Formação docente no ensino superior de Química: contribuições dos programas de aperfeiçoamento de ensino

The literature on the challenges of teacher education in undergraduate chemistry teaching is limited. In the present study, the application of didactic proposals elaborated by two authors of this paper, graduate students and teaching assistants of the teaching improvement program at University of São Paulo, was investigated in terms of their contribution to the teaching assistants' education and undergraduate students' receptivity toward them. Such proposals were based on the jigsaw cooperative learning strategy and applied in two undergraduate courses. The results indicate students' good receptivity and suggest their importance to teaching assistants' education.

Reaproveitamento de óxidos de manganês de pilhas descartadas para eletrocatálise da reação de redução de oxigênio em meio básico

The oxygen reduction reaction was studied in alkaline media using manganese oxides obtained from spent batteries as electrocatalysts. Three processes were used to recover manganese oxides from spent batteries. The particles obtained were in the range from 8 to 11 nm. The electrochemical experiments indicated a good electrocatalytic activity toward oxygen reduction using the different samples and showing approximately a direct transference of 4 electrons during the process. Even though all the processes were efficient, the best result was observed for the prepared sample using reactants of low cost.

Comparação de técnicas de determinação de ésteres em cachaça

An analytical comparison of three different techniques for quantitative profile of esters in cachaça is reported. The Ministério da Agricultura Pecuária e Abastecimento (MAPA) recommends the use of GC/FID or volumetry. Despite being laborious and lacking in chemical speciation, the volumetric technique for total ester content shows to be appropriate, reproducible, and accurate for the analysis of cachaça. However, the GC/FID suggested by MAPA, considering only ethyl acetate, shows inaccuracy, underestimating the total ester content by a median factor of 72%, mainly due to the absence of ethyl lactate analysis. On the other hand, the GC/MS technique that comprises the analysis and speciation of nine esters, including ethyl lactate, proved to be reproducible, simple, fast and accurate for the analysis of total ester content in cachaça. Thus, the total ester content results obtained using GC/FID must be considered with precaution.

Teores de carbamato de etila em aguardentes de cana e mandioca: parte II

Herein, we report the concentration of ethyl carbamate (EC) and copper in 380 samples of sugar-cane spirit and 45 samples of manioc spirit as determined by GC-MS and FAAS respectively. The cyanide content determined spectrophotometrically is reported for the manioc spirit. Sugar cane spirit produced by alembic distillation (70,0 µg L-1) shown a lower content of EC than samples produced by column distillation (270 µg L-1). No simple correlation between the content of EC and copper for sugar cane spirit as well among the concentration of EC, copper, and cyanide for manioc spirit could be observed.

Estudo da eletrocristalização de Ni e Ni-P sobre ultramicroeletrodo de platina

This work describes a comparative study of the electrocrystallization of Ni and Ni-P on Pt ultramicroelectrodes using chronoamperometric measurements. It was possible to confirm that in all cases a progressive nucleation was the predominant mechanism. Moreover, the application of the Atomistic Theory to the experimental rate of nuclei formation showed that the number of atoms in the critical nucleus was zero, except for Ni-P on Pt at low overpotentials were a value of one was observed. Furthermore, the physical characterisation of the different deposits on Pt by atomic force microscopy allowed observing the coalescence of the hemispherical nuclei of Ni and Ni-P at t max thus confirming the results obtained from the current-time analysis.

Recovery of p-TBC from a butadiene washing stream in a pilot plant

Results obtained in a pilot-scale unit designed for COD removal and p-TBC (p-tert-butylcatechol) recovery from a butadiene washing stream (pH 14, 200,000 mg COD L-1, highly toxic) at a petrochemical industry are presented. By adding H3PO4, phase separation is achieved and p-TBC is successfully recovered (88 g L-1 of washing stream). Information (time for phase separation and organic phase characterization) was gathered for designing a future industrial unit. The estimated heat generation rate was 990 kJ min-1 and 15 min were enough to promote phase separation for a liquid column of approximately 1.15 m.

Search for cytotoxic agents in multiple Laurencia complex seaweed species (Ceramiales, Rhodophyta) harvested from the Atlantic Ocean with emphasis on the Brazilian State of Espírito Santo

The development of new anti-cancer drugs of algal origin represents one of the least explored frontiers in medicinal chemistry. In this regard, the diversity of micro- and macroalgae found in Brazilian coastal waters can be viewed as a largely untapped natural resource. In this report, we describe a comparative study on the cytotoxic properties of extracts obtained from the Laurencia complex: Laurencia aldingensis, L. catarinensis, L. dendroidea, L. intricata, L. translucida, L. sp, and Palisada flagellifera. All of these species were collected in the coastal waters of the State of Espírito Santo, Brazil. Four out of the twelve samples initially investigated were found to show significant levels of toxicity towards a model tumor cell line (human uterine sarcoma, MES-SA). The highest levels of cytotoxicity were typically associated with non-polar (hexane) algal extracts, while the lowest levels of cytotoxicity were found with the corresponding polar (methanol) extracts. In this report, we also describe a biological model currently in development that will not only facilitate the search for new anti-cancer drug candidates of algal origin, but also permit the identification of compounds capable of inducing the destruction of multi-drug resistant tumors with greater efficiency than the pharmaceuticals currently in clinical use.

