Unusual 1,6-diphenyl-1,3,5-hexatriene (DPH) spectrophotometric behavior in water/ethanol and water/DMSO mixtures

The absorption spectra of DPH at fixed concentration do not change with water content in organic solvents. It exhibits monomer bands, such as those obtained in ethanol. The absorption did not change for solutions up to 54 and 46% of water in ethanol and DMSO, respectively, for [DPH] = 5.0 × 10-6 mol L-1 at 30 °C. However, at the same experimental conditions, a gradual sharp decay of the DPH fluorescence is observed. It is proposed that water molecules below these water concentration limits act as quenchers of the excited states of DPH. Stern-Volmer quenching constants by intensities measurements are 7.4 × 10-2 (water/ethanol) and 2.6 × 10-2 L mol-1 (water/DMSO). DPH lifetime measurements in the absence and presence of water resulted in 7.1 × 10-2 L mol-1 in water/ethanol, which pointed out that the process is a dynamic quenching by water molecules. For experiments using DPH as probe, this process can affect data, leading to misunderstanding interpretation.

Aplicação de indentação instrumentada na caracterização mecânica de poliuretana derivada de óleo de mamona

Neste trabalho são investigadas as propriedades mecânicas de poliuretana derivada do óleo de mamona, utilizando a técnica de indentação instrumentada com penetradores de geometrias piramidal e esférica. Foi analisada a influência da forma do penetrador utilizado nos ensaios de indentação instrumentada para se obter valores das propriedades mecânicas de polímero derivado de óleo de mamona. Os penetradores utilizados são de pontas piramidais dos tipos Berkovich e canto de cubo e esférico de raio igual a 150 μm em um Nanoindenter XP TM com cargas aplicadas entre 1 e 200 mN. As penetrações variam de acordo com o formato do penetrador, sendo maiores para pontas agudas. A dureza e o módulo de elasticidade foram determinados, utilizando o método de Oliver e Pharr. Verificou-se que os valores medidos para a dureza são maiores para penetradores mais agudos. Os valores obtidos com a ponta piramidal Berkovich foram de 0,14 GPa para pequenas penetrações e 0,12 GPa para maiores penetrações. Já os valores obtidos com ponta canto de cubo foram 25 a 30% maiores. Isso está relacionado com os volumes das regiões que apresentam deformações plásticas elevadas, no caso de penetradores agudos comparados com os volumes das regiões que sofrem deformações viscoelásticas. A viscosidade aparente determinada, utilizando penetrador esférico em testes de força aplicada constante, é igual a (22 ± 2) × 10(12) Pa.s.

Caracterização mecânica e térmica da borracha natural formulada e vulcanizada dos clones: GT 1, IAN 873, PB 235 e RRIM 600

Neste trabalho estudou-se o desempenho mecânico e térmico de compostos de borracha natural (Hevea brasiliensis) de 4 diferentes clones (GT 1, IAN 873, PB 235 e RRIM 600) cultivados no Estado de São Paulo, assim como de uma mistura destes clones e de uma borracha comercial, GEB-1. Estas borrachas foram formuladas e vulcanizadas com tempos de 5, 7 e 9 minutos. A caracterização foi realizada por calorimetria exploratória diferencial, termogravimetria, ensaios de resistência à tração, análise dinâmico-mecânica, medidas de dureza Shore A, microscopia eletrônica de varredura e espectroscopia na região do infravermelho. Os resultados permitiram concluir que o tempo de vulcanização e o tipo de clone não influenciaram na temperatura de transição vítrea (Tg) dos compostos. Os valores de Tg obtidos por DMA foram de cerca de -62 °C, e os resultados ensaios de dureza apresentaram valores próximos de 60 para todos os compostos estudados. Os ensaios de resistência à tração mostraram que o melhor desempenho mecânico foi obtido pelo clone RRIM 600. De acordo com os resultados obtidos neste trabalho, todos os clones atingiram as propriedades reportadas na literatura, podendo ser utilizados, em princípio, nas indústrias de artefatos de borracha separadamente ou na forma de mistura.

