Synthesis, structure, and redox states of homoleptic d-block metal complexes with bis-1,2,4-triazin-3-yl-pyridine and 1,2,4-triazin-3-yl-bipyridine extractants

it has been established that triazinyl bipyridines (hemi-BTPs) and bis-triazinyl pyridines (BTPs), ligands which are currently being investigated as possible ligands for the separation of actinides from lanthanides in nuclear waste, are able to form homoleptic complexes with first row transition metals such as cobalt(IT), copper(II), iron(II), manganese(II), nickel(II) and zinc(II). The metal complexes exhibit six-co-ordinate octahedral structures and redox states largely analogous to those of the related terpyridine complexes. The reactivity of the different redox states of cobalt bis-hemi-BTP complex in aqueous environments has been studied with two-phase electrochemistry by immobilisation of the essentially water-insoluble metal complexes on graphite electrodes and the immersion of this modified electrode in an aqueous electrolyte. It was found that redox potentials for the metal-centred reactions were pH-independent whereas the potentials for the ligand-centred reactions were strongly pH-dependent. The reductive degradation of these complexes has been investigated by computational methods. Solvent extraction experiments have been carried out for a range of metals and these show that cobalt(II) and nickel(II) as well as palladium(II), cadmium(II) and lead(II) were all extracted with the ligands 1e and 2c with higher distribution ratios that was observed for americium(III) under the same conditions. The implications of this result for the use of these ligands to separate actinides from nuclear waste are discussed. (c) 2005 Elsevier Ltd. All rights reserved.

Transcriptional Response to Hypoxia in the Aquatic Fungus Blastocladiella emersonii

Global gene expression analysis was carried out with Blastocladiella emersonii cells subjected to oxygen deprivation (hypoxia) using cDNA microarrays. In experiments of gradual hypoxia (gradual decrease in dissolved oxygen) and direct hypoxia (direct decrease in dissolved oxygen), about 650 differentially expressed genes were observed. A total of 534 genes were affected directly or indirectly by oxygen availability, as they showed recovery to normal expression levels or a tendency to recover when cells were reoxygenated. In addition to modulating many genes with no putative assigned function, B. emersonii cells respond to hypoxia by readjusting the expression levels of genes responsible for energy production and consumption. At least transcriptionally, this fungus seems to favor anaerobic metabolism through the upregulation of genes encoding glycolytic enzymes and lactate dehydrogenase and the downregulation of most genes coding for tricarboxylic acid (TCA) cycle enzymes. Furthermore, genes involved in energy-costly processes, like protein synthesis, amino acid biosynthesis, protein folding, and transport, had their expression profiles predominantly down-regulated during oxygen deprivation, indicating an energy-saving effort. Data also revealed similarities between the transcriptional profiles of cells under hypoxia and under iron(II) deprivation, suggesting that Fe(2+) ion could have a role in oxygen sensing and/or response to hypoxia in B. emersonii. Additionally, treatment of fungal cells prior to hypoxia with the antibiotic geldanamycin, which negatively affects the stability of mammalian hypoxia transcription factor HIF-1 alpha, caused a significant decrease in the levels of certain upregulated hypoxic genes.

Development and Application of a Highly Selective Biomimetic Sensor for Detection of Captopril, an Important Ally in Hypertension Control

A biomimetic sensor is proposed as a promising new analytical method for determination of captopril in different classes of samples. The sensor was prepared by modifying a carbon paste electrode with iron (II) phthalocyanine bis(pyridine) [FePe(dipy)] complex. Amperometric measurements in a batch analytical mode were first carried out in order to optimize the sensor response. An applied potential lower than 0.2 V vs Ag vertical bar AgCl in 0.1 mol L(-1) of TRIS buffer at pH 8.0 provided the best response, with a linear range of 2.5 x 10(-5) to 1.7 x 10(-4) mol L(-1). A detailed investigation of the selectivity of the sensor, employing seventeen other drugs, was also performed. Recovery studies were carried out using biological and environment samples in order to evaluate the sensor`s potential for use with these sample classes. Finally, the performance of the biomimetic sensor was optimized in a flow injection (FIA) system using a wall jet electrochemical cell. Under optimized flow conditions, a broad linear response range, from 5.0 x 10(-4) to 2.5 x 10(-2) mol L(-1), was obtained for captopril, with a sensitivity of 210 +/- 1 mu A L mol(-1).