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.

A novel disposable electrochemical microcell: construction and characterization

An alternative technique for the fabrication of disposable electrochemical microcells containing working, reference and auxiliary electrodes on a single device is reported. The procedure is based on thermal-transfer of toner masks onto CD-R (recordable compact discs) gold surfaces to define the layout of the electrodes (contour). In a subsequent step, the layout is manually painted with a permanent marker pen. The unprotected gold surface is conveniently etched (chemical corrosion) and the ink is then easily removed with ethanol, generating gold surfaces without contamination. The final and reproducible area of the electrodes is defined by heat transference of a second toner mask. Silver epoxy is deposited on one of the gold bands which is the satisfactorily used as reference electrode. These microcells were electrochemically characterized by cyclic, linear, and square wave voltammetry, and several electroactive species were used as model systems. The area reproducibility of the electrodes for different microcells was studied and a relative standard deviation better than 1,0% (n = 10) was obtained. Disposable electrochemical microcells were successfully used in analysis of liquid samples with volumes lower than 200 µL and good stability and reproducibility (RSD less than 2.0%) were achieved. These microcells were also evaluated for quantification of paracetamol and dipyrone in pharmaceutical formulations.

Nursery performance of the pink shrimp Farfantepenaeus paulensis (Crustacea: Decapoda: Penaeidae) postlarvae in different salinities

Nursery performance, development, and RNA:DNA ratio were investigated in Farfantepenaeus paulensis (Pérez-Farfante, 1967) postlarvae acclimated from a salinity of 30‰ to higher (35‰) or lower (16, 22 and 29‰) salinities and reared for 20 days. Overall, higher final weight, yield and growth rate were observed at a salinity of 29‰. RNA:DNA ratio indicated reduced growth potential at a salinity of 35‰. Low salinities resulted in more developed individuals. Thus, early postlarval F. paulensis should not be stocked in salinities higher than that of the original hatchery, otherwise in lower salinities postlarvae should be older and/or have an extended nursery phase. Results may assist in the development of nursery rearing protocols for F. paulensis, an alternative species for aquaculture in subtropical areas.

The Southern Brazilian shelf: general characteristics, quaternary evolution and sediment distribution

Extending from latitude 34ºS to 22ºS the Southern Brazilian shelf constitutes the only part of the Brazilian shelf with a subtropical to temperate environment. The studies on the different geological aspects of the area began in the 1960's and have recently been reassessed after studies related to the determination of the Economic Exclusive Zone. In terms of morphology, the Southern Brazilian shelf may be divided into three sectors, the São Paulo Bight, the Florianópolis-Mostardas Sector and the Rio Grande Cone, characterized by conspicuous differences in terms of geological determining factors, bathymetry, declivities and the presence of canyons and channels. Despite the existence of hundreds of radiocarbon datings the sea level changes curve of southern Brazil during the Last Glacial Cycle is still a matter of debate. A recent controversy on the Middle and late Holocene sea level changes curve raised the question of the amplitude of the oscillations which occurred in the period. Also, a few but relatively consistent radiocarbon datings suggest the occurrence of a high sea level during Isotope Stage 3. In terms of sedimentary cover the Southern Brazilian shelf exhibits a very strong hydrodynamic control, both latitudinal and bathymetrical. The sector southward from 25ºS is characterized by the influence of the plume of water carrying sediments originating from the Río de La Plata. Actually its presence is conspicuous up to 28ºS, with the area between this latitude and 25ºS constituting a transitional zone. In terms of bathymetry the outer shelf is marked by the "floor-polisher" effect of the Brazil Current, which is responsible for the maintenance of a relict facies in areas deeper than 100 meters.