Antioxidant and antimicrobial properties of 2-(4,5-dihydro-1H-pyrazol-1-yl)-pyrimidine and 1-carboxamidino-1H-pyrazole derivatives

Five previously synthesized 4-trifluoromethyl-2-(5-aryl-3-styryl-1H-pyrazol-1yl)-pyrimidines and six 5-aryl-3-styryl-1-carboxamidino-1H-pyrazole derivatives were screened for their antioxidant proprieties. The antioxidant activities were evaluated by using the DPPH and the HRP/luminol/H2O2 chemiluminescence assay systems and for their antimicrobial activity (MIC). The results were good for those series in some concentration in comparison with the standards.

Characterization studies of 1-(4-cyano-2-oxo-1,2-dihydro-1-pyridyl)-3-(4-cyano-1,2-dihydro-1-pyridyl)propane formed from the reaction of hydroxide Ion with 1,3-Bis-(4-cyano pyridinium)propane

The aqueous alkaline reaction of 1,3-bis(4-cyanopyridinium)propane dibromide, a reactant constituted of two pyridinium rings linked by a three-methylene bridge, generates a novel compound,1 -(4-cyano-2-oxo-1,2-dihydro-1-pyridyl)-3-(4-cyano-1,2-dihydro-1-pyridyl)propane. The reaction pathway is attributed to the proximity of the OH- ion inserted between two pyridinium moieties, which occurs only in bis(pyridinium) derivatives connected by short methylene spacers, where charge-conformational effects are important.

Non-coding RNAs in schistosomes: an unexplored world

Non-coding RNAs (ncRNAs) were recently given much higher attention due to technical advances in sequencing which expanded the characterization of transcriptomes in different organisms. ncRNAs have different lengths (22 nt to >1, 000 nt) and mechanisms of action that essentially comprise a sophisticated gene expression regulation network. Recent publication of schistosome genomes and transcriptomes has increased the description and characterization of a large number of parasite genes. Here we review the number of predicted genes and the coverage of genomic bases in face of the public ESTs dataset available, including a critical appraisal of the evidence and characterization of ncRNAs in schistosomes. We show expression data for ncRNAs in Schistosoma mansoni. We analyze three different microarray experiment datasets: (1) adult worms' large-scale expression measurements; (2) differentially expressed S. mansoni genes regulated by a human cytokine (TNF-α) in a parasite culture; and (3) a stage-specific expression of ncRNAs. All these data point to ncRNAs involved in different biological processes and physiological responses that suggest functionality of these new players in the parasite's biology. Exploring this world is a challenge for the scientists under a new molecular perspective of host-parasite interactions and parasite development.

Cyclic nitroxides inhibit the toxicity of nitric oxide-derived oxidants: mechanisms and implications

The substantial therapeutic potential of tempol (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy) and related cyclic nitroxides as antioxidants has stimulated innumerous studies of their reactions with reactive oxygen species. In comparison, reactions of nitroxides with nitric oxide-derived oxidants have been less frequently investigated. Nevertheless, this is relevant because tempol has also been shown to protect animals from injuries associated with inflammatory conditions, which are characterized by the increased production of nitric oxide and its derived oxidants. Here, we review recent studies addressing the mechanisms by which cyclic nitroxides attenuate the toxicity of nitric oxidederived oxidants. As an example, we present data showing that tempol protects mice from acetaminophen-induced hepatotoxicity and discuss the possible protection mechanism. In view of the summarized studies, it is proposed that nitroxides attenuate tissue injury under inflammatory conditions mainly because of their ability to react rapidly with nitrogen dioxide and carbonate radical. In the process the nitroxides are oxidized to the corresponding oxammonium cation, which, in turn, can be recycled back to the nitroxides by reacting with upstream species, such as peroxynitrite and hydrogen peroxide, or with cellular reductants. An auxiliary protection mechanism may be down-regulation of inducible nitric oxide synthase expression. The possible therapeutic implications of these mechanisms are addressed.

