Avaliação da exposição a fungos e partículas em explorações avícolas e suinícolas: estudo

O projeto “Avaliação da Exposição a Fungos e Partículas em Explorações Avícolas e Suinícolas” contemplou um elevado número de colheitas ambientais e biológicas e respectivo processamento laboratorial, sendo apenas possível a sua concretização graças ao financiamento disponibilizado pela Autoridade para as Condições de Trabalho. Foi realizado um estudo transversal para avaliar a contaminação causada por fungos e partículas em 7 explorações avícolas e 7 explorações suinícolas. No que concerne à monitorização biológica, foram medidos os parâmetros espirométricos, utilizando o espirómetro MK8 Microlab, avaliada a existência de sintomas clínicos associados com a asma e outras doenças alérgicas, através de questionário adaptado European Community Respiratory Health Survey e, ainda, avaliada a sensibilização aos agentes fúngicos (IgE). Foram ainda adicionados dois objetivos ao estudo, designadamente: aferir a existência de três espécies/estirpes potencialmente patogénicas/toxinogénicas com recurso à biologia molecular e avaliar a exposição dos trabalhadores à micotoxina aflatoxina B1 por recurso a indicador biológico de exposição. Foram colhidas 27 amostras de ar de 25 litros nas explorações avícolas e 56 de 50 litros nas explorações suinícolas através do método de impacto. As colheitas de ar e a medição da concentração das partículas foram realizadas no interior e no exterior dos pavilhões, sendo este último considerado como local de referência. Simultaneamente, a temperatura e a humidade relativa também foram registadas. As colheitas das superfícies foram realizadas através da técnica de zaragatoa, tendo sido utilizado um quadrado de metal inoxidável de 10 cm de lado, de acordo com a International Standard ISO 18593 – 2004. As zaragatoas obtidas (20 das explorações avícolas e 48 das explorações suinícolas) foram inoculadas em malte de extract agar (2%) com cloranfenicol (0,05 g/L). Além das colheitas de ar e de superfícies, foram também obtidas colheitas da cama das explorações avícolas (7 novas e 14 usadas) e da cobertura do pavimento das explorações suinícolas (3 novas e 4 usadas) e embaladas em sacos esterilizados. Cada amostra foi diluída e inoculada em placas contendo malte extract agar. Todas as amostras foram incubadas a 27,5ºC durante 5 a 7 dias e obtidos resultados quantitativos (UFC/m3; UFC/m2; UFC/g) e qualitativos com a identificação das espécies fúngicas. Para a aplicação dos métodos de biologia molecular foram realizadas colheitas de ar de 300 litros utilizando o método de impinger com a velocidade de recolha de 300 L/min. A identificação molecular de três espécies potencialmente patogénicas e/ou toxinogénicas (Aspergillus flavus, Aspergillus fumigatus e Stachybotrys chartarum) foram obtidas por PCR em tempo real (PCR TR) utilizando o Rotor-Gene 6000 qPCR Detection System. As medições de partículas foram realizadas por recurso a equipamento de leitura direta (modelo Lighthouse, 2016 IAQ). Este recurso permitiu medir a concentração (mg/m3) de partículas em 5 dimensões distintas (PM 0.5; PM 1.0; PM 2.5; PM 5.0; PM10). Nas explorações avícolas, 28 espécies/géneros de fungos foram isolados no ar, tendo