Analysis of mangrove forest succession, using sediment cores: a case study in the Cananéia -Iguape coastal system, São Paulo Brazil

Sediment cores are an essential tool for the analysis of the dynamics of mangrove succession. Coring was used to correlate changes in depositional environments and lateral sedimentary facies with discrete stages of forest succession at the Cananéia-Iguape Coastal System in southeastern Brazil. A local level successional pattern was examined based on four core series T1) a sediment bank; T2) a smooth cordgrass Spartina alterniflora bank; T3) an active mangrove progradation fringe dominated by Laguncularia racemosa, and; T4) a mature mangrove forest dominated by Avicennia schaueriana. Cores were macroscopically described in terms of color, texture, sedimentary structure and organic components. The base of all cores exhibited a similar pattern suggesting common vertical progressive changes in depositional conditions and subsequent successional colonization pattern throughout the forest. The progradation zone is an exposed bank, colonized by S. alterniflora. L. racemosa, replaces S. alterniflora as progradation takes place. As the substrate consolidates A. schaueriana replaces L. racemosa and attains the greatest structural development in the mature forest. Cores collected within the A. schaueriana dominated stand contained S. alterniflora fragments near the base, confirming that a smooth cordgrass habitat characterized the establishment and early seral stages. Cores provide a reliable approach to describe local-level successional sequences in dynamic settings subject to drivers operating on multiple temporal and spatial scales where spatial heterogeneity can lead to multiple equilibria and where similar successional end-points may be reached through convergent paths.

Radiocarbon geochronology of the sediments of the São Paulo Bight (southern Brazilian upper margin)

The aim of this work was to generate an inventory of the data on radiocarbon datings obtained from sediments of the São Paulo Bight (southern Brazilian upper margin) and to analyze the data in terms of Late Quaternary sedimentary processes and sedimentation rates. A total of 238 radiocarbon datings from materials collected using differents ampling procedures was considered for this work. The sedimentation rates varied from less than 2 to 68 cm.kyr-1. The highest sedimentation rate values were found in a low-energy (ría type) coastal system as well as in the upwelling zones of Santa Catarina and Cabo Frio. The lowest rates were found on the outer shelf and upper slopes. Our results confirm the strong dependency of the shelf currents, with an emphasis to the terrigenous input from the Río de La Plata outflow which is transported via the Brazilian Coastal Current, as well as of the coupled Brazil Current - Intermediate Western Boundary Current (BC-IWBC) dynamics on the sedimentary processes. At least three indicators ofthe paleo sea level were found at 12200 yr BP (conventional radiocarbon age) (103 meters below sea level - mbsl),8300-8800 cal yr BP (13 mbsl) and 7700-8100 cal yr BP (6 mbsl).

A new species of Rineloricaria (Siluriformes: Loricariidae: Loricariinae) from rio Daraá, rio Negro basin, Amazon, Brazil

Rineloricaria daraha, new species, is described from the rio Daraá, tributary of rio Negro, northwestern Amazonas State, Brazil. The new species is diagnosed by having seven branched pectoral-fin rays, finger-like papillae on the lower lip, a large multi-angular preanal plate, and at least four quadrangular plates of variable size surrounding the preanal plate. The new species is known only from rio Daraá and its waterfalls.

Análise das relações taxonômicas e sistemáticas entre espécies de triatomíneos (Hemiptera, Reduviidae) de colônias mantidas pelo Serviço Especial de Saúde de Araraquara, inferida de seqüências do 16S rDNA mitocondrial

Foram analisadas seqüências de nucleotídeos do gene 16S do rDNA mitocondrial em 14 populações de triatomíneos mantidos em colônias no insetário SESA de Araraquara- SP, comparando-as com seqüências do mesmo gene disponíveis no GenBank. Os fragmentos variaram de 311 a 317 pb com baixa variação intra-específica entre as distâncias genéticas (0% a 0,6%), exceto para os relacionamentos entre espécimes de Triatoma sordida (1%) e espécimes de T. brasiliensis (1,3%) atribuídos a populações geográficas diferentes. A parafilia de Rhodniini e do gênero Panstrongylus foi evidenciada pelas analises, confirmando resultados anteriores entre estes e os estreitos relacionamentos de R. prolixus com R. robustus e de T. infestans e T. platensis. O relacionamento entre T. maculata e T. pseudomaculata não foi solucionado, uma vez que, esses táxons apareceram tanto em monofilia quanto em parafilia: T. pseudomaculata (SESA) está agrupado com T. maculata (seqüência do GenBank) e associados a T . brasiliensis (SESA), enquanto T. maculata (SESA) aparece agrupado com T. pseudomaculata do SESA e do GenBank. Os resultados evidenciam a utilidade do gene 16S como marcador de espécies de triatomíneos e sua importância em questões de sistemática e taxonomia. Há necessidade de novos estudos envolvendo outros marcadores associados a caracteres sistemáticos clássicos de morfologia, ecologia e comportamento para decisões sistemáticas adequadas uma vez, que teriam impacto não apenas sistemático mas, para as estratégias de controle.