60 resultados para State changes
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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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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
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We show that diffusion can play an important role in protein-folding kinetics. We explicitly calculate the diffusion coefficient of protein folding in a lattice model. We found that diffusion typically is configuration- or reaction coordinate-dependent. The diffusion coefficient is found to be decreasing with respect to the progression of folding toward the native state, which is caused by the collapse to a compact state constraining the configurational space for exploration. The configuration- or position-dependent diffusion coefficient has a significant contribution to the kinetics in addition to the thermodynamic free-energy barrier. It effectively changes (increases in this case) the kinetic barrier height as well as the position of the corresponding transition state and therefore modifies the folding kinetic rates as well as the kinetic routes. The resulting folding time, by considering both kinetic diffusion and the thermodynamic folding free-energy profile, thus is slower than the estimation from the thermodynamic free-energy barrier with constant diffusion but is consistent with the results from kinetic simulations. The configuration- or coordinate-dependent diffusion is especially important with respect to fast folding, when there is a small or no free-energy barrier and kinetics is controlled by diffusion. Including the configurational dependence will challenge the transition state theory of protein folding. The classical transition state theory will have to be modified to be consistent. The more detailed folding mechanistic studies involving phi value analysis based on the classical transition state theory also will have to be modified quantitatively.
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We investigate the dynamics of a Duffing oscillator driven by a limited power supply, such that the source of forcing is considered to be another oscillator, coupled to the first one. The resulting dynamics come from the interaction between both systems. Moreover, the Duffing oscillator is subjected to collisions with a rigid wall (amplitude constraint). Newtonian laws of impact are combined with the equations of motion of the two coupled oscillators. Their solutions in phase space display periodic (and chaotic) attractors, whose amplitudes, especially when they are too large, can be controlled by choosing the wall position in suitable ways. Moreover, their basins of attraction are significantly modified, with effects on the final state system sensitivity. (c) 2005 Elsevier Ltd. All rights reserved.
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The Pluriserial Ribeira Magmatic System-590 of the Late Precambrian Ribeira Fold Belt comprises seven groups of high-K rocks of crustal or mantle origin with ages ranging between 620 and 570 Ma. One of these groups is represented by transalkaline suites akin to appinitic lamprophyres. The suites assemble one or more of following lithologies: (+/- quartz) gabbros and monzogabbros, (+/- quartz) diorites and monzodiorites, (+/- quartz) monzonites and syenites in addition to rare granites. All these rocks occur together in the Piracaia pluton, State of São Paulo. The mineralogy of the Piracaia suite comprises variable amounts of plagioclase (An 60-10), alkali-feldspars (orthoclase, microcline, albite), ortho- (Fe-hypersthene) and clinopyroxenes (augite), amphiboles (hornblende and rare late Fe-hastingsite), abundant biotite, quartz, opaques, sphene, allanite and zircon. Several magmatic pulses constructed the pluton. The Piracaia magma bulk trend evolved initially along the silica-undersaturation plane with simultaneous fractionation of accessory, mafic and felsic minerals. These are segregated in feldspar-rich cumulates. In the late stage, the evolutionary trend followed two distinct paths: one along the or-ab thermal barrier with the crystallization of syenites; the second one along the thermal valley in the or-ab-qz subsystem, producing quartz-syenites and granites. The source of the Piracaia magma was a 'vein-plus-wall-rock-system '. Together the pulses reflect increasing and decreasing participation of peridotites and mica pyroxenites, respectively, in the magmatogenic process. The magmatic pulses were stored in magma chambers, several drained by deep faults or fractures, which were successively reactivated and recharged. Each new pulse underwent mixing with earlier residual magma, followed by fractionation. During ascent through the hot and thickened post-collisional crust, the magma pulses underwent minor compositional changes by crustal contamination. The concentration of valuable elements (Cu, Zn, Gd) in the Piracaia pluton occurred during two phases of the magmatic evolution. Cu and Zn were enriched in cumulates and Gd was concentrated in residual quartz-syenitic veins. Due to their homogeneous dark colour and texture, the monzodiorites are exploited both for polished dimension stones and supports for sensitive scientific instruments. (C) 2001 Elsevier B.V. Ltd. All rights reserved.
