A kinetic study of the thermally initiated free radical reactions of styrene with octanedithiol as a model for the reactions of multifunctional thiols with divinylbenzene

The kinetics of chain reactions of octanedithiol with styrene, thermally initiated with TX29B50 (a 50:50 wt% solution of TX29 diperoxy initiator in a phthalate plasticizer), have been studied over a range of initiator concentrations, a range of mixture formulations and a range of temperatures. This system has been investigated as a model system for the reactions of polyfunctional thiols with divinyl benzene. The reactions have been shown to follow first-order kinetics for both the thiol and the ene species and to be characterized by a dependence on the initiator concentration to the power of one half. The kinetic rate parameters have been shown to adhere to Arrhenius behaviour. A kinetic model for the chain reactions for this system has been proposed. (C) 2003 Society of Chemical Industry.

Albert-László Barabási, Linked – The New Science of Networks, Perseus, Cambridge, 2002. Duncan J. Watts, Six Degrees – The Science of a Connected Age, William Heinemann, Londres, 2003.

Com a criação da teoria das redes, assistiu-se nos últimos anos a uma revolução científica de carácter interdisciplinar Não é uma teoria inteiramente nova, tendo sido precedida pela criação por P. Erdvos, nos anos sessenta, da teoria dos grafos aleatórios. Esta última é uma teoria puramente matemática, donde termos escrito “grafo” em lugar de “rede”. Apenas recentemente podemos falar de uma efectiva teoria das redes reais, e isso devido ao abandono de algumas das ideias essenciais avançadas por Erdvos, em especial a ideia de partir de um conjunto previamente dado de nós, os quais de seguida vão sendo conectados aleatoriamente com probabilidade p. Este quadro geral começou a ser modificado pelo chamado modelo dos “mundo-pequenos” proposto em 1998 por Duncan Watts e Steve Strogatz, modificação que se tornou ainda mais radical quando, em 1999, Albert Barabási e colaboradores propuseram um modelo no qual os nós vão progressivamente nascendo e conectados por uma função de preferência: um nó conecta-se em proporção às ligações que os outros nós já possuem, pelo que quantas mais ligações um nó possui maior a probabilidade de receber ulteriores ligações.

Evaluation of organophosphorus and synthetic pyrethroid insecticides against six vector mosquitoe species

Three organophosphorus compounds- malathion, folithion and temephos- and two synthetic pyrethroids- alphamethrin and deltamethrin- were used for monitoring the susceptibility status of larvae and adults of six vector mosquitoe species: Culex quinquefasciatus (Filariasis) and Aedes albopictus (Dengue) (both laboratory and field strains); laboratory strains of Aedes aegypti (Dengue), Anopheles slephensi and Anopheles culicifacies (Malaria), and Culex tritaeniorhynchus (Japanese encephalitis) in India. From the LC50 values obtained for these insecticides, it was found that all mosquito species including the field strains of Cx. quinquefasciatus and Ae. albopictus were highly susceptible Except for Cx. quinquefasciatus (field strain) against malathion, 100% mortality was observed at the discriminating dosages recommended by World Health Organization. The residual effect of alphamethrin, deltamethrin, malathion and folithion at 25 mg (ai)/m² on different surfaces against six species of vector mosquitoes showed that alphamethrin was the most effective on all four treated surfaces (mud, plywood, cement and thatch). Nevertheless, residual efficacy lasted longer on thatch than on the other surfaces. Therefore, synthetic pyrethroids such as alphamethrin can be effectively employed in integrated vector control operations.

Air fungal contamination in two elementary schools in Lisbon, Portugal

A descriptive study was developed to monitor air fungal contamination in two elementary schools in Lisbon, Portugal. Eight air samples of 250 litres through impaction method were collected in canteen, library, classrooms and also, outside premises as reference place. Simultaneously, were also monitored environmental parameters, including temperature, and humidity through the equipment Babouc, LSI Sistems and according to the International Standard ISO 7726 - 1998. Considering both schools, sixteen different species of fungi in air were identified, being the 2 most commonly isolated Cladosporium sp. (51,1%) and Penicillium sp. (27,5%). Besides these genera Trichoderma, Aspergillus, Alternaria, Chrysonilia, Botritys, Ulocladium, Athrium, Aureobasidium, Phoma, Scedosporium e Geotrichum were also isolated. Regarding yeasts, Candida sp., Cryptococcus sp. and Rhodotorula sp. were isolated. The youngest school, as well canteens in each school, presented the worst results concerning the air fungal contamination, maybe due to the higher number of occupants. There was no significant relationship (p>0,05) between fungal contamination and temperature and humidity.

