New analytical procedure based on a cellulose bag and ionic exchanger with p-aminobenzoic acid groups for differentiation of labile and inert metal species in aquatic systems

A new procedure was developed for the in situ characterization of the lability of metal species in aquatic systems by using a system equipped with a diffusion membrane and cellulose organomodified with p-aminobenzoic acid groups (DM-Cell-PAB). To this end, the DM-Cell-PAB system was prepared by adding cellulose organomodified with p-aminobenzoic acid groups (Cell-PAB) to pre-purified cellulose bags. After the DM-Cell-PAB system was sealed, it was examined in the laboratory to evaluate the influence of complexation time, mass of exchanger, pH, metal ions (Cu, Cd, Fe, Mn, and Ni), and concentration of organic matter on the relative lability of metal species. It was found that the pH and kinetics strongly influence the process of metal complexation by the DM-Cell-PAB system. At all pH levels, Cd, Mn, and Ni showed lower complexation with Cell-PAB resin than Cu and Fe metals. Note that relative lability of metals complexed to aquatic humic substances (AHS) in the presence of Cell-PAB resin showed the following order: Cu congruent to Fe >> Ni > Mn=Cd. The results presented here also indicate that increasing the AHS concentration decreases the lability of metal species by shifting the equilibrium to AHS-metal complexes. Our results indicate that the system under study offers an interesting alternative that can be applied to in situ experiments for differentiation of labile and inert metal species in aquatic systems.

Synthesis and characterization of melanin in DMSO

Recently soluble melanin derivatives have been obtained by a synthetic procedure carried out in DMSO (D-melanin). In this work a comparative study of the structural characteristics of synthetic melanin derivatives obtained by oxidation of L-DOPA in H2O and DMSO are presented. To this end, Fourier-transform infrared spectroscopy as well as proton and carbon nuclear magnetic resonance techniques has been employed. In addition, aging effects have been investigated for D-melanin. The results suggest that sulfonate groups (-SO2CH3) from the oxidation of DMSO, are incorporated into melanin, which confers protection to the phenolic hydroxyl group present in its structure. The solubility of D-melanin in DMSO is attributed to the presence of these groups. When D-melanin is left in air for long time periods, the sulfonate groups leave the structure, and an insoluble compound is obtained. NaOH and water have been used, in order to accelerate the release of the sulfonate groups attached to D-melanin, thereby corroborating the proposed structure and the synthesis mechanism. © 2013.

Theoretical investigation of geometric configurations and vibrational spectra in citric acid complexes

The performance of advanced electronic ceramics is directly related to the synthesis route employed. Sol-gel methods are widely used for this purpose. However, the physicochemical intermediate steps are still not well understood. Better understanding and control of these processes can improve the final quality of samples. In this work, we studied theoretically the formation of metal complexes between citric acid and lithium or barium metal cations with different citric acid/metal proportions, using Density Functional Theory electronic structure calculations. Infrared and Raman scattering spectra were simulated for the more stable geometric configurations. Using this methodology, we identified some features of complexes formed in the synthesis process. Our results show that the complexes can be distinguished by changes in the bands assigned to C=O, COH-, and COO- group vibrations. An estimate of the most stable complexes is made based on total energy.

Seasonal variability of a conditional stability constant and the characterization of sedimentary humic substances from typical agricultural and urban areas

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

Estudo de nanocompósitos luminescentes baseados em complexos de Eu(III) e Ir(III) ancorados à nanopartículas de sílica por bases de Schiff

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Comparison of the dehydration kinetics of solid state compounds of 2-methoxybenzylidenepyruvate with some divalent metal ions

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Complexos fosfínicos e suas aplicações na medicina

Phosphines are well known to chemists. The ligands themselves are widely used in organic synthesis (e.g. The Wittig reaction) and transition metal phosphine complexes have been studied extensively primarily for their applications as hydrogenation catalysts (e.g. Wilkinson's catalyst). In this article attention is focused on the biological properties of phosphines and metal phosphine complexes since the triethylphosphine Au(I) complex, auranofin, has been used as antiarthritic drug for clinical use. This fact has provided a stimulus for exploration of the biological chemistry of phosphines and their metal complexes. Metal phosphine complexes also offer potential as heart-imaging agents and anticancer drugs.