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The effect of calcination temperature during the formation of the solid solution Sn(0.9)Ti(0.1)O(2) doped with 1.00 mol % CoO and 0.05 mol % Nb(2)O(5) is presented. The structural characteristics of this system were studied using X-ray diffraction, and the changes in phase formation were analyzed using the Rietveld method. With an increase in calcination temperature, there is increasing miscibility of Ti into the (Ti,Sn)O(2) phase and near 1000 degrees C, and the remaining TiO(2) (anatase) was transformed into the rutile phase. The sintering process, monitored using dilatometry, suggests two mass transport mechanisms, one activated close to 900 degrees C associated with the presence of TiO(2) (anatase) and the second mechanism, occurring between 1200 and 1300 degrees C, is attributed to a faster grain boundary diffusion caused by oxygen vacancies. (C) 2008 International Centre for Diffraction Data.
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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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An understanding of isoniazid (INH) drug resistance mechanism in Mycobacterium tuberculosis should provide significant insight for the development of newer anti-tubercular agents able to control INH-resistant tuberculosis (TB). The inhA-encoded 2-trans enoyl-acyl carrier protein reductase enzyme (InhA) has been shown through biochemical and genetic studies to be the primary target for INH. In agreement with these results, mutations in the inhA structural gene have been found in INH-resistant clinical isolates of M. tuberculosis, the causative agent of TB. In addition, the InhA mutants were shown to have higher dissociation constant values for NADH and lower values for the apparent first-order rate constant for INH inactivation as compared to wild-type InhA. Here, in trying to identify structural changes between wild-type and INH-resistant InhA enzymes, we have solved the crystal structures of wild-type and of S94A, I47T and I21V InhA proteins in complex with NADH to resolutions of, respectively, 2.3 angstrom, 2.2 angstrom, 2.0 angstrom, and 1.9 angstrom. The more prominent structural differences are located in, and appear to indirectly affect, the dinucleotide binding loop structure. Moreover, studies on pre-steady-state kinetics of NADH binding have been carried out. The results showed that the limiting rate constant values for NADH dissociation from the InhA-NADH binary complexes (k(off)) were eleven, five, and tenfold higher for, respectively, I21V, I47T and S94A INH-resistant mutants of InhA as compared to INH-sensitive wildtype InhA. Accordingly, these results are proposed to be able to account for the reduction in affinity for NADH for the INH-resistant InhA enzymes. (c) 2006 Elsevier Ltd. All rights reserved.
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The reactions of the pseudohalide-bridged dimer [Pd(N,C-dmba)(mu -SCN)](2) (1) (dmba = N,N-dimethylbenzylamine) with cis-Ph2PCH=CHPPh2 (cis-dppet) (1:1 molar ratio) and of [Pd(N,C-dmba)(mu -NCO)](2) (2) with Ph2PCH2CH2PPh2 (dppe) (1:2 molar ratio) gave mononuclear [Pd(C-dmba)(SCN)(cis-dppet)].H2O (1a) and [Pd(C-dmba)(NCO)(dppe)] (2a), respectively, with the diphosphines acting as chelating ligands. Reaction of (2) with Fe(C5H4PPh2)(2) (dppf) (1:1 molar ratio) yielded [{Pd(N,C-dmba)(NCO)}(2)(mu -dppf)] (2b), a bimetallic species containing two palladium atoms bridged by the diphosphine, whereas reaction in a 1:2 molar ratio gave the mononuclear [Pd(N,C-dmba)(dppf)][NCO]. CH2Cl2 (2c), with the diphosphine acting as a chelating ligand. The compounds have been characterized by elemental analysis, i.r., P-31{H-1}, C-13- and H-1-n.m.r. spectroscopies. Conductivity measurements together with spectroscopic data showed that (1a) and (2a) do not have the same structure in the solid state and in MeCl solution, whereas for compounds (2b) and (2c) no structural changes were observed when the solids were dissolved in MeCl.
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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)