Investigation of interfacial processes at tetraruthenated zinc porphyrin films using electrochemical surface plasmon resonance and electrochemical quartz crystal microbalance

In the present work we describe the investigation of interfacial and superficial processes on tetraruthenated zinc porphyrin (ZnTRP) films immobilized on gold electrode surface. In situ and real time measurements employing electrochemical surface plasmon resonance (ESPR)and electrochemical quartz crystal microbalance (EQCM) have given new insights into the electrochemical oxidation of ferrocyanide and phenolic compounds (acetaminophen, dopamine, and catechol) on ZnTRP modified electrodes. The decrease of diode like behavior in the presence of such phenolic species in contrast with ferrocyanide was clearly assigned to the inclusion of those species in the porphyrin film, creating new conduction pathways connecting the gold electrode surface with the film/solution interface. In fact, there are evidences that they can intercalate in the film (catechol > dopamine > acetaminophen), whereas ferrocyanide is completely excluded. Accordingly, the molecular size may play a fundamental role in such a process. (C) 2009 Published by Elsevier Ltd.

Nitrate reduction on Pt single crystals with Pd multilayer

Nitrate reduction on palladium multilayers deposited on platinum single crystal electrodes was studied by cyclic voltammetry and FTIR spectroscopy in acid and alkaline media. The results are compared with those obtained with bulk palladium single crystals. The reaction is sensitive to the electrode surface structure, the reactivity depending on the solution pH. In acid solution nitrate was reduced at potentials below the potential of zero total charge (pztc), when the electrode is negatively charged. Competition between nitrate, hydrogen and anion adsorption and NO formation and accumulation at the surface are proposed as the main reasons for the slow reaction rate. On the bulk palladium single crystal electrodes, NO formation leads to a fast blockage of the surface resulting in a very low activity for nitrate reduction. In alkaline solution, nitrate is reduced at more positive potentials with significantly higher current being measured on the Pd multilayer on Pt(100) electrode. (C) 2008 Elsevier Ltd. All rights reserved.

Deposition of selenium thin layers on gold surfaces from sulphuric acid media: Studies using electrochemical quartz crystal microbalance, cyclic voltammetry and AFM

In this paper we report here new considerations about the relationship between the mass and charge variations (m/z relationship) in underpotential deposition (UPD), bulk deposition and also in the H(2)Se formation reaction. Nanogravimetric experiments were able to show the adsorption of H(2)SeO(3) on the AuO surface prior to the voltammetric sweep and that, after the AuO reduction, 0.40 monolayer of H(2)SeO(3) remains adsorbed on the newly reduced Au surface, which was enough to gives rise to the UPD layer. The UPD results indicate that the maximum coverage with Se(ads) on polycrystalline gold surface corresponds to approximately 0.40 monolayer, in good agreement with charge density results. The cyclic voltammetry experiments demonstrated that the amount of bulk Se obtained during the potential scan to approximately 2 Se monolayers, which was further confirmed by electrochemical quartz crystal microbalance (EQCM) measurements that pointed out a mass variation corresponding of 3 monolayers of Se. In addition, the Se thin films were obtained by chronoamperometric experiments, where the Au electrode was polarized at +0.10V during different times in 1.0 M H(2)SO(4) + 1.0 mM SeO(2). The topologic aspects of the electrodeposits were observed in Atomic Force Microscope (AFM) measurements. Finally, in highly negative potential polarizations, the H(2)Se formation was analyzed by voltammetric and nanogravimetric measurements. These finding brings a new light on the selenium electrodeposition and point up to a proposed electrochemical model for molecule controlled surface engineering. (c) 2009 Elsevier Ltd. All rights reserved.

Polymerization shrinkage stress of composites photoactivated by different light sources

The purpose of this study was to compare the polymerization shrinkage stress of composite resins (microfilled, microhybrid and hybrid) photoactivated by quartz-tungsten halogen light (QTH) and light-emitting diode (LED). Glass rods (5.0 mm x 5.0 cm) were fabricated and had one of the surfaces air-abraded with aluminum oxide and coated with a layer of an adhesive system, which was photoactivated with the QTH unit. The glass rods were vertically assembled, in pairs, to a universal testing machine and the composites were applied to the lower rod. The upper rod was placed closer, at 2 mm, and an extensometer was attached to the rods. The 20 composites were polymerized by either QTH (n=10) or LED (n=10) curing units. Polymerization was carried out using 2 devices positioned in opposite sides, which were simultaneously activated for 40 s. Shrinkage stress was analyzed twice: shortly after polymerization (t40s) and 10 min later (t10min). Data were analyzed statistically by 2-way ANOVA and Tukey's test (a=5%). The shrinkage stress for all composites was higher at t10min than at t40s, regardless of the activation source. Microfilled composite resins showed lower shrinkage stress values compared to the other composite resins. For the hybrid and microhybrid composite resins, the light source had no influence on the shrinkage stress, except for microfilled composite at t10min. It may be concluded that the composition of composite resins is the factor with the strongest influence on shrinkage stress.

