On an Electrode Modified by a Supramolecular Ruthenium Mixed Valence (Ru(II)/Ru(III)) Diphosphine-Porphyrin Assembly

Three novel polymetallic ruthenium (III) meso-tetra(4-pyridyl)porphyrins containing peripheral ""RuCl(3)(dppb)"" moieties have been prepared and characterized. The X-ray structure of the tetraruthenated {NiTPyP[RuCl(3)(dppb)](4)} porphyrin complex crystallizes in the triclinic space group FT. This structure is discussed and compared with the crystal data for the mer-[RuCl(3)(dppb)(py)]. The {TPyP[RuCl(3)(dppb)](4)} and {CoTPyP[RuCl(3)(dppb)](4)} porphyrins were used to obtain electrogenerated films on ITO and glass carbon electrode surfaces, respectively. Such tetraruthenated porphyrins form films of a mixed-valence species {TPyP[Ru(dppb)](4)(mu Cl(3))(2)}(2)(4n2+) and {CoTPyP[Ru(dppb)](4)(mu Cl(3))(2)}(2n)(4n2+) on the electrode surface. The modified electrode with {CoTPyP[RuCl(3)(dppb)](4)} is very stable and can be used to detect organic substrates such as catechol.

Major- and trace-element composition of olivine, perovskite, clinopyroxene, Cr-Fe-Ti oxides, phlogopite and host kamafugites and kimberlites, Alto Paranaiba, Brazil

An integrated whole-rock petrographic and geochemical study has been carried out on kamafugites and kimberlites of the Late Cretaceous Alto Paranaiba igneous province, in Brazil, and their main minerals, olivine, clinopyroxene, perovskite, phlogopite, spinels and ilmenite. Perovskite is by far the dominant repository for light lanthanides, Nb, Ta, Th and U, and occasionally other elements, reaching concentrations up to 3.4 x 10(4) chondrite values for light lanthanides and 105 chondrite for Th. A very strong fractionation between light and heavy lanthanides (chondrite-normalized La/Yb from similar to 175 to similar to 2000) is also observed. This is likely the first comprehensive dataset on natural perovskite. Clinopyroxene has variable trace-element contents. likely due to the different position of this phase in the crystallization sequence; Sc reaches values as high as 200 ppm whereas the lanthanides show very variable enrichment in light over heavy REE, and commonly show a negative Eu anomaly. The olivine, phlogopite (and tetra-ferriphlogopite), Cr-Ti oxide and ilmenite are substantially barren minerals for lanthanides and most other trace elements, with the exception of Ba, Cs and Rb in mica, and V, Nb and Ta in ilmenite. Estimated mineral/whole-rock partition coefficients for lanthanides in perovskite are similar to previous determinations, though much higher than those calculated in experiments with synthetic compositions, testifying once more to the complex behavior of these elements in a natural environment. The enormous potential for exploitation of lanthanides, Th, U and high-field-strength elements in the Brazilian kamafugites, kimberlites and related rocks is clearly shown.

Effect of some antioxidants on oxidative DNA damage induced by autoxidation of microquantities of sulfite in the presence of Ni(II)/Gly-Gly-L-His

Ni(II)GGH (GGH, glycylglycyl-L-histidine) reacts rapidly with S(IV), in air-saturated solution, to produce Ni(III)GGH. A mechanism is proposed where Ni(III) oxidizes SO(3)(2-) to SO(3)(center dot-), which reacts with dissolved oxygen to produce SO(5)(center dot-), initiating radical chain reactions. DNA strand breaks and 8-oxo-7,8-dihydro-20-deoxyguanosine (8-oxodGuo) formation were observed in air-saturated solutions containing micromolar concentrations of nickel(II) and S(IV). The efficacies of melatonin, (-)-epigallocatechin-gallate (from green tea), resveratrol, tannic, and ascorbic acids in terms of their inhibitory activities of DNA strand breaks and 8-oxodGuo formation were evaluated.

