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The pK a values of the imidazole ligands bound to FePP was found to be 9.0 and 10.8 for the Fe3+ species and 13.0 and 14.1 for the Fe2+ form; the ionization properties of the heme bound 4MeImH ligand are most likely very similar to those of ImH.32,55.
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The reduction of the 5c MP8 species was direct when a gold electrode coated with PATS-3 was used
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Re-oxidation was accelerated using TMPD as a redox mediator
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The sample transmission is very low in this region, which is the transmission limit of the detector, and water absorbs strongly. While it is possible to detect absorption bands in concentrated samples, the noise level is too high in the FTIR difference spectra
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The sample transmission is very low in this region, which is the transmission limit of the detector, and water absorbs strongly. While it is possible to detect absorption bands in concentrated samples, the noise level is too high in the FTIR difference spectra.
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An assignment corresponding to a major ν (Fe-N4(Pyr, stretching in the normal mode can be excluded. The frequencies of the 412(+)/394- 398(, cm-1 bands do not match with the lengths of the Fe-N(pyrrole) bonds that are longer in planar ferrohemes than in ruffled ferrihemes. The frequency of a ν (Fe-N4Pyr, mode would be higher for the ferric species than for the ferrous species. We propose a folding or tilting mode of the pyrroles, but we cannot exclude a minor contribution of the Fe-N coordinates
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An assignment corresponding to a major ν (Fe-N4(Pyr)) stretching in the normal mode can be excluded. The frequencies of the 412(+)/394- 398(-) cm-1 bands do not match with the lengths of the Fe-N(pyrrole) bonds that are longer in planar ferrohemes than in ruffled ferrihemes. The frequency of a ν (Fe-N4(Pyr)) mode would be higher for the ferric species than for the ferrous species. We propose a folding or tilting mode of the pyrroles, but we cannot exclude a minor contribution of the Fe-N coordinates.
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