Anatomia foliar de Eugenia florida DC. (Myrtaceae)

Foi feito o estudo anatômico da folha de Eugenia florida DC., espécie arbórea da família Myrtaceae, coletada no Campus da Fundação Oswaldo Cruz, Rio de Janeiro, RJ. A espécie apresenta importantes propriedades farmacológicas, incluindo-se atividade antiviral. O presente estudo teve como objetivo fornecer dados, revelados através da microscopia óptica e da microscopia eletrônica de varredura, que possam contribuir para o conhecimento da espécie e, conseqüentemente, para a segurança em sua identificação. Anatomicamente, a folha é hipostomática, com organização dorsiventral do mesofilo. Apresenta tricomas simples apenas sobre a nervura mediana da face adaxial. As células epidérmicas apresentam contorno sinuoso em vista frontal e cutícula estriada. O parênquima paliçádico destaca-se pela grande quantidade de cristais prismáticos de oxalato de cálcio. Em posição subepidérmica ocorrem cavidades secretoras de óleos essenciais, pouco numerosas, nas duas faces da lâmina foliar. As células epidérmicas situadas sobre as estruturas secretoras constituem característica de valor diagnóstico e são reconhecíveis pela célula de topo, que é reniforme, circundada pelas adjacentes, que apresentam disposição radiada. A comparação entre folhas de sol e de sombra revela que, nas primeiras, as estruturas secretoras são completamente diferenciadas, ao contrário das folhas de sombra, além de apresentarem maior concentração de compostos ergásticos.

Morfo-anatomia foliar de Myrcia multiflora (Lam.) DC. - Myrtaceae

Folhas de Myrcia multiflora (Lam.) DC. são usadas na medicina popular como hipoglicemiantes. O objetivo deste trabalho foi caracterizar morfológica e anatomicamente as folhas desta planta, de modo que os dados obtidos possam ser utilizados como referência em exames de controle de qualidade de amostras de fármacos, com vistas a verificar a autenticidade. Folhas inteiras foram diafanizadas e coradas para o estudo da nervação. Secções transversais do pecíolo e transversais e paradérmicas da lâmina foliar foram analisadas em microscópio óptico (MO) e a superfície do limbo foi observada, também, em microscopia eletrônica de varredura (MEV). Foram aplicados testes histoquímicos em material fresco, para identificação e localização de glicídios, amido, taninos, lignina, cristais e sílica. Morfologicamente, a folha é simples, oval-elíptica, com margem inteira, base aguda, ápice acuminado e textura cartácea. A venação é do tipo camptódromo-broquidódromo. Anatomicamente, a folha é hipostomática, com mesofilo compacto e dorsiventral, com três estratos de parênquima paliçádico. A epiderme é uniestratificada, silicificada em algumas regiões e as células exibem paredes anticlinais retas. Em posição subepidérmica ocorrem numerosas cavidades secretoras de óleos essenciais. Os feixes vasculares são colaterais e acompanhados por séries cristalíferas. Os dados obtidos são comparados com os de outras espécies de Myrtaceae e conclui-se que as características morfológicas e anatômicas de M. multiflora contribuem para a diagnose.

Mineralogical characterization of a highly-weathered soil by the Rietveld Method

The mineralogical characterization through mineral quantification of Brazilian soils by X-ray diffraction data using the Rietveld Method is not common. A mineralogical quantification of an Acric Ferralsol from the Ponta Grossa region, state of Paraná, Brazil, was carried out using this Method with X-Ray Diffraction data to verify if this method was suitable for mineral quantification of a highly-weathered soil. The A, AB and B3 horizons were fractioned to separate the different particle sizes: clay, silt, fine sand (by Stokes Law) and coarse sand fractions (by sieving), with the procedure free of chemical treatments. X-ray Fluorescence, Inductively Coupled Plasma Atomic Emission Spectrometry, Infrared Spectroscopy and Mössbauer Spectroscopy were used in order to assist the mineral identification and quantification. The Rietveld Method enabled the quantification of the present minerals. In a general way, the quantitative mineralogical characterization by the Rietveld Method revealed that quartz, gibbsite, rutile, hematite, goethite, kaolinite and halloysite were present in the clay and silt fractions of all horizons. The silt fractions of the deeper horizons were different from the more superficial ones due to the presence of large amounts of quartz. The fine and the coarse sand fractions are constituted mainly by quartz. Therefore, a mineralogical quantification of the finer fraction (clay and silt) by the Rietveld Method was successful.

