Óxidos do tipo perovskita para reação de redução de no com CO

In this work, the perovskite-type oxides LaNiO3, LaMnO3, La0,7Sr0,3NiO3 and La0,7Sr0,3MnO3 were prepared by co-precipitation and tested in the NO reduction with CO at 400 and 500 ºC for 10 h. The catalysts were characterized by X-ray diffraction, temperature programmed reduction with hydrogen, nitrogen adsorption and chemical analysis. The nonstoichiometric oxygen was quantified by temperature programmed reduction, and the catalytic tests showed that the La0,7Sr0,3MnO3 catalyst presented the higher performance for the reduction reaction of NO with CO. The partial substitution of lanthanum by strontium increased the NO conversion and the N2 yield.

Biocompósitos de matriz glioxal-fenol reforçada com celulose microcristalina

Glioxal pode ser obtido a partir de biomassa (como da oxidação de lipídeos) e não é tóxico ou volátil, tendo sido por isso utilizado no presente trabalho como substituto de formaldeído na preparação de resina fenólica do tipo novolaca, sendo usado como catalisador o ácido oxálico, que também pode ser obtido de fontes renováveis. A resina glioxal-fenol foi utilizada na preparação de compósitos reforçados com celulose microcristalina (CM, 30, 50 e 70% em massa), uma celulose com elevada área superficial. As imagens de microscopia eletrônica de varredura (MEV) das superfícies fraturadas demonstraram que os compósitos apresentaram boa interface reforço/matriz, consequência da elevada área superficial da CM e presença de grupos polares (hidroxilas) tanto na matriz como na celulose, o que permitiu a formação de ligações hidrogênio, favorecendo a compatibilidade entre ambas. A análise térmica dinâmico-mecânica (DMTA) demonstrou que todos os compósitos apresentaram elevado módulo de armazenamento à temperatura ambiente. Além disso, o compósito reforçado com 30% de CM apresentou baixa absorção de água, comparável à do termorrígido fenólico, que é utilizado em escala industrial. Os resultados demonstraram que compósitos com boas propriedades podem ser preparados usando elevada proporção de materiais obtidos de biomassa.

Synthesis of Fe/Ti oxides from a single source alkoxide precursor under inert atmosphere

The heterometal alkoxide [FeCl{Ti2(OPr i)9}] (1) was employed as a single source precursor for the preparation of Fe/Ti oxides under inert atmosphere. Three different synthetic procedures were adopted in the processing of 1, either employing aqueous HNO3 or HCl solutions, or in the absence of mineral acids. Products were characterised by powder X-ray diffractometry, scanning electron microscopy combined with energy dispersive X-ray spectroscopy (SEM/EDS) and Raman, electron paramagnetic resonance (EPR) and Mössbauer spectroscopies. Oxide products contained titanium(IV) and either iron(III) or iron(II), depending on reaction conditions and thermal treatment temperatures. An interesting iron(III)→iron(II) reduction was observed at 1000 ºC in the HNO3-containing system, leading to the detection of ilmenite (FeTiO3). SEM/EDS studies revealed a highly heterogeneous metal distribution in all products, possibly related to the presence of a significant content of carbon and of structural defects (oxygen vacancies) in the solids.

Ethanol electrooxidation on Pt-Sn and Pt-Sn-W bulk alloys

Ethanol oxidation has been studied on Pt-Sn and Pt-Sn-W electrodes prepared in an arc-melting furnace. Different electrochemical techniques like cyclic voltammetry and chronoamperometry were used to evaluate the catalytic activity of these materials. The electro-oxidation process was also investigated by in situ infrared reflectance spectroscopy in order to determine adsorbed intermediates and reaction products. Experimental results indicated that Pt-Sn and Pt-Sn-W alloys are able to oxidize ethanol mainly to acetaldehyde and acetic acid. Adsorbed CO was also detected, demonstrating the viability of splitting the C-C bond in the ethanol molecule during the oxidation process. The adsorbed CO was further oxidized to CO2.This reaction product was clearly detected by SNIFTIRS. Pt-Sn-W catalyst showed a better electrochemical performance than Pt-Sn that, in it turn, is better than Pt-alone.