Structural Investigation of MFe(2)O(4) (M = Fe, Co) Magnetic Fluids

Ferrites of the type M(II)Fe(2)O(4) (M = Fe and Co) have been prepared by the traditional coprecipitation method. These ferrites were modified by the adsorption of fatty acids derived from soybean and castor oil and were then dispersed in cyclohexane, providing very stable magnetic fluids, readily usable in nonpolar media. The structural properties of the ferrites and modified ferrites as well as the magnetic fluids were characterized by XRD (X-ray powder diffraction), TEM (transmission electron microscopy), DRIFTS (diffusion reflectance infrared Fourier transform spectroscopy), FTMR (Fourier transform near-infrared), UV-vis, normal Raman spectroscopy, and surface-enhanced Raman scattering (SERS). XRD and TEM analysis have shown that the magnetic nanoparticles (nonmodified and modified) present diameters in the range of 10-15 nm. DRIFTS measurements have shown that the carboxylate groups of soybean and castor oil fatty acids adsorb on the ferrite surface, forming three different structures: a bridging bidentate, a bridging monodentate, and a bidentate chelate structure. The FTIR and Raman spectra of nonmodified Fe(3)O(4) and CoFe(2)O(4) nanoparticles have shown that the number of observed phonons is not compatible with the expected O(h)(7) symmetry, since IR-only active phonons were observed. in the Raman spectra and vice versa. SERS measurements of a CoFe(2)O(4) thin film on a SERS-active gold electrode at different applied potentials made possible the assignment of the signals near 550 and 630 cm(-1) to Co-O motions and the signals near 470 and 680 cm(-1) to Fe-O motions.

Modelling water adsorption on Au(210) surfaces: II. Monte Carlo simulations

Canonical Monte Carlo simulations for the Au(210)/H(2)O interface, using a force field recently proposed by us, are reported. The results exhibit the main features normally observed in simulations of water molecules in contact with different noble metal surfaces. The calculations also assess the influence of the surface topography on the structural aspects of the adsorbed water and on the distribution of the water molecules in the direction normal to the metal surface plane. The adsorption process is preferential at sites in the first layer of the metal. The analysis of the density profiles and dipole moment distributions points to two predominant orientations. Most of the molecules are adsorbed with the molecular plane parallel to surface, while others adsorb with one of the O-H bonds parallel to the surface and the other bond pointing towards the bulk liquid phase. There is also evidence of hydrogen bond formation between the first and second solvent layers at the interface. (c) 2007 Elsevier B.V. All rights reserved.

Extração de metais (K, Mg, Ba, Ca, Cr, Mn, Li, Fe) de água produzida utilizando sistema microemulsionado

The produced water is a byproduct formed due to production of petroleum and carries with it a high amount of contaminants such as oil particles in suspension, organic compounds and metals. Thus, these latter pollutants are very difficult to treat because of its high solubility in water. The objective of this work is to use and evaluate a microemulsioned system to remove metals ( K , Mg , Ba , Ca , Cr , Mn , Li , Fe ) of synthetic produced water. For the extraction of metals, it was used a pseudoternary diagram containing the following phases: synthetic produced water as the aqueous phase (AP), hexane as organic phase (OP), and a cosurfactant/surfactant ratio equal to four (C/S = 4) as the third phase, where the OCS (saponified coconut oil) was used as surfactant and n-butanol as cosurfactant. The synthetic produced water was prepared in a bench scale and the region of interest in the diagram for the removal of metals was determined by experimental design called. Ten points located in the phase Winsor II were selected in an area with a large amount of water and small amounts of reagents. The samples were analyzed in atomic absorption spectrometer, and the results were evaluated through a statistical assesment, allowing the efficiency analysis of the effects and their interactions. The results showed percentages of extraction above 90% for the metals manganese, iron, chromium, calcium, barium and magnesium, and around 45% for metals lithium and potassium. The optimal point for the simultaneous removal of metals was calculated using statistical artifact multiple response function (MR). This calculation showed that the point of greatest extraction of metals occurs was the J point, with the composition [72% AP, 9% OP, 19% C/S], obtaining a global extraction percentage about 80%. Considering the aspects analyzed, the microemulsioned system has shown itself to be an effective alternative in the extraction of metals on synthetic produced water remediation

Produção de mudas de caramboleiras 'B-10' e 'Golden Star': II - marcha de absorção e acúmulo de nutrientes

