-Gordon com valores iniciais e termos não-homogêneos acoplados. A resposta dinâmica formada pela resposta transiente e a resposta forçada é obtida para uma perturbação inicial da elevação. A ação do vento como forçante nas equações de momento 2D, através do transporte de Eckman, conduz a uma equação de águas rasas forçada. Uma decomposição da resposta forçada é realizada com uma resposta permanente, que satisfaz a equação de Helmholtz , e com o uso da base dinâmica gerada pela resposta impulso. Um modelo hidrodinâmico 3D introduzido por Casulli e governado por equações não-lineares de águas rasas é integrado na vertical para a obtenção de um modelo 2D. Com isto, as condições de contorno devido a tensão do vento e a fricção devido a topografia do fundo, transformam-se em forçantes do modelo. O modelo foi integrado com um método semi-implícito em diferenças finitas, utilizando-se o método Semi-Lagrangeano para a parte advectiva. Simulações simbólicas foram realizadas para o ajuste geostrófico devido a perturbações de duração infinita e finita para a elevação e para o efeito da tensão do vento. Foram realizadas simulações numéricas para variadas geometrias, em particular a Baia de Guanabara e a Lagoa do Patos.

A (semi-)parametric functional coefficient autoregressive conditional duration model

In this paper, we propose a class of ACD-type models that accommodates overdispersion, intermittent dynamics, multiple regimes, and sign and size asymmetries in financial durations. In particular, our functional coefficient autoregressive conditional duration (FC-ACD) model relies on a smooth-transition autoregressive specification. The motivation lies on the fact that the latter yields a universal approximation if one lets the number of regimes grows without bound. After establishing that the sufficient conditions for strict stationarity do not exclude explosive regimes, we address model identifiability as well as the existence, consistency, and asymptotic normality of the quasi-maximum likelihood (QML) estimator for the FC-ACD model with a fixed number of regimes. In addition, we also discuss how to consistently estimate using a sieve approach a semiparametric variant of the FC-ACD model that takes the number of regimes to infinity. An empirical illustration indicates that our functional coefficient model is flexible enough to model IBM price durations.

The experience of semi-formal infrastructure finance in developing countries: proposals for Brazil and Latin America

This paper has the purpose of analyzing the role of civil society in funding and providing nfrastructure projects in developing countries. Considering that local associations around the world have been directly engaged on some infrastructure projects – some scholars define it as “semi-formal finance” –, the intention is to demonstrate that the experiences on such arrangements in developing countries have been responsible for fostering infrastructure investments in the poorer regions where the government is more absent. Based upon legal, economic and social aspects, this paper aims to contribute to a broader debate for the development of infrastructure in emerging countries. The conclusion is that, under a more social approach, the legal and economic mechanisms in developing countries are able to consider such arrangements in the benefit of their development.

Associação do meio (urbano, semi-urbano e rural) ao crescimento físico humano, à maturação biológica, à actividade física e à aptidão na criança e no adolescente madeirense

O objectivo central do presente estudo consistiu em investigar a associação do meio (urbano, semi-urbano e rural) ao crescimento físico humano, à maturação biológica, à actividade física e à aptidão na criança e no adolescente madeirense. Amostra foi constituída por 1498 sujeitos, 758 rapazes e 740 raparigas, que participaram no ‘Estudo de Crescimento da Madeira’. As características de crescimento físico humano incluem a altura, o peso, os diâmetros ósseos, os perímetros musculares e as pregas de adiposidade subcutânea. A idade esquelética foi estimada usando o método Tanner-Whitehouse (TW2). A actividade física e a aptidão foram avaliadas através do questionário de Baecke e da bateria de testes motores Eurofit, respectivamente. Os rapazes e as raparigas do meio urbano e semi-urbano apresentaram uma tendência para valores médios mais elevados nos perímetros musculares e nas pregas de adiposidade subcutânea. Apenas aos 14-15 anos, os rapazes do meio urbano estavam avançados na sua maturação esquelética (escalas RUS, Carpal e TW2 20-ossos). As crianças e adolescentes madeirenses do meio urbano apresentaram valores mais elevados de prática regular e sistemática de um ou mais desportos. Os resultados para as componentes da aptidão física não favorecem um único meio sócio-geográfico. Os rapazes do meio urbano e/ou semi-urbano foram mais proficientes na flexibilidade, força e resistência muscular, e potência, enquanto os rapazes rurais apresentaram melhores resultados na resistência aeróbia, força estática, e velocidade/agilidade. As raparigas do meio urbano e/ou semi-urbano apresentaram melhores resultados na velocidade/agilidade, enquanto as raparigas do meio rural foram mais proficientes na força estática e na força e resistência muscular. A eliminação dos diferenciais negativos no crescimento físico humano, na maturação biológica, na actividade física e na aptidão associados ao meio sócio-geográfico irá resultar numa melhor saúde das crianças e adolescentes madeirenses.