Aspergillus versicolor sido a espécie mais frequente (20.9%), seguida por Scopulariopsis brevicaulis (17.0%) e Penicillium sp. (14.1%). Entre o género Aspergillus, Aspergillus flavus apresentou o maior número de esporos (>2000 UFC/m3). Em relação às superfícies, A. versicolor foi detetada em maior número (>3 × 10−2 UFC/m2). Na cama nova, Penicillium foi o género mais frequente (59,9%), seguido por Alternaria (17,8%), Cladosporium (7,1%) e Aspergillus (5,7%). Na cama usada, Penicillium sp. foi o mais frequente (42,3%), seguido por Scopulariopsis sp. (38,3%), Trichosporon sp. (8,8%) e Aspergillus sp. (5,5%). Em relação à contaminação por partículas, as partículas com maior dimensão foram detectadas em maiores concentrações, designadamente as PM5.0 (partículas com a dimensão de 5.0 bm ou menos) e PM10 (partículas com a dimensão de 10 bm ou menos). Neste setting a prevalência da alteração ventilatória obstrutiva foi superior nos indivíduos com maior tempo de exposição (31,7%) independentemente de serem fumadores (17,1%) ou não fumadores (14,6%). Relativamente à avaliação do IgE específico, foi apenas realizado em trabalhadores das explorações avícolas (14 mulheres e 33 homens), não tendo sido encontrada associação positiva (p<0.05%) entre a contaminação fúngica e a sensibilização a antigénios fúngicos. No caso das explorações suinícolas, Aspergillus versicolor foi a espécie mais frequente (20,9%), seguida por Scopulariopsis brevicaulis (17,0%) e Penicillium sp. (14,1%). No género Aspergillus, A. versicolor apresentou o maior isolamento no ar (>2000 UFC/m3) e a maior prevalência (41,9%), seguida por A. flavus e A. fumigatus (8,1%). Em relação às superfícies analisadas, A. versicolor foi detetada em maior número (>3 ×10−2 UFC/m2). No caso da cobertura do pavimento das explorações suinícolas, o género Thicoderma foi o mais frequente na cobertura nova (28,0%) seguida por A. versicolor e Acremonium sp. (14,0%). O género Mucor foi o mais frequente na cobertura usada (25,1%), seguido por Trichoderma sp. (18,3%) e Acremonium sp. (11,2%). Relativamente às partículas, foram evidenciados também valores mais elevados na dimensão PM5 e, predominantes nas PM10. Neste contexto, apenas 4 participantes (22,2%) apresentaram uma alteração ventilatória obstrutiva. Destes, as obstruções mais graves encontraram-se nos que também apresentavam maior tempo de exposição. A prevalência de asma na amostra de trabalhadores em estudo, pertencentes aos 2 contextos em estudo, foi de 8,75%, tendo-se verificado também uma prevalência elevada de sintomatologia respiratória em profissionais não asmáticos. Em relação à utilização complementar dos métodos convencionais e moleculares, é recomendável que a avaliação da contaminação fúngica nestes settings, e, consequentemente, a exposição profissional a fungos, seja suportada pelas duas metodologias e, ainda, que ocorre exposição ocupacional à micotoxina aflatoxina B1 em ambos os contextos profissionais. Face aos resultados obtidos, é importante salientar que os settings alvo de estudo carecem de uma intervenção integrada em Saúde Ocupacional no âmbito da vigilância ambiental e da vigilância da saúde, com o objetivo de diminuir a exposição aos dois factores de risco estudados (fungos e partículas).

