Proteínas tirosina fosfatases: propriedades e funções biológicas

Protein phosphorylation-dephosphorylation catalyzed by the opposing and dynamic action of protein kinases and phosphatases probably, is the most crucial chemical reaction taking place in living organisms. Protein phosphatases are classified according to their substrate specificity and sensitivity to inhibitory or activator agents, into two families of protein phosphatases: serine/threonine phosphatases and tyrosine phosphatases (PTPs). PTPs can be divided into 3 groups: tyrosine specific phosphatases, dual and low molecular weight phosphatases. The role of tyrosine phosphorylation in mitogenic signaling is well documented, and one would predict that vanadate, pervanadate and other oxidant agents (protein tyrosine phosphatase inhibitors) may act as a growth stimulator.

Recuperação de metais de catalisadores mássicos e monometálicos

This work presents a study on the dissolution of some commercial monometallic and non-supported deactivated catalysts in HF + H2O2 mixtures (and, eventually, other media) under mild experimental conditions, after a previous oxidation step. The samples were neither crushed nor grinded. The best experimental conditions were dependent on the nature of the support and of the active phase. For example, the Pt/Al2O3 catalyst was dissolved in about 10 minutes, without agitation and heating; however, dissolution of the Pd/Al2O3, Ni/Al2O3, Ni/SiO2, Cu/Al2O3 and V2O5 samples required a temperature of 60 ºC and an agitation of 400 rpm. A careful addition of a NaOH solution allowed a quantitative precipitation of aluminium as criolite (Na3AlF6) or precipitation of Si as Na2SiF6; NaF was obtained as a by-product. As expected, processing of Pd/C, V2O5 and CuO.Cr2O3 samples was relatively simple. Metals recovery from catalysts reached a quantitative level in all samples studied; it is particularly interesting that platinum and palladium could be easily recovered in a single step process, thus separing them from aluminium.

Estudo da biodisponibilidade de metais nos sedimentos da Lagoa da Pampulha

The presence of metals in the sediments of Pampulha Lake was investigated in order to determine the bioavailability of metals in these sediments for the cultivation of vegetables such as lettuce. The chemical analyses of metals and As were accomplished by the k0 neutron activation technique. The plans for recovering this lake foresee the removal of the deposited sediments and transport of the discarded material to a specific area after the dam. The present study suggests that this strategy of discarding sediments doesn't imply any risk for the local population, in relation to the bioavailability of metals in these sediments.

Propriedades espectroscópicas e parâmetros ópticos-eletrônicos dos complexos Ln(NO3)3.2DTPO.4H2O (Ln = Nd e Er)

Complexes with the composition Ln(NO3)3.2DTPO.4H2O (Ln = Nd and Er) were synthesized and characterized by infrared and visible absorption spectra (solid state and solution). The results of the absorption spectra in the solid state suggest that metal-ligand bonds are essentially electrostatic in all complexes. The absorption spectra of the nitrate salt solution presented smaller values of the oscillator strength when compared to the spectra of the complexes in the same solvent.

Distribuição de metais pesados em sedimentos do sistema estuarino da Ilha de Vitória-ES

Heavy-metal concentration in sediment is an important parameter for identifying pollution sources and assessing pollution levels in aquatic ecosystems. In this context, the present study aimed at determining concentrations of heavy metals in sediments from the Vitória estuarine system, Brazil. Twenty nine stations were surveyed to assess the spatial distribution of heavy metals. The metals for silt-clay fractions (<63 µm) were analyzed through atomic absorption spectrometry. A discriminant analysis segregated the stations in four groups representing four areas within the estuarine system. The Espírito Santo Bay showed the lowest metal concentrations, while the Vitória harbor canal showed the highest. We concluded that concentrations of heavy metals reflect natural conditions and the contribution of human activities from sewage and industrial effluents. It was not possible to directly associate metal concentrations to specific pollution sources.

Hidrogenação eletrocatalítica de substratos orgânicos: estudo da eficiência dos metais nobres níquel, paládio e platina usando eletrodos modificados

Nickel, palladium and platinum micro-crystals were dispersed in films covering a vitreous carbon plate electrode by ion exchange followed by electroreduction of their ions. These modified electrodes were used in the electrocatalytic hydrogenation of several substrates of different classes and their efficiency is reported. A comparison among them was performed based on the structural characteristics of the metals. A modified electrode containing platinum showed to be more efficient than a palladium modified electrode and the one of nickel was the less efficient.

Aplicação da equação de Poisson-Boltzmann ao cálculo de propriedades dependentes do pH em proteínas

The ability of biomolecules to catalyze chemical reactions is due chiefly to their sensitivity to variations of the pH in the surrounding environment. The reason for this is that they are made up of chemical groups whose ionization states are modulated by pH changes that are of the order of 0.4 units. The determination of the protonation states of such chemical groups as a function of conformation of the biomolecule and the pH of the environment can be useful in the elucidation of important biological processes from enzymatic catalysis to protein folding and molecular recognition. In the past 15 years, the theory of Poisson-Boltzmann has been successfully used to estimate the pKa of ionizable sites in proteins yielding results, which may differ by 0.1 unit from the experimental values. In this study, we review the theory of Poisson-Boltzmann under the perspective of its application to the calculation of pKa in proteins.