Causal attributions in Brazilian children's reasoning about health and illness

INTRODUCTION: At a time when a great number of diseases can be prevented by changing one's habits and life style, investigations have focused on understanding what adults and children believe to be desirable health practices and uncovering the factors associated with successful adherence to such practices. For these, causal attributions for health and illness were investigated among 96 Brazilian elementary school students. METHODS: Ninety six subjects, aged 6 to 14, were interviewed individually and their causal attributions were assessed through 14 true-false items (e.g. people stay well [healthy] because they are lucky). The relationship between the children's causal attributions and demographic characteristics were also examined. RESULTS: Overall, the results were consistent with previous researches. "Taking care of oneself" was considered the most important cause of good health. "Viruses and germs" and "lack of self-care" were the most selected causes of illness. Analyses revealed significant relationship between subjects' causal attribution and their age, school grade level, socioeconomic status and gender. CONCLUSIONS: The study findings suggest that there may be more cross-cultural similarities than differences in children's causal attributions for health and illness. Finding ways to help individuals engage in appropriate preventive-maintenance health practices without developing an exaggerated notion that the individuals can control their own health and illness is a challenge which remains to be addressed by further research.

Crescer com saúde. Perspectiva dos professores do 1.º ciclo acerca da postura dos alunos e análise postural de crianças com 6 a 7 anos inseridas na comunidade escolar

O presente estudo teve como objectivos conhecer a percepção dos professores do ensino básico acerca da postura corporal dos alunos na sala de aula e analisar a postura de alunos do 1º ano do ensino básico. Este estudo foi realizado numa escola do 1º Ciclo, com 6 professores voluntários e 40 alunos do 1º ano. Na I parte referente ao estudo qualitativo, realizou-se uma discussão por grupo focal, com um roteiro de perguntas que os professores foram discutindo livremente expondo as suas opiniões. Concluiu-se que há por parte dos professores noção de como é a postura corporal dos alunos na sala de aula, como essa postura corporal, pode influenciar de forma, positiva ou negativa o estado de saúde do aluno na sala de aula e comprometer a qualidade de vida dos alunos. Na II parte quantitativa os alunos foram avaliados através do registo fotográfico, num programa de avaliação postural, demonstrando os resultados que na amostra em estudo não foi encontrado desvio vertical significativo entre a cintura escapular e a cintura pélvica. No entanto, foi encontrado desvio horizontal significativo do alinhamento das omoplatas entre si e das espinhas ilíacas postero-superiores entre si, já indicando um início de desvio postural com carácter escoliótico. Conclui-se pois que os alunos avaliados apresentavam problemas posturais com necessidade de serem acompanhados por Fisioterapeutas.

Complexes of copper(II) with 3-(ortho-substituted phenylhydrazo)pentane-2,4-diones: syntheses,properties and catalytic activity for cyclohexane oxidation