A participação do Brasil no mercado externo de frutas tem aumentado consideravelmente e com potencial para crescer ainda mais. A constante ascensão dos dados de exportação brasileira é resultado da combinação de avanços tecnológicos do setor produtivo e de acesso a novos mercados consumidores. A caramboleira apresenta-se como uma excelente opção de cultivo de frutas exóticas, com grande potencial para atender ao mercado interno e às exportações. Assim, objetivou-se avaliar a marcha de absorção e de acúmulo de nutrientes em mudas de caramboleiras cultivadas em solução nutritiva. O experimento foi realizado em parcelas subdivididas, sendo utilizadas como parcela as duas cultivares de caramboleira ('B-10' e 'Golden Star') e, como subparcelas, cinco épocas de coleta de plantas, realizadas aos 208; 233; 258; 283 e 308 dias após o transplantio para a solução nutritiva. O delineamento foi inteiramente casualizado, com três repetições. As mudas foram cultivadas em vasos (8L) com solução nutritiva (pH=5,5 ± 0,5), com aeração. O experimento iniciou-se em 24-08-2005. Nos diferentes órgãos das mudas (folhas, caule e raízes), determinaram-se a marcha de absorção, o acúmulo de nutrientes e os índices nutricionais. Não houve diferenças no acúmulo de nutrientes entre as mudas de caramboleira de ambas as cultivares, sendo a ordem decrescente dos nutrientes em cada muda de 'B-10', no final do período experimental: N > K > Ca > Mg > S > P > Fe > Mn > B > Cu > Zn. Para a 'Golden Star', a ordem foi: N > K > Ca > Mg > P > S > Fe > Mn > B > Cu > Zn. Para as duas cultivares, o acúmulo médio foi maior nas folhas > caule > raízes. O período de maior exigência para 'B-10' foi entre 208 - 233 e, para 'Golden Star', entre 233 - 283 dias após o transplantio. As diferentes taxas de acumulação líquida dos nutrientes, nos diferentes órgãos da caramboleira, nem sempre acompanharam a taxa de acumulação de nutrientes do respectivo órgão.

Extração e exportação de nutrientes em cultivares de batata: II - micronutrientes

Cultivares de batata mais produtivas possivelmente exigem maior quantidade de micronutrientes, porém no Brasil há carência de informações sobre extração e exportação de micronutrientes pelas principais cultivares de batata utilizadas. O objetivo deste trabalho foi avaliar a produtividade de tubérculos, a extração e a exportação de micronutrientes nas cultivares de batata Ágata, Asterix, Atlantic, Markies e Mondial. O experimento foi conduzido durante a safra de inverno, em um Latossolo Vermelho, no município de Itaí (SP). As parcelas foram constituídas pelas cinco cultivares, e as subparcelas, por épocas de coletas, realizadas no momento do plantio e a cada sete dias após a emergência. As cultivares Mondial e Asterix, mais produtivas, apresentaram maior extração de micronutrientes, com quantidades médias por hectare de 71 g de B, 122 g de Cu, 2.228 g de Fe, 618 g de Mn e 405 g de Zn. As menores quantidades extraídas foram observadas na cultivar Atlantic, com valores de 50, 81, 1.960, 544 e 270 g ha-1 de B, Cu, Fe, Mn e Zn, respectivamente. A fase de maior demanda por B ocorre logo após o início da formação de tubérculos, aos 34 DAP, enquanto a maior demanda por Fe e Mn inicia-se a partir dos 42 DAP e vai até 63 DAP. O Cu e o Zn são absorvidos em maiores proporções a partir dos 64 DAP até o final do ciclo. A quantidade de B, Cu, Mn e Zn exportada foi dependente da cultivar, com valores por hectare variando de 48 a 22 g de B, 79 a 16 g de Cu, 65 a 37 g de Mn e 167 a 83 g de Zn. A quantidade de Fe exportada não variou entre as cultivares, sendo, em média, de 243 g ha-1. A quantidade de micronutrientes extraída e exportada pela batateira variou com as cultivares utilizadas, indicando necessidade de manejo diferencial da adubação.

Extração e exportação de nutrientes pelo híbrido de mamona Savana: II – micronutrientes

Information about micronutrients extraction and exportation by castor bean hybrids of short stature, and the periods of highest demand for each micronutrient, are most importance for correct management to fertilization. This study aimed to evaluate the micronutrients extraction and exportation by Savana hybrid castor bean, on season and out-of-season growing. The experiments were conducted during season of 2005/2006 and out-of-season of 2006 in an Oxisol. The experimental design was a randomized block with four replications. The plots were consisted by harvest times of plants, which were carried out at 17, 31, 45, 59, 73, 97 and 120 days after emergence (DAE) during the season and at 17, 31, 45, 59, 80; 100 and 120 DAE in the out-of-season. In both seasons the order of micronutrients extraction by hybrid Savanna is: Fe> Mn> Zn> B> Cu> Mo, but with larger amounts of season cultivation. The time of greatest Zn and Mo absorption during the season and the Fe in out-of-season occurs at 80 DAE, although the other micronutrients are absorbed at higher rates between 50 and 65 DAE. In season the yield, nutrients extraction and exportation from soil are higher than out-of-season, but the nutrients extraction and exportation per ton show less variation between growing seasons. Fifty percent of zinc and 60% of Cu uptaken, on average, in out-of-season is exported with grains, but for the other micronutrients the proportion exported with grains is less than 40%.