Electrocatalytic oxidation of methanol by the [Ru3O(OAc)6(py)2(CH3OH)]3+cluster: improving the metal-ligand electron transfer by accessing the higher oxidation states of a multicentered system

The [Ru3O(Ac)6(py)2(CH3OH)]+ cluster provides an effective electrocatalytic species for the oxidation of methanol under mild conditions. This complex exhibits characteristic electrochemical waves at -1.02, 0.15 and 1.18 V, associated with the Ru3III,II,II/Ru3III,III,II/Ru 3III,III,III /Ru3IV,III,III successive redox couples, respectively. Above 1.7 V, formation of two RuIV centers enhances the 2-electron oxidation of the methanol ligand yielding formaldehyde, in agreement with the theoretical evolution of the HOMO levels as a function of the oxidation states. This work illustrates an important strategy to improve the efficiency of the oxidation catalysis, by using a multicentered redox catalyst and accessing its multiple higher oxidation states.

Análise de pinturas rupestres do Abrigo do Janelão (Minas Gerais) por microscopia raman

Rock art paintings from Abrigo do Janelão (Minas Gerais, Brazil) were non-destructively investigated by Raman Microscopy, aiming at the identification of materials used, their interaction and degradation. This technique is particularly tailored for heterogeneous samples and allows unequivocal identification of the substances present in the investigated sample. Pigments, were identified together with products of microbiological degradation; no binders were detected. White pigment was identified as calcite (CaCO3), whereas charcoal was used as black, goethite (α-FeOOH) as yellow and hematite (α-Fe2O3) as red. Whewellite (CaC2O4.H2O) and weddelite (CaC2O4.2H2O) were detected and their origin was assigned to degradation products from microbiological activity.

Polychaete assemblage of an impacted estuary, Guanabara Bay, Rio de Janeiro, Brazil

Thirty-eight stations were sampled in Guanabara Bay, Rio de Janeiro, Brazil, to assess the spatio-temporal diversity and biomass of sublittoral polychaetes. Samples were collected during the dry (September 2000) and rainy season (May 2001) in shallow sublittoral sediments. The polychaete spatial composition showed a heterogeneous distribution throughout the bay. A negative gradient of diversity and biomass was observed towards the inner parts of the bay and sheltered areas. A wide azoic area was found inside the bay. Some high-biomass and low-diversity spots were found near a sewage-discharge point. In these areas, the polychaete biomass increased after the rainy season. A diversified polychaete community was identified around the bay mouth, with no dramatic changes of this pattern between the two sampling periods. Deposit-feeders were dominant in the entire study area. The relative importance of carnivores and omnivores increased towards the outer sector, at stations with coarse sediment fractions. Guanabara Bay can be divided into three main zones with respect to environmental conditions and polychaete diversity and biomass patterns: A) High polychaete diversity, hydrodynamically exposed areas composed of sandy, oxidized or moderately reduced sediments with normoxic conditions in the water column. B) Low diversity and high biomass of deposit and suspension-feeding polychaete species in the middle part of the bay near continental inflows, comprising stations sharing similar proportions of silt, clay and fine sands. C) Azoic area or an impoverished polychaete community in hydrodynamically low-energy areas of silt and clay with extremely reduced sediments, high total organic matter content and hypoxic conditions in the water column, located essentially from the mid-bay towards the north sector. High total organic matter content and hypoxic conditions combined with slow water renewal in the inner bay seemed to play a key role in the polychaete diversity and biomass. Sedimentation processes and organic load coming from untreated sewage into the bay may have negatively affected the survivorship of the fauna.