Síntese, caracterização e propriedades espectroscópicas de criptatos de lantanídeo do tipo [LnÌ(bipy)2py(CO2Et) 2(3+)]

This work reports on the synthesis, characterization (infrared and hidrogen nmr spectra) and photophysical properties (luminescence spectra and emission quantum yield) of the lanthanide cryptates [LnÌ(bipy)2py(CO2Et) 2]3+ with Ln = Eu3+, Tb3+ or Gd3+, which can be applied as efficient Light-Conversion-Molecular-Devices. From emission spectra of [EuÌ(bipy)2py(CO2Et) 2]3+ it was possible to assign C3 symmetry to the metal ion. The spectroscopic studies show a higher emission quantum yield (q=25%) for [TbÌ(bipy)2py(CO2Et) 2]3+ in aqueous solution, whereas the europium cryptate presents q=14%. This is justified by a more efficient energy transfer between triplet and emission levels of terbium (T->5D4).

Remoção de metais pesados de efluentes aquosos pela zeólita natural escolecita - influência da temperatura e do pH na adsorção em sistemas monoelementares

Cation exchange capabilities of a Brazilian natural zeolite, identified as scolecite, were evaluated for application in wastewater control. We investigated the process of sorption of chromium(III), nickel(II), cadmium(II) and manganese(II) in synthetic aqueous effluents, including adsorption isotherms of single-metal solutions. The natural zeolite showed the ability to take up the tested heavy metals in the order Cr(III) > Cd(II) > Ni(II) > Mn(II), and this could be related to the valence and the hydration radius of the metal cations. The influence of temperature (25, 40 and 60 ºC) and initial pH value (from 4 to 6) was also evaluated. It was found that the adsorption increased substantially when the temperature was raised to 60 ºC and that maximum adsorption capacity was observed at pH 6. These results demonstrate that scolecite can be used for removal of heavy metals from aqueous effluents, under optimized conditions.

Estudo de efeito dos sais precursores sobre as propriedades eletrocatalíticas de eletrodos de Ti-SnO2/Sb preparados por decomposição térmica

The physical and electrochemical properties of Ti-SnO2/Sb electrodes obtained by the thermal decomposition of solutions of the precursor salts SnCl2×2H2O/SbCl3 and SnSO4/Sb2(SO4)3 were investigated. The reversibility of the cyclic voltammetric response of the Fe(CN)6(4-)/Fe(CN)6(3-) redox couple was assessed using the obtained electrodes. Their catalytic activity for the oxygen-evolving reaction and maximum capacity for electronic transfer were also evaluated by potential and current linear scans in 0.5 mol L-1 H2SO4. Additionally, scanning electron microscopy analyses allowed the visualization of the morphology of the oxide films obtained. The best results were presented by the electrodes obtained from the chloride salt precursors.

Conformações distorcida e planar do anel porfirínico em complexos e hemoproteínas: propriedades físico-químicas e implicações espectroscópicas

The different conformations of porphyrin rings are strongly related with the electronic configurations of the metallic center in the ferriheme coordination compounds and heme proteins. The usual electronic configuration, (d xy)²(d xz,d yz )³ presents a planar conformation of the porphyrin ring and the less common electronic configuration (d xz,d yz)4(d xy )¹ occurs in the case of a strongly ruffled ring. These states are responsible for distinct chemical and spectroscopic properties of the porphyrin systems. The importance of the ring conformations, their characteristics, implications and applications are discussed.

Eletrodos de pasta de carbono modificados com ácidos húmicos: estudo e determinação de metais em meio aquoso

Since 1992, the carbon paste electrodes modified with humic acids have been used for studying the behavior of metals in aqueous solutions. Many parameters influence the performance of the electrodes, such as the humic acid ratio, the nature of the humic acid, the accumulation time, the pH, the scan rate, and the preparation of the electrodes itself. There are various methos of preparing the electrodes. The goal of this paper is to review some of them. The advantages of using electrodes modified with humic acids as electrochemical sensors for evaluating metals in aqueous solution are stressed.

Propriedades eletrônicas e estruturais do PbTiO3: teoria do funcional de densidade aplicada a modelos periódicos

Calculations based on density functional theory at the B3LYP hybrid functional level applied to periodic models have been performed to characterize the structural and electronic properties of PbTiO3. Two different slab terminations (PbO and TiO2) have been considered to obtain and discuss the results of band structure, density of states, charge distribution on bulk and surface relaxation. It is observed that the relaxation processes are most prominent for the Ti and Pb surface atoms. The electron density maps confirm the partial covalent character of the Ti-O bonds. The calculated optical band gap and other results are in agreement with experimental data.

Estrutura e propriedades de elipticinas

The ellipticines constitute a broad class of molecules with antitumor activity. In the present work we analyzed the structure and properties of a series of ellipticine derivatives in the gas phase and in solution using quantum mechanical and Monte Carlo methods. The results showed a good correlation between the solvation energies in water obtained with the continuum model and the Monte Carlo simulation. Molecular descriptors were considered in the development of QSAR models using the DNA association constant (log Kapp) as biological data. The results showed that the DNA binding is dominated by electronic parameters, with small contributions from the molecular volume and area.

Efeito do cromo nas propriedades catalíticas da MCM-41

The effect of chromium on the catalytic properties of MCM-41 was evaluated in order to develop new catalysts for the trimethylbenzene transalkylation with benzene to produce ethylbenzene, a high-value aromatic in the industry. It was found that chromium decreases the specific surface area but increases the acidity, turning MCM-41 into an active and selective catalyst for ethylbenzene and toluene production. The coke produced on the catalyst is hydrogenated and mainly located outside the pores and thus can be easily removed. The catalyst is more active and selective than mordenite, a commercial catalyst, and thus more promising for commercial applications.