EPR and magnetic studies of a carboxylate-bridged dinuclear copper(II) compound: [cu2(flu)4(dmf)2]

We report magnetic and EPR (electron paramagnetic resonance) spectroscopy studies of [Cu2(flu)4(dmf)2] (flu = flufenamate and dmf = dimethylformamide), which has CuII ions in tetracarboxylate "paddle wheel" dinuclear units. Susceptibility measurements at 10 < T < 275 K allowed the evaluation of an antiferromagnetic intradinuclear exchange coupling J0 = -294 ± 5 cm-1 between CuII ions (Hex = "J0 S1·S2). EPR experiments at 300 K in powder and single-crystals at 9.5 and 34.4 GHz indicated g// = 2.373, g⊥ = 2.073 and zero field splitting parameters D = (-0.334 ± 0.001) cm"1 and E ca. 0. EPR signal intensity measurements at X-band in the range 4 < T < 295 K indicated that J0 = "283 ± 5 cm"1. A higher limit |J´| < 5×10-3 cm-1 for the interdinuclear exchange coupling between neighbor units at ca.14.24 Å was estimated from the angular variation of the single crystal spectra around the magic angles. The results are discussed in terms of the structure of the dinuclear unit and the bridges connecting CuII ions and compared with values reported for similar compounds.

Different coordination modes for disulfoxides towards diorganotin(IV) dichlorides. X-ray crystal structures of 1,2-cis-bis-(phenylsulfinyl)ethene (rac-,cis-cbpse) and adducts [{Ph2SnCl2(meso-bpse)}n] and [{n-Bu2SnCl2(pdtd)}2]

The reactions of meso-1,2-bis(phenylsulfinyl)ethane (meso-bpse) with Ph2SnCl2, 2-phenyl-1,3-dithiane trans-1-trans-3-dioxide (pdtd) with n-Bu2SnCl2 and 1,2-cis-bis-(phenylsulfinyl)ethene (rac-,cis-cbpse) with Ph2SnCl2, in 1:1 molar ratio, yielded [{Ph2SnCl2(meso-bpse)}n], [{n-Bu2SnCl2(pdtd)}2] and [{Ph2SnCl2(rac,cis-cbpse)}x] (x = 2 or n), respectively. All adducts were studied by IR, Mössbauer and 119Sn NMR spectroscopic methods, elemental analysis and single crystal X-ray diffractometry. The X-ray crystal structure of [{Ph2SnCl2(meso-bpse)}n] revealed the occurrence of infinite chains in which the tin(IV) atoms appear in a distorted octahedral geometry with Cl atoms in cis and Ph groups in trans positions. The X-ray crystal structure of [{n-Bu2SnCl2(pdtd)}2] revealed discrete centrosymmetric dimeric species in which the tin(IV) atoms possess a distorted octahedral geometry with bridging disulfoxides in cis and n-butyl moieties in trans positions. The spectroscopic data indicated that the adduct containing the rac,cis-cbpse ligand can be dimeric or polymeric. The X-ray structural analysis of the free rac-,cis-cbpse sulfoxide revealed that the crystals belong to the C2/c space group.

Characterization of oil shale residue and rejects from irati formation by electron paramagnetic resonance

In this study, sedimentary organic matter of oil shale rejects, calschist, shale fine and the so called retorted shale from Irati formation was characterized. EPR was used to analyse the samples regarding loss of signal in g = 2.003 associated to the organic free radical with the calcined samples and washing with hydrogen peroxide. The radical signal was detected in all samples, however, for the calschist and shale fine samples another signal was identified at g = 2.000 which disappeared when the sample was heated at 400 ºC. Hydrogen peroxide washing was also performed and it was noted that after washing the signal appeared around g = 2.000 for all samples, including retorted shale, which might be due to the quartz E1 defect.