Condições de vida e mortalidade infantil no município do Embu, São Paulo

OBJETIVO: Descrever a distribuição do coeficiente de mortalidade infantil e seus componentes no município do Embu, São Paulo, no período de 1995 a 1998, segundo os estratos de condições de vida. MÉTODOS: Estudo descritivo com análise por conglomerados,dos 135 setores censitários do município de Embu, agrupados em quatro estratos de condições de vida: estrato 1, com melhores condições de moradia, renda e escolaridade; estratos 2 e 3, intermediários; estrato 4, no qual todas as moradias eram aglomerados subnormais ou favelas. Foram calculados os coeficientes de mortalidade infantil, neonatal e pós-neonatal, a proporção entre óbitos neonatais e pós-neonatais, o risco atribuível populacional e mortalidade proporcional por causas, para os anos de 1995 a 1998, segundo os quatro estratos de condições de vida estabelecidos. RESULTADOS: O estrato 4 apresentou maiores coeficientes de mortalidade infantil e risco atribuível populacional em relação aos estratos intermediários, em todos os anos do estudo. Esse estrato apresentou, também, as menores proporções entre mortalidade neonatal e pós-neonatal. O risco atribuível populacional no estrato 4 foi maior que os demais estratos para as afecções perinatais (159,4), doenças respiratórias (271,4) e doenças infecciosas (415,6). Identificaram-se dados demográficos semelhantes em áreas próximas aos limites geograficamente constituídos pelo estudo e heterogeneidade de eventos num mesmo território. CONCLUSÕES: Identificou-se uma relação entre desigualdades sociais e mortalidade infantil, segundo os critérios de condições de vida estabelecidos para este estudo, entretanto, não houve distribuição homogênea nos quatro estratos populacionais, revelando dificuldades em utilizá-los como parâmetros para desigualdades sociais em grandes centros urbanos.

Concentrações de vitamina A no leite humano e características socioeconômicas e nutricionais maternas: resultados de estudos brasileiros

OBJETIVOS: agregar e discutir os resultados de estudos realizados no Brasil que avaliaram a concentração de vitamina A no leite materno. FONTES DOS DADOS: foram pesquisadas as bases LILACS, Banco de Teses da Capes, SciELO (Scientific Electronic Library), e Plataforma Lattes -seção de produção científica. As palavras-chaves utilizadas foram: gestantes, lactante, concentração de vitamina A no leite humano, Brasil. As buscas foram realizadas em 2006 e atualizadas em março de 2008. Foram incluídos todos os estudos localizados. SÍNTESE DOS DADOS: foram localizados 14 estudos, publicados entre 1988 e 2008, heterogêneos quanto ao tamanho da amostra, fase do leite, período do dia da coleta e método de determinação das concentrações de vitamina A. Foram descritas concentrações médias de vitamina A no leite humano entre 0,62 e 4,50 µmol/L. CONCLUSÕES: não houve consenso sobre a relação entre concentração de vitamina A no leite humano e vitamina A dietética, estado nutricional materno, características obstétricas e demográficas e duração da gestação. Sugere-se que estudos futuros utilizem, amostras de leite maduro, coletadas aleatoriamente ao longo dos diferentes períodos do dia, e a utilização do high performance liquid chromatography - HPLC - como método de determinação de vitamina A.

Searching for molecular markers in head and neck squamous cell carcinomas (HNSCC) by statistical and bioinformatic analysis of larynx-derived SAGE libraries