Development of a dynamic headspace solid-phase microextraction procedure coupled to GC–qMSD for evaluation the chemical profile in alcoholic beverages

In the present study, a simple and sensitive methodology based on dynamic headspace solid-phase microextraction (HS-SPME) followed by thermal desorption gas chromatography with quadrupole mass detection (GC–qMSD), was developed and optimized for the determination of volatile (VOCs) and semi-volatile (SVOCs) compounds from different alcoholic beverages: wine, beer and whisky. Key experimental factors influencing the equilibrium of the VOCs and SVOCs between the sample and the SPME fibre, as the type of fibre coating, extraction time and temperature, sample stirring and ionic strength, were optimized. The performance of five commercially available SPME fibres was evaluated and compared, namely polydimethylsiloxane (PDMS, 100 μm); polyacrylate (PA, 85 μm); polydimethylsiloxane/divinylbenzene (PDMS/DVB, 65 μm); carboxen™/polydimethylsiloxane (CAR/PDMS, 75 μm) and the divinylbenzene/carboxen on polydimethylsiloxane (DVB/CAR/PDMS, 50/30 μm) (StableFlex). An objective comparison among different alcoholic beverages has been established in terms of qualitative and semi-quantitative differences on volatile and semi-volatile compounds. These compounds belong to several chemical families, including higher alcohols, ethyl esters, fatty acids, higher alcohol acetates, isoamyl esters, carbonyl compounds, furanic compounds, terpenoids, C13-norisoprenoids and volatile phenols. The optimized extraction conditions and GC–qMSD, lead to the successful identification of 44 compounds in white wines, 64 in beers and 104 in whiskys. Some of these compounds were found in all of the examined beverage samples. The main components of the HS-SPME found in white wines were ethyl octanoate (46.9%), ethyl decanoate (30.3%), ethyl 9-decenoate (10.7%), ethyl hexanoate (3.1%), and isoamyl octanoate (2.7%). As for beers, the major compounds were isoamyl alcohol (11.5%), ethyl octanoate (9.1%), isoamyl acetate (8.2%), 2-ethyl-1-hexanol (5.9%), and octanoic acid (5.5%). Ethyl decanoate (58.0%), ethyl octanoate (15.1%), ethyl dodecanoate (13.9%) followed by 3-methyl-1-butanol (1.8%) and isoamyl acetate (1.4%) were found to be the major VOCs in whisky samples.

Volatile flavour constituent patterns of terras madeirenses red wines extracted by dynamic headspace solid‐phase microextraction

A suitable analytical procedure based on static headspace solid-phase microextraction (SPME) followed by thermal desorption gas chromatography–ion trap mass spectrometry detection (GC–ITDMS), was developed and applied for the qualitative and semi-quantitative analysis of volatile components of Portuguese Terras Madeirenses red wines. The headspace SPME method was optimised in terms of fibre coating, extraction time, and extraction temperature. The performance of three commercially available SPME fibres, viz. 100 lm polydimethylsiloxane; 85 lm polyacrylate, PA; and 50/30 lm divinylbenzene/carboxen on polydimethylsiloxane, was evaluated and compared. The highest amounts extracted, in terms of the maximum signal recorded for the total volatile composition, were obtained with a PA coating fibre at 308C during an extraction time of 60 min with a constant stirring at 750 rpm, after saturation of the sample with NaCl (30%, w/v). More than sixty volatile compounds, belonging to different biosynthetic pathways, have been identified, including fatty acid ethyl esters, higher alcohols, fatty acids, higher alcohol acetates, isoamyl esters, carbonyl compounds, and monoterpenols/C13-norisoprenoids.