Reactions of copper(II) with 3-phenylhydrazopentane-2,4-diones X-2-C6H4-NHN = C{C(= O)CH3}(2) bearing a substituent in the ortho-position [X = OH (H2L1) 1, AsO3H2 (H3L2) 2, Cl (HL3) 3, SO3H (H2L4) 4, COOCH3 (HL5) 5, COOH (H2L6) 6, NO2 (HL7) 7 or H (HL8) 8] lead to a variety of complexes including the monomeric [CuL4(H2O)(2)]center dot H2O 10, [CuL4(H2O)(2)] 11 and [Cu(HL4)(2)(H2O)(4)] 12, the dimeric [Cu-2(H2O)(2)(mu-HL2)(2)] 9 and the polymeric [Cu(mu-L-6)](n)] 13 ones, often bearing two fused six-membered metallacycles. Complexes 10-12 can interconvert, depending on pH and temperature, whereas the Cu(II) reactions with 4 in the presence of cyanoguanidine or imidazole (im) afford the monomeric compound [Cu(H2O)(4){NCNC(NH2)(2)}(2)](HL4)(2)center dot 6H(2)O 14 and the heteroligand polymer [Cu(mu-L-4)(im)](n) 15, respectively. The compounds were characterized by single crystal X-ray diffraction (complexes), electrochemical and thermogravimetric studies, as well as elemental analysis, IR, H-1 and C-13 NMR spectroscopies (diones) and ESI-MS. The effects of the substituents in 1-8 on the HOMO-LUMO gap and the relative stability of the model compounds [Cu(OH)(L-8)(H2O)]center dot H2O, [Cu(L-1)(H2O)(2)]center dot H2O and [Cu(L-4)(H2O)(2)]center dot H2O are discussed on the basis of DFT calculations that show the stabilization follows the order: two fused 6-membered > two fused 6-membered/5-membered > one 6-membered metallacycles. Complexes 9, 10, 12 and 13 act as catalyst precursors for the peroxidative oxidation (with H2O2) of cyclohexane to cyclohexanol and cyclohexanone, in MeCN/H2O (total yields of ca. 20% with TONs up to 566), under mild conditions.

Hexanuclear and undecanuclear iron(III) carboxylates as catalyst precursors for cyclohexane oxidation

Two multinuclear complexes [Fe-6(mu(3)-O)(2)(mu(4)-O-2)L-10(OAc)(2)(H2O)(2)]center dot 2.625Et(2)O center dot 2.375H(2)O (1) and [(Fe11Cl)-Cl-III-(mu(4)-O)(3)(mu(3)-O)(5)L-16(dmf)(2.5)(H2O)(0.5)]center dot Et2O center dot 1.25dmf center dot 3.8H(2)O (2), where HL = 3,4,5-trimethoxybenzoic acid and dmf = dimethylformamide, have been prepared from trinuclear iron(III) carboxylates via their structural rearrangement in dimethylformamide or diethyl ether-dimethylformamide 9:1, respectively, and slow vapor diffusion of diethyl ether into the reaction mixture. Both compounds have been characterized by X-ray diffraction, optical, Mossbauer spectroscopy, and magnetic measurements. Complex 1 possesses a hexanuclear ferric peroxido-dioxido {Fe-6(O-2)(O)(2)}(12+) core unit, which adopts a recliner conformation, while complex 2 contains an unprecedented {Fe11O8Cl}(16+) core, in which 9 ferric ions are six-coordinate and the remaining two are five-coordinate. Another structural feature of note of the undecanuclear core is the presence of a deformed cubane entity {Fe-4(mu(3)-O)(mu(4)-O)(3)}(4+). Both complexes act as catalyst precursors for the oxidation of cyclohexane to cyclohexanol and cyclohexanone with aqueous H2O2, in the presence of pyrazinecarboxylic acid. Remarkable TONs and TOFs (the latter mainly for 1) with concomitant quite good yields have been achieved under mild conditions. Moreover, 1 exhibits remarkably high activity in an exceptionally short reaction time (45 min), being unprecedented for any metal catalyzed alkane oxidation by H2O2. The catalytic reactions proceed via Fenton type chemistry.

Analysis of six fungicides and one acaricide in still and fortified wines using solid-phase microextraction-gas chromatography/tandem mass spectrometry

A multiresidue gas chromatographic method for the determination of six fungicides (captan, chlorthalonil, folpet, iprodione, procymidone and vinclozolin) and one acaricide (dicofol) in still and fortified wines was developed. Solid-phase microextraction (SPME) was chosen for the extraction of the compounds from the studied matrices and tandem mass spectrometry (MS/MS) detection was used. The extraction consists in a solvent free and automated procedure and the detection is highly sensitive and selective. Good linearity was obtained with correlation coefficients of regression (R2) > 0.99 for all the compounds. Satisfactory results of repeatability and intermediate precision were obtained for most of the analytes (RSD < 20%). Recoveries from spiked wine ranged from 80.1% to 112.0%. Limits of quantification (LOQs) were considerably below the proposedmaximumresidue limits (MRLs) for these compounds in grapes and below the suggested limits for wine (MRLs/10), with the exception of captan.