Immunomodulatory Effects of Palladium(II) Complexes of 1,2,4-Triazole on Murine Peritoneal Macrophages

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Adsorption of Cu(II) and Co(II) complexes on a silica gel surface chemically modified with 2-mercaptoimidazole

The isotherms of adsorption of MeX2 (Me = Cu2+, Co2+; X = Cl-, Br-, ClO4-) by silica gel chemically modified with 2-mercaptoimidazole (SiMI) were studied in acetone and ethanol solutions, at 25 degrees C. Covalently attached 2-mercaptoimidazole molecule to silica gel surface adsorbs MeX2 from solvent by forming a surface complex. The metal is bonded to the surface through the nitrogen atom of attached 2-mercaptoimidazole. At low loading, the electronic and ESR spectral parameters indicated that the Cu2+ complexes are in a distorted-tetragonal symmetry field. The d-d electronic transition spectra showed that for Cu(ClO4)(2) complex, the peak of absorption did not change for any degree of metal loading and for Cl- and Br- complexes, the peak maxima shifted to higher energy with lower metal loading. The CoX2(X = Cl-, Br-, ClO4-) analogues possess a distorted-tetrahedral field.

Adsorption of copper(II) and cobalt(II) complexes on a silica gel surface chemically modified with 3-amino-1,2,4-triazole

The isotherms of adsorption of MX2 (M = Cu2+, Co2+; X = Cl-, Br-, ClO4) by silica gel chemically modified with 3-amino-1,2,4-triazole (SiATR) were studied in acetone and ethanol solutions, at 25 degrees C. The 3-amino-1,2,4-triazole molecule, covalently bound to the silica gel surface, adsorbs MX2 from solvent by forming a surface complex. At low loading, the electronic and electron spin resonance spectral parameters indicated that the Cu2+ complexes have distorted tetragonal symmetry. The CoX2 (X = Cl-, Br-) analogues exhibit a distorted-tetrahedral geometry, whilstthe (SiATR)mCo)ClO4)(2) complex has a tetragonally distorted octahedral geometry, with four equatorial nitrogen atoms around the cobalt. (C) 1998 Elsevier B.V. B.V. All rights reserved.

Structure of copper(II) complexes adsorbed on functionalized polyhedral oligomeric silsesquioxane

The 3-amino-1,2,4-triazole-modified silsesquioxane nanoplatforms have been prepared and characterized. The silsesquioxane nanocages readily react with CuX(2) in aqueous solution to form copper complex-substituted silsesquioxanes. Adsorption isotherms of CuX(2) from aqueous solution were studied at 25 degrees C. The electronic and ESR spectral parameters indicated that the copper ion is in a distorted-tetragonal symmetry field. (C) 2007 Elsevier B.V. All rights reserved.

Approach combining on-line metal exchange and tangential-flow ultrafiltration for in-situ characterization of metal species in humic hydrocolloids

This paper deals with the development and optimization of an analytical procedure using ultrafiltration and a flow-injection system, and its application in in-situ experiments to characterize the lability and availability of metal species in humic-rich hydrocolloids. The on-line system consists of a tangential flow ultrafiltration device equipped with a 3-kDa filtration membrane. The concentration of free ions in the filtrate was determined by atomic-absorption spectrometry, assuming that metals not complexed by aquatic humic substances (AHS) were separated from the complexed species (M-AHS) retained by the membrane. For optimization, exchange experiments using Cu(II) solutions and AHS solutions doped with the metal ions Ni(II), Mn(II), Fe(III), Cd (II), and Zn(II) were carried out to characterize the stability of the metal-AHS complexes. The new procedure was then applied in-situ at a tributary of the Ribeira do Iguape river (Iguape, São Paulo State, Brazil) and evaluated using the ions Fe(III) and Mn(II), which are considered to be essential constituents of aquatic systems. From the exchange between metal-natural organic matter (M-NOM) and the Cu(II) ions it was concluded that Cu(II) concentrations > 485 mu g L(-1) were necessary to obtain maximum exchange of the complexes Mn-NOM and Fe-NOM, corresponding to 100% Mn and 8% Fe. Moreover, the new analytical procedure is simple and opens up new perspectives for understanding the complexation, transport, stability, and lability of metal species in humic-rich aquatic environments.