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171.
Yikilmaz E Porta J Grove LE Vahedi-Faridi A Bronshteyn Y Brunold TC Borgstahl GE Miller AF 《Journal of the American Chemical Society》2007,129(32):9927-9940
The active site metal ion of superoxide dismutase (SOD) is reduced and reoxidized as it disproportionates superoxide to dioxygen and hydrogen peroxide. Thus, the reduction midpoint potential (Em) is a critical determinant of catalytic activity. In E. coli Fe-containing SOD (FeSOD), reduction of Fe3+ is accompanied by protonation of a coordinated OH-, to produce Fe2+ coordinated by H2O. The coordinated solvent's only contact with the protein beyond the active site is a conserved Gln residue. Mutation of this Gln to His or Glu resulted in elevation of the Em by 220 mV and more than 660 mV, respectively [Yikilmaz et al., Biochemistry 2006, 45, 1151-1161], despite the fact that overall protein structure was preserved, His is a chemically conservative replacement for Gln, and neutral Glu is isostructural and isoelectronic with Gln. Therefore, we have investigated several possible bases for the elevated Em's, including altered Fe electronic structure, altered active site electrostatics, altered H-bonding and altered redox-coupled proton transfer. Using EPR, MCD, and NMR spectroscopies, we find that the active site electronic structures of the two mutants resemble that of the WT enzyme, for both oxidation states, and Q69E-FeSOD's apparent deviation from WT-like Fe3+ coordination in the oxidized state can be explained by increased affinity for a small anion. Spontaneous coordination of an exogenous anion can only stabilize oxidized Q69E-Fe3+SOD and, therefore, cannot account for the increased Em of Q69E FeSOD. WT-like anion binding affinities and active site pK's indicate that His69 of Q69H-FeSOD is neutral in both oxidation states, like Gln69 of WT-FeSOD, whereas Glu69 appears to be neutral in the oxidized state but ionized in the reduced state of Q69E-FeSOD. A 1.1 A resolution crystal structure of Q69E-Fe2+SOD indicates that Glu69 accepts a strong H-bond from coordinated solvent in the reduced state, in contrast to the case in WT-FeSOD where Gln69 donates an H-bond. These data and DFT calculations lead to the proposal that the elevated Em of Q69E-FeSOD can be substantially explained by (1) relief from enforced H-bond donation in the reduced state, (2) Glu69's capacity to provide a proton for proton-coupled Fe3+ reduction, and (3) strong hydrogen bond acceptance in the reduced state, which stabilizes coordinated H2O. Our results thus support the hypothesis that the protein matrix can apply significant redox tuning via its influence over redox-coupled proton transfer and the energy associated with it. 相似文献
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174.
Yavuz Kysal amil Ik Emine DogÜda Birsen Tozkoparan Mevlüt Ertan 《Acta Crystallographica. Section C, Structural Chemistry》2004,60(5):o356-o357
The title compound, C25H17F2N3OS, was synthesized from 6‐(benzylidene)thiazolo[3,2‐b][1,2,4]triazol‐5(6H)‐one. The fused thiazolo[3,2‐b][1,2,4]triazole system is essentially planar, and bifurcated C—H⋯O, C—H⋯N and C—H⋯F interactions are present between molecules. 相似文献
175.
We theoretically investigate the electronic properties of p-type δ-doped GaAs inserted into a quantum well under the electric field, at T = 0 K. We will investigate the influence of the electric field on the δ-doping concentration for a uniform distribution. The depth of confining potential, the density profile, the Fermi level, the subband energies and the subband populations calculate by solving the Schrodinger and Poisson equations self consistently. It is found that the changes of the electronic properties are quite sensitive to the applied electric field and the doping concentration. As different from single n-type δ-doped structure, we see a replace between the ground light-hole (lh1 ) subband and the first excited heavy-hole (hh2) subband whenever the external electric field reaches a critical value. We find the abrupt changing of the subband energies and the subband populations whenever the applied electric field reaches a certain value. Also, it is found that the heavy-hole subbands contain many more energy states than the light-hole ones, the population of the heavy-hole levels represent approximately 91% of all the carriers. 相似文献
176.
We have developed a novel approach to obtain high metal sorption capacity utilizing a membrane containing chitosan and an immobilized reactive dye (i.e. Reactive Yellow-2). The composite membrane was characterized by SEM, FT-IR, swelling test, and elemental analysis. The membrane has uniform small pores distribution and the pore dimensions are between 5 and 10 μm, and the HEMA:chitosan ratio was 50:1. The reactive dye immobilized composite membrane was used in the removal of heavy metal ions [i.e., Pb(II), Hg(II) and Cd(II)] from aqueous medium containing different amounts of these ions (5-600 mg l−1) and at different pH values (2.0-7.0). The maximum adsorption capacities of heavy metal ions onto the composite membrane under non-competitive conditions were 64.3 mmol m−2 for Pb(II), 52.7 mmol m−2 for Hg(II), 39.6 mmol m−2 for Cd(II) and the affinity order was Pb(II) > Hg(II)>Cd(II). 相似文献