Estratégias de pré-concentração em eletroforese capilar (CE): parte 1. Manipulação da velocidade eletroforética do analito

Capillary electrophoresis has become a well-established and routine-based separation technique. It is based on the differences between charged analyte mobility in aqueous or organic electrolytes. Its major limitation is the sensitivity due to small sample injection volumes and the narrow diameter of the capillaries, especially when UV detection is used. There are a number of ways to increase the concentration sensitivity. This report shows some on-line preconcentration strategies to perform it in free solution capillary electrophoresis that are based on manipulation of the analyte electrophoretic velocity during the sample introduction (stacking, field amplification and transient isotachophoresis).

Síntese de poli(1,1'-ferrocenilenovinileno) via acoplamento de McMurry

Com base nas grandes modificações das propriedades de materiais poliméricos resultantes da inclusão de unidades organometálicas, descrevem-se neste trabalho a síntese e a caracterização de um polímero organometálico conjugado com estrutura semelhante à de poli(p-fenilenovinileno) (PPV), o qual apresenta grupos 1,1'-ferrocenileno no lugar de 1,4fenileno em sua cadeia principal. Sintetizado por meio de reação de acoplamento de McMurry de 1,1'-ferrocenodialdeído, o poli(1,1'-ferrocenilenovinileno) (PFV) se apresentou na forma de um sólido de cor laranja, amorfo e insolúvel tanto em solventes polares quanto em apolares. Para caracterização do PFV, empregaram-se os métodos de espectroscopia no infravermelho (FTIR), espectroscopia Raman e análise termogravimétrica (TGA).

Enzymatic kinetic resolution of (RS)-1-(Phenyl)ethanols by Burkholderia cepacia lipase immobilized on magnetic nanoparticles

Lipase from Burkholderia cepacia immobilized on superparamagnetic nanoparticles using adsorption and chemisorption methodologies was efficiently applied as recyclable biocatalyst in the enzymatic kinetic resolution of (RS)-1-(phenyl)ethanols via transesterification reactions. (R)-Esters and the remaining (S)-alcohols were obtained with excellent enantiomeric excess (> 99%), which corresponds to a perfect process of enzymatic kinetic resolution (conversion 50%, E > 200). The transesterification reactions catalysed with B. cepacia lipase immobilized by the glutaraldehyde method showed the best results in terms of reusability, preserving the enzyme activity (conversion 50%, E > 200) for at least 8 successive cycles.

Spectroscopic characterization and investigation of the dynamic of charge compensation process of supramolecular films derived from tetra-2-pyridyl-1,4-pyrazine ligand

This work describes the infrared spectroscopy characterization and the charge compensation dynamics in supramolecular film FeTPPZFeCN derived from tetra-2-pyridyl-1,4-pyrazine (TPPZ) with hexacyanoferrate, as well as the hybrid film formed by FeTPPZFeCN and polypyrrole (PPy). For supramolecular film, it was found that anion flux is greater in a K+ containing solution than in Li+ solution, which seems to be due to the larger crystalline ionic radius of K+. The electroneutralization process is discussed in terms of electrostatic interactions between cations and metallic centers in the hosting matrix. The nature of the charge compensation process differs from others modified electrodes based on Prussian blue films, where only cations such as K+ participate in the electroneutralization process. In the case of FeTPPZFeCN/PPy hybrid film, the magnitude of the anions’s flux is also dependent on the identity of the anion of the supporting electrolyte.

Metal-free synthesis of indanes by iodine(III)-mediated ring contraction of 1, 2-dihydronaphthalenes

A metal-free protocol was developed to synthesize indanes by ring contraction of 1, 2-dihydronaphthalenes promoted by PhI(OH)OTs (HTIB or Koser's reagent). This oxidative rearrangement can be performed in several solvents (MeOH, CH3CN, 2 , 2, 2-trifluoroethanol (TFE), 1 , 1, 1, 3, 3, 3-hexafluoroisopropanol (HFIP), and a 1:4 mixture of TFE:CH2Cl2) under mild conditions. The ring contraction diastereoselectively gives functionalized trans-1, 3-disubstituted indanes, which are difficult to obtain in synthetic organic chemistry

A etnoarqueologia na Amazônia: contribuições e perspectivas

Desde a década de 1970, a etnoarqueologia tem sido realizada na região amazônica com diferentes temas, problemas e objetivos. Independentemente das suas perspectivas, esses trabalhos têm contribuído para o entendimento da pré-história amazônica, ampliando as possibilidades para interpretar o registro arqueológico. Além disso, contribuem na crítica e na revisão dos paradigmas tradicionais que dominaram por muito tempo as explicações sobre os modos de vida das populações amazônicas do presente e do passado. Esse artigo apresenta um panorama desses trabalhos etnoarqueológicos, salientando sua importância para o entendimento da pré-história amazônica e para a continuidade das pesquisas arqueológicas na região.