Synthesis, characterization and reactivity of new cobalt, palladium and nickel complexes bearing α-diimines and P, O ligands

This work describes the synthesis and characterization of a series of new α-diimine and P,O, β-keto and acetamide phosphines ligands, and their complexation to Ni(II), Co(II),Co(III) and Pd(II) to obtain a series of new compounds aiming to study their structural characteristics and to test their catalytic activity. All the compounds synthesized were characterized by the usual spectroscopic and spectrometric techniques: Elemental Analysis, MALDI-TOF-MS spectrometry, IR, UV-vis, 1H, 13C and 31P NMR spectroscopies. Some of the paramagnetic compounds were also characterized by EPR. For the majority of the compounds it was possible to solve their solid state structure by single crystal X-ray diffraction. Tests for olefin polymerization were performed in order to determine the catalytic activity of the Co(II) complexes. Chapter I presents a brief introduction to homogenous catalysis, highlighting the reactions catalyzed by the type of compounds described in this thesis, namely olefin polymerization and oligomerization and reactions catalyzed by the complexes bearing α-diimines and P,O type ligands. Chapter II is dedicated to the description of the synthesis of new α-diimines cobalt (II) complexes, of general formula [CoX2(α-diimine)], where X = Cl or I and the α-diimines are bis(aryl)acenaphthenequinonediimine) (Ar-BIAN) and 1,4-diaryl-2,3-dimethyl-1,4-diaza-1,3-butadiene (Ar-DAB). Structures solved by single crystal X-ray diffraction were obtained for all the described complexes. For some of the compounds, X-band EPR measurements were performed on polycrystalline samples, showing a high-spin Co(II) (S = 3/2) ion, in a distorted axial environment. EPR single crystal experiments on two of the compounds allowed us to determine the g tensor orientation in the molecular structure. In Chapter III we continue with the synthesis and characterization of more cobalt (II)complexes bearing α-diimines of general formula [CoX2(α-diimine)], with X = Cl or I and α-diimines are bis(aryl)acenaphthenequinonediimine) (Ar-BIAN) and 1,4-diaryl-2,3-dimethyl- 1,4-diaza-1,3-butadiene (Ar-DAB). The structures of three of the new compounds synthesized were determined by single crystal X-ray diffraction. A NMR paramagnetic characterization of all the compounds described is presented. Ethylene polymerization tests were done to determine the catalytic activity of several of the Co(II) complexes described in Chapter II and III and their results are shown. In Chapter IV a new rigid bidentate ligand, bis(1-naphthylimino)acenaphthene, and its complexes with Zn(II) and Pd(II), were synthesized. Both the ligand and its complexes show syn and anti isomers. Structures of the ligand and the anti isomer of the Pd(II) complex were solved by single crystal X-ray diffraction. All the compounds were characterized by elemental analysis, MALDI-TOF-MS spectrometry, and by IR, UV-vis, 1H, 13C, 1H-1H COSY, 1H-13C HSQC, 1H-13C HSQC-TOCSY and 1H-1H NOESY NMR when necessary. DFT studies showed that both conformers of [PdCl2(BIAN)] are isoenergetics and can be obtain experimentally. However, we can predict that the isomerization process is not available in square-planar complex, but is possible for the free ligand. The molecular geometry is very similar in both isomers, and only different orientations for naphthyl groups can be expected. Chapter V describes the synthesis of new P, O type ligands, β-keto phosphine, R2PCH2C(O)Ph, and acetamide phosphine R2PNHC(O)Me, as well as a series of new cobalt(III) complexes namely [(η5-C5H5)CoI2{Ph2PCH2C(O)Ph}], and [(η5- C5H5)CoI2{Ph2PNHC(O)Me}]. Treating these Co(III) compounds with an excess of Et3N, resulted in complexes η2-phosphinoenolate [(η5-C5H5)CoI{Ph2PCH…C(…O)Ph}] and η2- acetamide phosphine [(η5-C5H5)CoI{Ph2PN…C(…O)Me}]. Nickel (II) complexes were also obtained: cis-[Ni(Ph2PN…C(…O)Me)2] and cis-[Ni((i-Pr)2PN…C(…O)Me)2]. Their geometry and isomerism were discussed. Seven structures of the compounds described in this chapter were determined by single crystal X-ray diffraction. The general conclusions of this work can be found in Chapter VI.

From seashore to seashore: the cross-Atlantic agenda of the publisher António de Sousa Pinto

During the whole of the nineteenth century and the first decades of the twentieth century the transatlantic book trade was plainly asymmetrical, with Brazil seen by book vendors in Portugal as a natural extension of their market, destined to import books — a situation due largely to the incipient nature of Brazilian book production. However, the rapid development of the Brazilian printing and publishing industry in the first half of the twentieth century brought profound changes in the circulation of print material and in the traditional movements in the transatlantic book trade. Aware of those changes, some publishers and booksellers sought ways of expanding their businesses, by creating new openings for the circulation of books between the two countries. Taking the particular case of António de Sousa Pinto and his three Luso-Brazilian publishing ventures of the 1940s (Livros de Portugal, Edições Dois Mundos and Livros do Brasil), this article tries to understand the way publishers behaved in bringing together the two sides of the Atlantic closer together for the Lusophone book.

Accessibility and Local Development: Interaction between Cross-border Accessibility and Local Development in Portugal and Spain

One of de EU major concerns is cohesion and cross-border regional development. Usually cross-border regions are less dynamic, acting as bottlenecks mainly in peripheral territories. This paper is focused on the Portuguese-Spanish border using socio-economic and accessibility data. It considers Spatial Econometrics to produce statistical evidence on the relationship between accessibility and development at a local scale. A pilot study is conducted on North and Center region using variables such as population age, graduation characteristics, migrations, unemployment and daily accessibility to main towns in future this evaluation will be applied to the entire cross-border area between Portugal and Spain.