Background: Head and neck squamous cell carcinoma (HNSCC) is one of the most common malignancies in humans. The average 5-year survival rate is one of the lowest among aggressive cancers, showing no significant improvement in recent years. When detected early, HNSCC has a good prognosis, but most patients present metastatic disease at the time of diagnosis, which significantly reduces survival rate. Despite extensive research, no molecular markers are currently available for diagnostic or prognostic purposes. Methods: Aiming to identify differentially-expressed genes involved in laryngeal squamous cell carcinoma (LSCC) development and progression, we generated individual Serial Analysis of Gene Expression (SAGE) libraries from a metastatic and non-metastatic larynx carcinoma, as well as from a normal larynx mucosa sample. Approximately 54,000 unique tags were sequenced in three libraries. Results: Statistical data analysis identified a subset of 1,216 differentially expressed tags between tumor and normal libraries, and 894 differentially expressed tags between metastatic and non-metastatic carcinomas. Three genes displaying differential regulation, one down-regulated (KRT31) and two up-regulated (BST2, MFAP2), as well as one with a non-significant differential expression pattern (GNA15) in our SAGE data were selected for real-time polymerase chain reaction (PCR) in a set of HNSCC samples. Consistent with our statistical analysis, quantitative PCR confirmed the upregulation of BST2 and MFAP2 and the downregulation of KRT31 when samples of HNSCC were compared to tumor-free surgical margins. As expected, GNA15 presented a non-significant differential expression pattern when tumor samples were compared to normal tissues. Conclusion: To the best of our knowledge, this is the first study reporting SAGE data in head and neck squamous cell tumors. Statistical analysis was effective in identifying differentially expressed genes reportedly involved in cancer development. The differential expression of a subset of genes was confirmed in additional larynx carcinoma samples and in carcinomas from a distinct head and neck subsite. This result suggests the existence of potential common biomarkers for prognosis and targeted-therapy development in this heterogeneous type of tumor.

The expression of genes coding for distinct types of glycine-rich proteins varies according to the biology of three metastriate ticks, Rhipicephalus (Boophilus) microplus, Rhipicephalus sanguineus and Amblyomma cajennense

Background: Ticks secrete a cement cone composed of many salivary proteins, some of which are rich in the amino acid glycine in order to attach to their hosts' skin. Glycine-rich proteins (GRPs) are a large family of heterogeneous proteins that have different functions and features; noteworthy are their adhesive and tensile characteristics. These properties may be essential for successful attachment of the metastriate ticks to the host and the prolonged feeding necessary for engorgement. In this work, we analyzed Expressed Sequence Tags (ESTs) similar to GRPs from cDNA libraries constructed from salivary glands of adult female ticks representing three hard, metastriate species in order to verify if their expression correlated with biological differences such as the numbers of hosts ticks feed on during their parasitic life cycle, whether one (monoxenous parasite) or two or more (heteroxenous parasite), and the anatomy of their mouthparts, whether short (Brevirostrata) or long (Longirostrata). These ticks were the monoxenous Brevirostrata tick, Rhipicephalus (Boophilus) microplus, a heteroxenous Brevirostrata tick, Rhipicephalus sanguineus, and a heteroxenous Longirostrata tick, Amblyomma cajennense. To further investigate this relationship, we conducted phylogenetic analyses using sequences of GRPs from these ticks as well as from other species of Brevirostrata and Longirostrata ticks. Results: cDNA libraries from salivary glands of the monoxenous tick, R. microplus, contained more contigs of glycine-rich proteins than the two representatives of heteroxenous ticks, R. sanguineus and A. cajennense (33 versus, respectively, 16 and 11). Transcripts of ESTs encoding GRPs were significantly more numerous in the salivary glands of the two Brevirostrata species when compared to the number of transcripts in the Longirostrata tick. The salivary gland libraries from Brevirostrata ticks contained numerous contigs significantly similar to silks of true spiders (17 and 8 in, respectively, R. microplus and R. sanguineus), whereas the Longirostrata tick contained only 4 contigs. The phylogenetic analyses of GRPs from various species of ticks showed that distinct clades encoding proteins with different biochemical properties are represented among species according to their biology. Conclusions: We found that different species of ticks rely on different types and amounts of GRPs in order to attach and feed on their hosts. Metastriate ticks with short mouthparts express more transcripts of GRPs than a tick with long mouthparts and the tick that feeds on a single host during its life cycle contain a greater variety of these proteins than ticks that feed on several hosts.