Phlebotomines (Diptera, Psychodidae) in the Ribeira Valley Speleological Province - 1. Parque Estadual Intervales, state of São Paulo, Brazil

The identification of the sandfly fauna and investigation of some ecological aspects of its populations in areas frequented by tourists of the PEI, an Atlantic forest reserve with many caves, were the objective of this study. Captures were undertaken monthly from January 2001 to December 2002, with automatic light traps installed in 13 ecotopes, including caves, forests, domiciliary and peridomiciliary environments, and by aspiration in armadillo burrows. Additionally, although not at regular intervals, Shannon traps were installed in forests and anthropic environments, aspirations were made on cave walls, among roots and fallen leaves, and some insects were captured while biting researchers. A total of 891 sandflies belonging to 21 species were captured. Six hundred specimens representing 19 species were captured with light traps, 215 in anthropic (2.24 insects/trap) and 385 in extra-domiciliary (1.46 insects/trap) environments. Brumptomyia troglodytes was the most abundant species (the Standardised Index of Species Abundance = 0.705). Pintomyia monticola predominated in the Shannon traps and showed anthropophilic and diurnal activity. Psathyromyia pascalei predominated in the aspirations; the largest number being in armadillo burrows. Eleven species were captured in caves; although some might be troglophiles, the majority used these ecotopes as resting places. Nyssomyia intermedia, Nyssomyia neivai and Migonemyia migonei, implicated in the transmission of cutaneous leishmaniasis in the Southeastern Brazilian region, were all found, though in such low densities as to suggest minimal risk of the disease in the PEI.

Diversidade, distribuição e abundância de flebotomíneos (Diptera: Psychodidae) no Paraná

Devido à crescente expansão da leishmaniose visceral americana (LVA) no Brasil, o presente estudo teve como objetivo identificar as espécies de flebotomíneos em áreas vulneráveis à transmissão dessa parasitose, bem como em outras sem qualquer informação sobre a presença desses dípteros no Paraná. As coletas de flebotomíneos foram realizadas em 46 localidades distribuídas em 37 municípios do Paraná, no período de março de 2004 a novembro de 2005. Em cada uma das localidades foram instaladas armadilhas de Falcão, durante três noites consecutivas, em vegetação natural e ambientes antrópicos (intra e peridomicílio). Ocasionalmente, foram instalas armadilhas de Shannon e feitas inspeções de paredes e aspiração em domicílio, peridomicílio e extradomicílio. O tratamento dos dados baseou-se na estimativa das freqüências e abundância das espécies, segundo cinco regiões de distintas paisagens originais. Coletaram-se 38.662 flebotomíneos de 23 espécies. Predominaram Nyssomyia neivai (Pinto) (75.6%), Ny. whitmani (Antunes & Coutinho) (10.1%), Migonemyia migonei (França) (7.8%), Expapillata firmatoi (Barreto et al.) (2.1%) and Pintomyia fischeri (Pinto) (1,6%); representando juntas 97,2% dos flebotomíneos coletados. Lutzomyia longipalpis (Lutz & Neiva) o principal vetor da LVA não foi encontrado. No entanto, capturou-se Lu. gaminarai (Cordero et al.), cujas fêmeas são morfologicamente semelhantes às de Lu. longipalpis. As espécies mais freqüentes e abundantes têm sido apontadas como vetores da leishmaniose tegumentar no Paraná e em outras áreas das Regiões Sudeste e Sul do Brasil. A presença de Lu. gaminarai no Paraná suscita a necessidade de estudos do seu comportamento, inclusive em relação à sua competência vetorial do agente da leishmaniose visceral.