Cross-cultural validity of the demand-control questionnaire: Swedish and Brazilian workers

OBJECTIVE To evaluate the cross-cultural validity of the Demand-Control Questionnaire, comparing the original Swedish questionnaire with the Brazilian version. METHODS We compared data from 362 Swedish and 399 Brazilian health workers. Confirmatory and exploratory factor analyses were performed to test structural validity, using the robust weighted least squares mean and variance-adjusted (WLSMV) estimator. Construct validity, using hypotheses testing, was evaluated through the inspection of the mean score distribution of the scale dimensions according to sociodemographic and social support at work variables. RESULTS The confirmatory and exploratory factor analyses supported the instrument in three dimensions (for Swedish and Brazilians): psychological demands, skill discretion and decision authority. The best-fit model was achieved by including an error correlation between work fast and work intensely (psychological demands) and removing the item repetitive work (skill discretion). Hypotheses testing showed that workers with university degree had higher scores on skill discretion and decision authority and those with high levels of Social Support at Work had lower scores on psychological demands and higher scores on decision authority. CONCLUSIONS The results supported the equivalent dimensional structures across the two culturally different work contexts. Skill discretion and decision authority formed two distinct dimensions and the item repetitive work should be removed.

Experimental and numerical evaluation of composite repairs on wood beams damaged by cross-graining

An experimental and Finite Element study was performed on the bending behaviour of wood beams of the Pinus Pinaster species repaired with adhesively-bonded carbon–epoxy patches, after sustaining damage by cross-grain failure. This damage is characterized by crack growth at a small angle to the beams longitudinal axis, due to misalignment between the wood fibres and the beam axis. Cross-grain failure can occur in large-scale in a wood member when trees that have grown spirally or with a pronounced taper are cut for lumber. Three patch lengths were tested. The simulations include the possibility of cohesive fracture of the adhesive layer, failure within the wood beam in two propagation planes and patch interlaminar failure, by the use of cohesive zone modelling. The respective cohesive properties were estimated either by an inverse method or from the literature. The comparison with the tests allowed the validation of the proposed methodology, opening a good perspective for the reduction of costs in the design stages of these repairs due to extensive experimentation.

Relationship of health workers with their organization and work: a cross-cultural study

ABSTRACT We analyzed the differences, by Student’s t-test and ANOVA, between nurses and physicians from Portugal, Poland, Spain, and United Kingdom regarding their relationship with their work and organization. In total, 1,401 professionals answered the HSA-QHPR questionnaire. There are different levels of connection between physicians and nurses. The United Kingdom has the lowest levels of connection with the work while Portugal has the highest levels of relationship with the organization. The results provide guidelines for the development of policies and differential strategies aimed at improving the quality of healthcare service.

MBR activated sludge filterability characterization in cross flow filtration

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para a obtenção do grau de Mestre em Engenharia do Ambiente, perfil Sanitária

Reactivity of bulky tris(Phenylpyrazolyl) methanesulfonate copper(I) complexes towards small unsaturated molecules

Reaction of the tris(3-phenylpyrazolyl)methane sulfonate species (Tpms(Ph))Li with the copper(I) complex [Cu(MeCN)(4)][PF6] affords [Cu(Tpms(Ph))(MeCN)] 1. The latter, upon reaction with equimolar amounts of cyclohexyl-(CyNC) or 2,6-dimethylphenyl (XylNC) isocyanides, or excess CO, furnishes the corresponding Cu(I)complexes [Cu(Tpms(Ph))(CNR)] (R = Cy 2, Xyl 3) or [Cu(Tpms(Ph))(CO)] 4. The ligated isocyanide in 2 or 3 (or the acetonitrile ligand in 1)is displaced by 3-iminoisoindolin-1-one to afford 5, the first copper(I) complex containing an 3-iminoisoindolin-1-one ligand. The ligated acetonitrile in 1 undergoes nucleophilic attack by methylamine to give the amidine complex [Cu(Tpms(Ph)){MeC(NH)NHMe}] 6, whereas only the starting materials were recovered from the attempted corresponding reactions of 2 and 3 with methylamine. Complexes 1 or 6 form the trinuclear hydroxo-copper(II)species [(mu-Cu){Cu(mu-OH) (2)(Tpms(Ph))}(2)] 7 upon air oxidation in moist methanol. In all the complexes the scorpionate ligand facially caps the metal in the N,N,O-coordination mode.