Nitric oxide release using natural rubber latex as matrix

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

Effect of hydrogen charging on the stability of SAE 10B22 steel surface in alkaline solutions

The influence of hydrogen charging into a quenched and tempered boron steel membrane electrode (SAE 10B22) was studied using borate buffer (pH 8.4) and NaOH solutions (pH 12.7), with or without the addition of 0.01 M EDTA. At the hydrogen input side, hydrogen charging influenced cyclic voltammograms increasing the anodic charge of iron(II) hydroxide formation, and decreasing the donor density of passive films. These results suggest that the hydrogen ingress caused instability of metallic surface, increasing the surface area activity. (C) 2005 Elsevier Ltd. All rights reserved.

Estudo da aplicação do processo foto-Fenton solar na degradação de efluentes de indústria de tintas

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

Study on the use of oxidant scrubbers for elimination of interferences due to nitrogen dioxide in analysis of atmospheric dimethylsulfide

Neste trabalho foi avaliado o desempenho de filtros para dióxido de nitrogênio, buscando evitar perdas durante a amostragem de sulfetos orgânicos, provocadas por oxidantes atmosféricos. Diferentes compostos e misturas foram usadas para recobrir superfícies sólidas empregadas na preparação destes filtros. Um sistema automatizado de análise em fluxo foi utilizado para comparar a eficiência de retenção de dióxido de nitrogênio pelos filtros. Entre os materiais testados na preparação dos filtros, as melhores escolhas foram papel ou lã de vidro impregnados com a mistura de sulfato de ferro (II), ácido sulfúrico e ácido pirogalico e ainda os filtros feitos de papel impregnados com trietanolamina. Os resultados obtidos em laboratório com mistura de gás padrão de dimetilsulfeto e experimentos em campo confirmaram a qualidade dos filtros e indicaram que eles podem ser utilizados para evitar a oxidação de sulfetos orgânicos durante a sua amostragem.

Synthesis and electrochemical behavior of single-crystal magnetite nanoparticles

Water-dispersed magnetite nanoparticle synthesis from iron(II) chloride in dimethyl sulfoxide (DMSO)-water solution at different DMSO-water ratios in alkaline medium was reported. TEM and XRD results suggest a single-crystal formation with mean particle size in the range 4-27 nm. Magnetic nanoparticles are formed by the oxidative hydrolysis reaction from green rust species that leads to FeOOH formation, followed by autocatalysis of the adsorbed available Fe(II) on the FeOOH surfaces. The available hydroxyl groups seem to be dependent on the DMSO-water ratio due to strong molecular interactions presented by the solvent mixture. Goethite phase on the magnetite surface was observed by XRD data only for sample synthesized in the absence of DMSO. In addition, cyclic voltammetry with carbon paste electroactive electrode (CV-CPEE) results reveal two reduction peaks near 0 and +400 mV associated with the presence of iron(III) in different chemical environments related to the surface composition of magnetite nanoparticles. The peak near +400 mV is related to a passivate thin layer surface such as goethite on the magnetite nanoparticle, assigned to the intensive hydrolysis reaction due to strong interactions between DMSO-water molecules in the initial solvent mixture that result in a hydroxyl group excess in the medium. Pure magnetite phase was only observed in the samples prepared at 30% (30W) and 80% (80W) water in DMSO in agreement with the structured molecular solvent cluster formation. The goethite phase present on the, magnetite nanoparticle surface like a thin passivate layer only was detectable using CV-CPEE, which is a very efficient, cheap, and powerful tool for surface characterization, and it is able to determine the passivate oxyhydroxide or oxide thin layer presence on the nanoparticle surface.