Mineralogia de um latossolo vermelho distrófico submetido a diferentes manejos por 24 anos

Atualmente, procuram-se sistemas de manejo que preservem ou melhorem as qualidades do solo, tanto mineralógicas como orgânicas, priorizando maior produtividade. Este trabalho teve como objetivo verificar qualitativamente, por meio das técnicas de fluorescência de raios X, difração de raios X e infravermelho com transformada de Fourier, os efeitos provocados pela utilização dos manejos: plantio convencional, preparo mínimo e plantio direto, por 24 anos, na mineralogia de um Latossolo Vermelho distrófico de Ponta Grossa, PR. Não foram observadas mudanças significativas na mineralogia do Latossolo estudado, por meio das técnicas utilizadas, quanto aos diferentes manejos durante os anos de sua aplicação. Pôde-se verificar, qualitativamente, a presença dos minerais gibbsita, caulinita, haloisita, montmorilonita, hematita, rutilo, anatásio, goethita e quartzo.

Utilização de um espectrógrafo de projeção como uma ferramenta para demonstrações sobre polarização da luz

This article describes the use of a projection spectrograph based on an overhead projector for use in classroom demonstrations on light polarization and optical activity. A simple adaptation on a previously developed apparatus allows illustrating several aspects of optical activity, such as circular and linear birefringence, including their wavelength dependence. Specifically, we use the projection spectrograph to demonstrate the optical activity of an aqueous solution of sugar (circular birefringence), of a quartz plate and of an overhead projector transparence film (linear birefringence). A historical survey about the optical activity discovery and the main principles involved is also presented.

Mechanical strength and thermal conductivity of low-porosity gypsum plates

The thermal conductivity and mechanical strength of gypsum and gypsum-cellulose plates made from commercial plaster by a new process have been measured. The gypsum parts made by the new process, 'novogesso', have high mechanical strength and low porosity. The gypsum strength derives from both the high aspect ratio of the gypsum crystals and the strong adhesion among them by nano-flat layers of confined water, which behaves as supercooled water. Another contribution to the strength comes from the nano-flatness of the lateral surfaces of the gypsum single crystals. The bending and compression strengths, σB and σc, of gypsum plates prepared by this new technique can be as high as 30 and 100 MPa, respectively. The way gypsum plates have been assembled as well as their low thermal conductivity allowed for the construction of a low-cost experimental house with thermal and acoustic comfort.

Effect of culture medium on biocalcification by Pseudomonas Putida, Lysinibacillus Sphaericus and Bacillus Subtilis

The objective of this study is to investigate the efficiency of calcium carbonate bioprecipitation by Lysinibacillus sphaericus, Bacillus subtilis and Pseudomonas putida, obtained from the Coleção de Culturas do Instituto Nacional de Controle de Qualidade em Saúde (INCQS), as a first step in determining their potential to protect building materials against water uptake. Two culture media were studied: modified B4 containing calcium acetate and 295 with calcium chloride. Calcium consumption in the two media after incubation with and without the bacterial inoculum was determined by atomic absorption analysis. Modified B4 gave the best results and in this medium Pseudomonas putida INQCS 113 produced the highest calcium carbonate precipitation, followed by Lysinibacillus sphaericus INQCS 414; the lowest precipitation was produced by Bacillus subtilis INQCS 328. In this culture medium XRD analysis showed that Pseudomonas putida and Bacillus subtilis precipitated calcite and vaterite polymorphs while Lysinibacillus sphaericus produced only vaterite. The shape and size of the crystals were affected by culture medium, bacterial strain and culture conditions, static or shaken. In conclusion, of the three strains Pseudomonas putida INQCS 113 in modified B4 medium gave the best results precipitating 96% of the calcium, this strain thus has good potential for use on building materials.

Extraction and concentration of biogenic calcium oxalate from plant leaves

The objective of this study was to extract and concentrate calcium oxalate (CaOx) crystals from plant leaves that form the above mentioned crystals. The chemical and physical studies of CaOx from plant to be performed depend on an adequate amount of the crystals. The plant used in this study was croton (Codiaeum variegatum). The leaves were ground in a heavy duty blender and sieved through a 0.20 mm sieve. The suspension obtained was suspended in distilled water. The crystals were concentrated at the bottom of a test tube. The supernatant must be washed until it is free of plant pigments and other organic substances. Biogenic CaOx crystals have well-defined and sharp peaks, indicating very high crystallinity. Moreover, the CaOx crystals were not damaged during the extraction procedure, as can be seen on the scanning electron microscope images. The porposed method can be considered efficient to extract and concentrate biogenic calcium oxalate.