Effectiveness of different solid-phase microextraction fibres for differentiation of selected Madeira island fruits based on their volatile metabolite profile: identification of novel compounds

A headspace solid-phase microextraction (HS-SPME) procedure based on five commercialised fibres (85 μm polyacrylate – PA, 100 μm polydimethylsiloxane – PDMS, 65 μm polydimethylsiloxane/divinylbenzene – PDMS/DVB, 70 μm carbowax/divinylbenzene – CW/DVB and 85 μm carboxen/polydimethylsiloxane – CAR/PDMS) is presented for the characterization of the volatile metabolite profile of four selected Madeira island fruit species, lemon (Citrus limon), kiwi (Actinidia deliciosa), papaya (Carica papaya L.) and Chickasaw plum (Prunus angustifolia). The isolation of metabolites was followed by thermal desorption gas chromatography–quadrupole mass spectrometry (GC–qMS) methodology. The performance of the target fibres was evaluated and compared. The SPME fibre coated with CW/DVB afforded the highest extraction efficiency in kiwi and papaya pulps, while in lemon and plum the same was achieved with PMDS/DVB fibre. This procedure allowed for the identification of 80 compounds, 41 in kiwi, 24 in plums, 23 in papaya and 20 in lemon. Considering the best extraction conditions, the most abundant volatiles identified in kiwi were the intense aldehydes and ethyl esters such as (E)-2-hexenal and ethyl butyrate, while in Chicasaw plum predominate 2-hexenal, 2-methyl-4-pentenal, hexanal, (Z)-3-hexenol and cyclohexylene oxide. The major compounds identified in the papaya pulp were benzyl isothiocyanate, linalool oxide, furfural, hydroxypropanone, linalool and acetic acid. Finally, lemon was shown to be the most divergent of the four fruits, being its aroma profile composed almost exclusively by terpens, namely limonene, γ-terpinene, o-cymene and α-terpinolene. Thirty two volatiles were identified for the first time in the fruit or close related species analysed and 14 volatiles are reported as novel volatile metabolites in fruits. This includes 5 new compounds in kiwi (2-cyclohexene-1,4-dione, furyl hydroxymethyl ketone, 4-hydroxydihydro-2(3H)-furanone, 5-acetoxymethyl-2-furaldehyde and ethanedioic acid), 4 in plum (4-hydroxydihydro-2(3H)-furanone, 5-methyl-2-pyrazinylmethanol, cyclohexylene oxide and 1-methylcyclohexene), 4 in papaya (octaethyleneglycol, 1,2-cyclopentanedione, 3-methyl-1,2-cyclopentanedione and 2-furyl methyl ketone) and 2 in lemon (geranyl farnesate and safranal). It is noteworthy that among the 15 volatile metabolites identified in papaya, 3-methyl-1,2-cyclopentanedione was previously described as a novel PPARγ (peroxisome proliferator-activated receptor γ) agonist, having a potential to minimize inflammation.

Effectiveness of high-throughput miniaturized sorbent- and solid phase microextraction techniques combined with gas chromatography–mass spectrometry analysis for a rapid screening of volatile and semi-volatile composition of wines: a comparative study