Occupational exposure to toxigenic fungi from Aspergillus flavus complex

Bioaerosols are mainly composed of fungal particles, bacteria and plant spores, being fungi responsible for the release of VOCs and micotoxins into indoor environments. Aspergillus flavus is a common opportunistic pathogen causing human infections and is involved in the production of aflatoxin and other secondary metabolites associated with toxic and allergic reactions. Poultry workers are exposed to high concentrations of fungi and are therefore more prone to develop associated pathologies. To evaluate occupational exposure of the workers to Aspergillus flavus and aflatoxins, six animal production facilities were selected, including 10 buildings, from which indoor air samples and outdoor reference samples were obtained. Twenty-five duplicate samples were collected by two methodologies: impactation onto malt extract agar of 25L air samples using a Millipore Air Tester were used to evaluate quantitative (CFU/m3) and qualitative (species identification, whenever possible) sample composition; 300 L air samples collected with the Coriolis Air Sampler into phosphate–saline buffer were used to isolate DNA, following molecular identification of Aspergillus section flavi using nor-1 specific primers by real-time PCR.

Disruption and phenotypic analysis of six open reading frames from chromosome VII of Saccharomyces cerevisiae reveals one essential gene

Six open reading frames (ORFs) located on chromosome VII of Saccharomyces cerevisiae (YGR205w, YGR210c, YGR211w, YGR241c, YGR243w and YGR244c) were disrupted in two different genetic backgrounds using short-flanking homology (SFH) gene replacement. Sporulation and tetrad analysis showed that YGR211w, recently identified as the yeast ZPR1 gene, is an essential gene. The other five genes are non-essential, and no phenotypes could be associated to their inactivation. Two of these genes have recently been further characterized: YGR241c (YAP1802) encodes a yeast adaptor protein and YGR244c (LSC2) encodes the b-subunit of the succinyl-CoA ligase. For each ORF, a replacement cassette with long flanking regions homologous to the target locus was cloned in pUG7, and the cognate wild-type gene was cloned in pRS416.

Daytime dive characteristics from six short-finned pilot whales Globicephala macrorhynchus off Madeira Island

Six time-depth recorders attached with suction-cups were deployed in resident and transient adult short-finned pilot whales to evaluate their daytime diving characteristics in their preferred habitat area off Madeira Island. Here, data on the proportion of time spent at the surface and at different dive phases (descent, bottom and ascent), dive depths and dive rates are presented. With mean attachment durations of 2 h 31 min (SD=2 h), the whales spent a considerable amount of time at the surface (mean=76.3%, SD=18.6) and presented a low diving rate (mean=6.8 dives h‾¹, SD=6.1; considering dive as submergence deeper than 10 m). The maximum dive depth recorded in this study was 988 m, and dives deeper than 500 m, which were recorded from resident and transient whales, suggest foraging activity along their preferred habitat area. The analysis of dives deeper than 100 m shows that the percentage of time spent on descent, bottom or ascent varied between dives, with means of ~40, 30 and 30%, respectively.

Agreement between data obtained from repeated interviews with a six-years interval

The objective of the study was to compare information collected through face-to-face interviews at first time and six years later in a city of Southeastern Brazil. In 1998, 32 mothers (N=32) of children aged 20 to 30 months answered a face-to-face interview with structured questions regarding their children's brushing habits. Six years later this same interview was repeated with the same mothers. Both interviews were compared for overall agreement, kappa and weighted kappa. Overall agreement between both interviews varied from 41 to 96%. Kappa values ranged from 0.00 to 0.65 (very bad to good) without any significant differences. The results showed lack of agreement when the same interview is conducted six years later, showing that the recall bias can be a methodological problem of interviews.