Study of the alkaline earth metals with 8-hydroxyquinolinate derivatives - Calcium complexes

Metal complexes of calcium with 5,7-dibromo, 7-iodo and 5-chloro-7-iodo-8-hydroxyquinolate were precipitated in aqueous ammonia and acetone medium, except for the solid state compound with 5,7-dichloro-8-hydroxyquinoline which hasn't been obtained under these conditions. The complexes obtained through the mentioned precipitation are Ca[(C9H4ONBr2)(2)](3).H2O, Ca[(C9H5ONI)(2)].2H(2)O and Ca[(C9H4ONICl)(2)].2.5H(2)O. Their intermediate from the thermal decomposition found through TG/DTA curves in air indicated the presence of different kinds of calcium carbonates related to the reversibility and crystalline structure, depending on the original compounds. The initial compounds and the intermediate from the thermal decomposition were also characterized through IR spectra and X-ray diffraction.

Competition between humic substances and α-amino acids by metal species

The aim of the present work was to carry out experimental comparison between humic substances (HS) and representative α-amino acids (methionine, methionine sulfoxide and cysteine hydrochloride) in relation to the complexation of biologically active trace elements (Al, Cu, Pb, Mn, Zn, Cd and Ni). A mobile time-controlled tangential-flow UF technique was applied to differentiate between HS-metal and α-aminoacids-metal complexes. Metal determinations were conventionally carried out using a ICP-OES. The results showed that HS may be considered as a selective complexing agents with higher metal bonding capability in relation to Al, Cu and Pb, the fact that may be clinically important.

Caracterização e dinâmica de metais em rios da Bacia Hidrográfica do Turvo/Grande. -

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

Antitubercular activity of Ru (II) isoniazid complexes

Despite the resistance developed by the Mycobacterium tuberculosis (MTb) strains, isoniazid (INK) has been recognized as one of the best drug for treatment of Tuberculosis (Tb). The coordination of INH to ruthenium metal centers was investigated as a strategy to enhance the activity of this drug against the sensitive and resistant strains of MTb. The complexes trans-[Ru(NH3)(4)(L)(INH)](2+) (L = SO2 or NH3) were isolated and their chemical and antituberculosis properties studied. The minimal inhibitory concentration (MIC) data show that [Ru(NH3)(5)(INH)](2+) was active in both resistant and sensitive strains, whereas free INK (non-coordinated) showed to be active only against the sensitive strain. The coordination of INH to the metal center in both [Ru(NH3)(5)(INH)](2+) and trans-[Ru(NH3)(4)(SO2)(INH)](2+) complexes led to a shift in the INH oxidation potential to less positive values compared to free INH. Despite, the ease of oxidation of INH did not lead to an increase in the in vitro INH activity against MTb, it might have provided sensitivity toward resistant strains. Furthermore, ruthenium complexes with chemical structures analogous to those described above were synthesized using the oxidation products of INK as ligands (namely, isonicotinic acid and isonicotinamide). These last compounds were not active against any strains of MTb. Moreover, according to DFT calculations the formation of the acyl radical, a proposed intermediate in the INH oxidation, is favored in the [Ru(NH3)(5)(INH)](2+) complex by 50.7 kcal mol(-1) with respect to the free INH. This result suggests that the stabilization of the acyl radical promoted by the metal center would be a more important feature than the oxidation potential of the INH for the antituberculosis activity against resistant strains. (C) 2015 Elsevier B.V. All rights reserved.

Distribuição de metais e caracterização das constantes de troca entre espécies metálicas e frações húmicas aquáticas de diferentes tamanhos moleculares

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

Redox Behavior of molybdenum and tungsten in phosphate glasses

In this work, vitreous samples were prepared in the binary system (100 - x)NaPO3-xMO(3) with M = Mo and W and x varying from 10 to 60. The transmittance properties in the UV, visible, and near-infrared were monitored as a function of MO3 concentration. In both cases, an increase in the amount of transition metal results in an intense and broad absorption band in the visible and near-infrared attributed to metal reduction under synthesis conditions. It was shown that this large absorption can be partially or totally removed using specific oxidizing agents or by improving synthesis parameters such as melting temperature or cooling rate of the melt. In addition, structural investigations by Raman and X-ray absorption spectroscopy suggest that reduction only occurs when the metal cation is in octahedral geometry and that the transmittance improvement is not related with any structural changes. These results were explained in terms of thermodynamic equilibrium of redox species in the melt and allowed to obtain for the first time transparent and chemically stable glasses containing high concentrations of MO3 with transition metals in octahedral geometry inside the glass network.

A química supramolecular de complexos pirazólicos

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

Isomerismo cis-trans: de Werner aos nossos dias

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