In this study the feasibility of different extraction procedures was evaluated in order to test their potential for the extraction of the volatile (VOCs) and semi-volatile constituents (SVOCs) from wines. In this sense, and before they could be analysed by gas chromatography–quadrupole first stage masss spectrometry (GC–qMS), three different high-throughput miniaturized (ad)sorptive extraction techniques, based on solid phase extraction (SPE), microextraction by packed sorbents (MEPS) and solid phase microextraction (SPME), were studied for the first time together, for the extraction step. To achieve the most complete volatile and semi-volatile signature, distinct SPE (LiChrolut EN, Poropak Q, Styrene-Divinylbenzene and Amberlite XAD-2) and MEPS (C2, C8, C18, Silica and M1 (mixed C8-SCX)) sorbent materials, and different SPME fibre coatings (PA, PDMS, PEG, DVB/CAR/PDMS, PDMS/DVB, and CAR/PDMS), were tested and compared. All the extraction techniques were followed by GC–qMS analysis, which allowed the identification of up to 103 VOCs and SVOCs, distributed by distinct chemical families: higher alcohols, esters, fatty acids, carbonyl compounds and furan compounds. Mass spectra, standard compounds and retention index were used for identification purposes. SPE technique, using LiChrolut EN as sorbent (SPELiChrolut EN), was the most efficient method allowing for the identification of 78 VOCs and SVOCs, 63 and 19 more than MEPS and SPME techniques, respectively. In MEPS technique the best results in terms of number of extractable/identified compounds and total peak areas of volatile and semi-volatile fraction, were obtained by using C8 resin whereas DVB/CAR/PDMS was revealed the most efficient SPME coating to extract VOCs and SVOCs from Bual wine. Diethyl malate (18.8 ± 3.2%) was the main component found in wine SPELiChrolut EN extracts followed by ethyl succinate (13.5 ± 5.3%), 3-methyl-1-butanol (13.2 ± 1.7%), and 2-phenylethanol (11.2 ± 9.9%), while in SPMEDVB/CAR/PDMS technique 3-methyl-1-butanol (43.3 ± 0.6%) followed by diethyl succinate (18.9 ± 1.6%), and 2-furfural (10.4 ± 0.4%), are the major compounds. The major VOCs and SVOCs isolated by MEPSC8 were 3-methyl-1-butanol (26.8 ± 0.6%, from wine total volatile fraction), diethyl succinate (24.9 ± 0.8%), and diethyl malate (16.3 ± 0.9%). Regardless of the extraction technique, the highest extraction efficiency corresponds to esters and higher alcohols and the lowest to fatty acids. Despite some drawbacks associated with the SPE procedure such as the use of organic solvents, the time-consuming and tedious sampling procedure, it was observed that SPELiChrolut EN, revealed to be the most effective technique allowing the extraction of a higher number of compounds (78) rather than the other extraction techniques studied.

Headspace solid-phase microextraction-gas chromatography-quadrupole mass spectrometric methodology for the establishment of the volatile composition of Passiflora fruit species

Dynamic headspace solid-phase microextraction (HS-SPME) followed by thermal desorption gas chromatography-quadrupole mass spectrometry analysis (GC-qMS), was used to investigate the aroma profile of different species of passion fruit samples. The performance of five commercially available SPME fibres: 65 μm polydimethylsiloxane/divinylbenzene, PDMS/DVB; 100 μm polydimethylsiloxane, PDMS; 85 μm polyacrylate, PA; 50/30 μm divinylbenzene/carboxen on polydimethylsiloxane, DVB/CAR/PDMS (StableFlex); and 75 μm carboxen/polydimethylsiloxane, CAR/PDMS; was evaluated and compared. Several extraction times and temperature conditions were also tested to achieve optimum recovery. The SPME fibre coated with 65 μm PDMS/DVB afforded the highest extraction efficiency, when the samples were extracted at 50 °C for 40 min with a constant stirring velocity of 750 rpm, after saturating the sample with NaCl (17%, w/v — 0.2 g). A comparison among different passion fruit species has been established in terms of qualitative and semi-quantitative differences in volatile composition. By using the optimal extraction conditions and GC-qMS it was possible to tentatively identify seventy one different compounds in Passiflora species: 51 volatiles in Passiflora edulis Sims (purple passion fruit), 24 in P. edulis Sims f. flavicarpa (yellow passion fruit) and 21 compounds in Passiflora mollissima (banana passion fruit). It was found that the ethyl esters comprise the largest class of the passion fruit volatiles, including 82.8% in P. edulis variety, 77.4% in P. edulis Sims f. flavicarpa variety and 39.9% in P. mollissima. The semi-quantitative results were then submitted to principal component analysis (PCA) in order to establish relationships between the compounds and the different passion fruit species under investigation.

Use of Fibres Obtained from the Cashew (Anacardium ocidentale, L) and Guava (Psidium guayava) Fruits for Enrichment of Food Products

OLIVEIRA, E. L. et al. Use of Fibres obtained from the Cashew (Anacardium ocidentale, L) and Guava (Psidium guayava) Fruits for Enrichment of Food Products. Brazilian Archives of Biology and Technology, Curitiba, PR, v. 48, p. 143-150, 2005.

Estado nutricional de escolares do semi-árido do nordeste brasileiro

SILVA, João B. da et al. Estado Nutricional de Escolares do Semi-Árido do Nordeste Brasileiro. Revista de Salud Pública, v. 11, n. 1, p. 62-71, 2009.