Parametric model for the analysis of concrete expansion due to alkali-aggregate reaction

The alkali-aggregate reaction (AAR) is a chemical reaction that provokes a heterogeneous expansion of concrete and reduces important properties such as Young's modulus, leading to a reduction in the structure's useful life. In this study, a parametric model is employed to determine the spatial distribution of the concrete expansion, combining normalized factors that influence the reaction through an AAR expansion law. Optimization techniques were employed to adjust the numerical results and observations in a real structure. A three-dimensional version of the model has been implemented in a finite element commercial package (ANSYS(C)) and verified in the analysis of an accelerated mortar test. Comparisons were made between two AAR mathematical descriptions for the mechanical phenomenon, using the same methodology, and an expansion curve obtained from experiment. Some parametric studies are also presented. The numerical results compared very well with the experimental data validating the proposed method.

Synthesis of diaryl selenides using electrophilic selenium species and nucleophilic boron reagents in ionic liquids

We described herein the use of imidazolium ionic liquids [bmim]PF(6) and [bmim]BF(4) in the selective, metal and catalyst-free synthesis of unsymmetrical diaryl selenides by electrophilic substitution in arylboron reagents with arylselenium halides (Cl and Br) at room temperature. This is a general substitution reaction and it was performed with arylboronic acids or potassium aryltrifluoroborates bearing electron-withdrawing or electron-donating groups, affording the corresponding diaryl selenides in good to excellent yields. The ionic liquid [bmim][PF(6)] was easily recovered and utilized for further substitution reactions.

Genomic islands in the pathogenic filamentous fungus Aspergillus fumigatus

We present the genome sequences of a new clinical isolate of the important human pathogen, Aspergillus fumigatus, A1163, and two closely related but rarely pathogenic species, Neosartorya fischeri NRRL181 and Aspergillus clavatus NRRL1. Comparative genomic analysis of A1163 with the recently sequenced A. fumigatus isolate Af293 has identified core, variable and up to 2% unique genes in each genome. While the core genes are 99.8% identical at the nucleotide level, identity for variable genes can be as low 40%. The most divergent loci appear to contain heterokaryon incompatibility ( het) genes associated with fungal programmed cell death such as developmental regulator rosA. Cross-species comparison has revealed that 8.5%, 13.5% and 12.6%, respectively, of A. fumigatus, N. fischeri and A. clavatus genes are species-specific. These genes are significantly smaller in size than core genes, contain fewer exons and exhibit a subtelomeric bias. Most of them cluster together in 13 chromosomal islands, which are enriched for pseudogenes, transposons and other repetitive elements. At least 20% of A. fumigatus-specific genes appear to be functional and involved in carbohydrate and chitin catabolism, transport, detoxification, secondary metabolism and other functions that may facilitate the adaptation to heterogeneous environments such as soil or a mammalian host. Contrary to what was suggested previously, their origin cannot be attributed to horizontal gene transfer ( HGT), but instead is likely to involve duplication, diversification and differential gene loss (DDL). The role of duplication in the origin of lineage-specific genes is further underlined by the discovery of genomic islands that seem to function as designated ""gene dumps'' and, perhaps, simultaneously, as "" gene factories''.

Cultivo da microalga marinha Chaetoceros calcitrans (BACILLARIOPHYCEAE) utilizando diferentes tipos de água marinha artificial

The use of microalgae as live food to a wide variety of organisms is one of the most important aspects in aquaculture. Several commercial formulations have been available in the marine aquarium market in order to prepare artificial sea water (ASW). The present study accounted microalgae Chaetoceros calcitrans performance cultured using different ASW in comparison to natural seawater(NSW). it was carried out using red Sea, Coralife and oceanic, three different ASW brands and NSW as control. nonaerated cultures were grew in 400 mL with Conwy culture medium with five replicates each under defined conditions. All cultures began with an algal inoculum of 208.000 cells/mL. a 5-mL aliquot was removed daily from each culture for cells counts. data obtained using polynomial regression test demonstrated that all ASW brands reached higher algal density rates than the one with NSW, though the three ASW brands were significantly heterogeneous. C. calcitrans raised with oceanic and red Sea brands showed similar growth rates and both were higher than Coralife brand. the results suggest that all three ASW brands studied can be used in the culture of this microalgae specie.