Reactivity of syringyl and guaiacyl lignin units and delignification kinetics in the kraft pulping of eucalyptus globulus wood using Py-Gc-Ms/FID

Eucalyptus globulus sapwood and heartwood showed no differences in lignin content (23.0% vs. 23.7%) and composition: syringyl-lignin (17.9% vs. 18.0%) and guaiacyl-lignin (4.8% vs. 5.2%). Delignification kinetics of S- and G-units in heartwood and sapwood was investigated by Py-GC–MS/FID at 130, 150 and 170 °C and modeled as double first-order reactions. Reactivity differences between S and G-units were small during the main pulping phase and the higher reactivity of S over G units was better expressed in the later pulping stage. The residual lignin composition in pulps was different from wood or from samples in the initial delignification stages, with more G and H-units. S/G ratio ranged from 3 to 4.5 when pulp residual lignin was higher than 10%, decreasing rapidly to less than 1. The S/H was initially around 20 (until 15% residual lignin), decreasing to 4 when residual lignin was about 3%.

Reactivity of human fetal and adult immortalized hepatocytes to potentially toxic bilirubin and bile acid species

Dissertação apresentada para a obtenção do Grau de Mestre em Genética Molecular e Biomedicina, pela Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia

Evolution of schistosomiasis in an hyperendemic area of the Minas Gerais state: two cross-sectional studies

Two cross-sectional studies on schistosomiasis mansoni were done in Comercinho, Minas Gerais (Brazil), at an interval of 7 years. In 1974 and 1981 feces examinations (KATO-KATZ method) were done in 89 and 90% of the population (about 1,500 inhabitants) and clinical examinations were done in 78 and 92% of the patients who excreted Schistosoma mansoni eggs in the feces, respectively. The rate of infection by S. mansoni did not change (69.9% in 1974 and 70.4% in 1981), but the geometrical mean of eggs per gram of feces (431 ± 4 and 334 ± 4, respectively) and the rate of splenomegaly (11 and 7%, respectively) decreased significantly in 1981, when compared to 1974. This reduction was observed only in the central zones of the town (zones 1-2) where the rate of dwellings with piped water increased from 17 to 44%. In the surroundings (zones 3-4), where the proportion of houses with piped water did not change significantly between 1974 (10%) and 1981 (7%), the geometrical mean of S. mansoni eggs and the rate of splenomegaly did not change either.

Solution-Processable Donor-Acceptor-Donor Oligomers with Cross-Linkable Functionality

Electron-acceptor units, combined with bithiophene substituted with flexible chains end-functionalized with cross-linkable moieties, provide soluble donor-acceptor-donor (DAD) it-conjugated oligomer-type molecules with cross-linking ability and broad absorption in the visible spectrum. A study on the cross-linking conditions of the new oligomers to yield insoluble polymer networks is presented, including conditions for obtaining polymer films over poly(3,4-ethylenedioxythiophene):polystyrene sulfonate-covered substrates. The combination of the DAD molecular design and cross-linking functionality opens prospects for applications in solution-processed small-molecule solar cells with morphologically-stable organic layers.

Overproduction of the english definitive article by portuguese learners: a cross-sectional study

The English article system is actually so complex that it presents many challenges for most non-native learners of English. The main difficulty of Portuguese learners, despite the numerous similarities between the two article systems, is noticeable in a marked tendency to produce the definite article where native speakers of English would not use it. This article reports the results of a cross-sectional study which examined the English definite article overproduction by a group of 12 Portuguese EFL learners with at least seven years of English instruction. The prediction is that these learners will exhibit evidence of transferring L1 features to their interlanguage when they overuse the definite article. The data were collected by means of a gap-filling task and a composition. The results found, as predicted, that these learners overused the in generic contexts. It is argued that this overuse is directly tied to and can be explained by transfer to somewhere and conceptual transfer principles.

Portuguese Red Cross - Conde d´Óbidos Palace National Headquarters

Ano VI; nº 2 - 2008 - p.103-106