832 resultados para Shifting mechanism
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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
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This paper develops a framework for the interpretation of ionic insertion/deinsertion reactions in an aqueous environment taking place in transition-metal hexacyanoferrates of the general formula KhFek3+ [Fe2+ (CN)(6)](l)center dot mH(2)O, also called Prussian Blue. Three different processes were fully separated in the electrochemistry of these films. It was clearly identified that one of these electrochemical processes involves the insertion/deinsertion of H3O+ (hydrated protons) through the channels of the KhFek3+ [Fe2+ (CN)(6)](l) center dot mH(2)O structure to reach the film electroneutrality during the electron transfer between Everitt's Salt and Prussian Blue. The other electrochemical processes involve K+ or H+ (proton) exchange through the water crystalline structure existing in the channels of the KhFek3+ [Fe2+(CN)(6)](l)center dot mH(2)O structure.
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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In this work, the effect of cerium (IV) ammonium nitrate (CAN) addition on the polymerization of bis-[triethoxysilyl]ethane (BTSE) film applied on carbon steel was studied. The electrochemical characterization of the films was carried out in 0.1 mol L(-1) NaCl solution by open-circuit potential measurements, anodic and cathodic polarization curves and electrochemical impedance spectroscopy (EIS). Morphological and chemical characterization were performed by atomic force microscopy (AFM), contact angle measurements, infrared-spectroscopy, nuclear magnetic resonance and thermogravimetric analysis. The results have clearly shown the improvement on the protective properties of the Ce(4+) modified film as a consequence of the formation of a more uniform and densely reticulated silane film. A mechanism is proposed to explain the accelerating role of Ce(4+) ions on the cross-linking of the silane layer. (C) 2008 Elsevier Ltd. All rights reserved.
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Polidocanol-solubilized osseous plate alkaline phosphatase was modulated by cobalt ions in a similar way as by magnesium ions. For concentrations up to 1 mu M, the Chelex-treated enzyme was stimulated by cobalt ions, showing K-d = 6.0 mu M, V = 977.5 U/mg, and site-site interactions (n = 2.5). Cobalt-enzyme was highly unstable at 37 degrees C, following a biphasic inactivation process with inactivation constants of about 0.0625 and 0.0015 min(-1). Cobalt ions stimulated the enzyme synergistically in the presence of magnesium ions (K-d = 5.0 mu M; V = 883.0 U/mg) or in the presence of zinc ions (K-d = 75.0 mu M; V = 1102 U/mg). A steady-state kinetic model for the modulation of enzyme activity by cobalt ions is proposed.
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The electric properties of the sodium niobate perovskite ceramic were investigated by impedance spectroscopy in the frequency range from 5 Hz to 13 MHz and from room temperature up to 1073 K, in a thermal cycle. Both capacitance and conductivity exhibit an anomaly at around 600 K as a function of the temperature and frequency. The electric conductivity as a function of angular frequency sigma(omega) follows the relation sigma(omega)=Aomega(s). The values of the exponent s lie in the range 0.15less than or equal tosless than or equal to0.44. These results were discussed considering the conduction mechanism as being a type of polaron hopping. (C) 2003 American Institute of Physics.
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The mechanism of the Yb(3+)-->Er(3+) energy transfer as a function of the donor and the acceptor concentration was investigated in Yb(3+)-Er(3+) codoped fluorozirconate glass. The luminescence decay curves were measured and analyzed by monitoring the Er(3+)((4)I(11/2)) fluorescence induced by the Yb(3+)((2)F(5/2)) excitation. The energy transfer microparameters were determined and used to estimate the Yb-Er transfer rate of an energy transfer process assisted by excitation migration among donors state (diffusion model). The experimental transfer rates were determined from the best fitting of the acceptor luminescence decay obtained using a theoretical approach analog to that one used in the Inokuti-Hirayama model for the donor luminescence decay. The obtained values of transfer parameter gamma [gamma(exp)] were always higher than that predicted by the Inokuti-Hirayama model. Also, the experimental transfer rate, gamma(2)(exp), was observed to be higher than the transfer rate predicted by the migration model. Assuming a random distribution among excited donors at the initial time (t=0) and that a fast excitation migration, which occurs in a very short time (t
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Agkistrodon contortrix laticinctus myotoxin is a Lys(49)- phospholipase A(2) (EC 3.1.1.4) isolated from the venom of the serpent A contortrix laticinctus (broad-banded copperhead). We present here three monomeric crystal structures of the myotoxin, obtained under different crystallization conditions. The three forms present notable structural differences and reveal that the presence of a ligand in the active site (naturally presumed to be a fatty acid) induces the exposure of a hydrophobic surface (the hydrophobic knuckle) toward the C terminus. The knuckle in A contortrix laticinctus myotoxin involves the side chains of Phe(121) and Phe(124) and is a consequence of the formation of a canonical structure for the main chain within the region of residues 118-125. Comparison with other Lys(49)-phospholipase A(2) myotoxins shows that although the knuckle is a generic structural motif common to all members of the family, it is not readily recognizable by simple sequence analyses. An activation mechanism is proposed that relates fatty acid retention at the active site to conformational changes within the C-terminal region, a part of the molecule that has long been associated with Ca2+-independent membrane damaging activity and myotoxicity. This provides, for the first time, a direct structural connection between the phospholipase active site and the C-terminal myotoxic site, justifying the otherwise enigmatic conservation of the residues of the former in supposedly catalytically inactive molecules.