Four new metal complexes with the amino acid deoxyalliin

The solid complexes [Co(C6H10NO2S) 2], [Ni(C6H10NO2S)2], [Cu(C6H10NO2S)2] and [Fe(C 6H10NO2S)2] were obtained from the reaction of cobalt(II), nickel(II), copper(II) and iron(II) salts with the potassium salt of the amino acid deoxyalliin (S-allyl-L-cysteine). Electronic absorption spectra of the complexes are typical of octahedral structures. Infrared spectroscopy confirms the ligand coordination to the metal ions through (COO-) and (NH2) groups. EPR spectrum of the Cu(II) complex indicates a slight distortion of its octahedral symmetry. Mössbauer parameters permitted to identify the presence of iron(II) and iron(III) species in the same sample, both of octahedral geometry. Thermal decomposition of the complexes lead to the formation of CoO, NiO, CuO and Fe2O3 as final products. The compounds show poor solubility in water and in the common organic solvents. ©2005 Sociedade Brasileira de Química.

Optimization of a novel nitric oxide sensor using a latex rubber matrix

This study present a novel NO sensor made of a spin trap (iron(II)-diethyldithiocarbamate complex, FeDETC) incorporated in a latex rubber matrix and works as a trap for NO, which is detectable by Electron Paramagnetic Resonance (EPR). We explored the optimization of our sensors changing systematically two fabrication parameters: the latex rubber matrix temperature of polymerization and FeDETC concentration inside the matrix. The sensor was prepared in four different temperatures: 4, 10, 20 and 40°C. The FeDETC concentration was also varied from 0.975 to 14.8 mM. We observed a variation of the EPR signals from the sensors prepared at different conditions. We found a high stability of the EPR response from our sensor, 40 days at RT. The best sensor was made with a latex rubber matrix polymerized at 10°C and with a FeDETC concentration of 14.8 mM. In vivo tests show good biocompatibility of our sensor. © 2007 Asian Network for Scientific Information.

Development and application of a highly selective biomimetic sensor for detection of captopril, an important ally in hypertension control

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

Desenvolvimento de sensor biomimético para determinação de captopril em amostras de interesse ambiental, biológico e farmacêutico

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Spectrophotometric determination of arsenic in soil samples using 2-(5-bromo-2-pyridylazo)-5-di-ethylaminophenol (Br-PADAP)

Um novo método, simples e sensível para a determinação de arsênio em solo é proposto neste trabalho. Este método é baseado na redução de prata (I) e ferro (III) pela arsina seguida da reação de complexação do ferro (II) com o reagente espectrofotométrico 2-(5-bromo-2-piridilazo)-5-di-etilaminofenol (Br-PADAP). A determinação de arsênio apresentou uma sensitividade de Sandell de 3.1x10^-4 cm^-2, foi linear na faixa de 0.1 µg ml^-1 to 2.0 µg ml^-1 (r₅₆₀ = 0.9995), apresentou uma absortividade molar de 2.45x10⁵ l mol^-1 cm^-1 e um limite de detecção de 1.4 ng ml^-1 (3s) estes dados foram obtidos para 10 ml de amostra. A seletividade foi melhorada com o uso de EDTA com agente mascarante. O método proposto foi aplicado na determinação do arsênio na presença de outros íons e em amostras de solo. Os resultados revelaram que antimônio (III), mercúrio (II), germânio (IV), platina (IV) interferem na análise em todas as proporções analisadas. As interferências podem ser facilmente removidas pelo uso do EDTA. A precisão e a exatidão deram resultados satisfatórios, com desvio padrão relativo abaixo de 5%. As recuperações de arsênio em solo variaram de 95,55 a 102,70% com uma média de 99,63%. Estes resultados demonstraram que o método proposto é aplicável para a análise do arsênio em diferentes amostras de solo.

Sensores sólidos para detecção de óxido nítrico baseados em cucurbit[6]uril e em siloxano-poli(oxipropileno)

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

Novel solid state nitric oxide sensor using siloxane-poly (oxypropylene) (PPO)

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