Abstract
Horse heart cytochrome c (cyt c) was chemically modified with poly(ethylene oxide) (PEO) to dissolve it in room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([emim][TFSI]). The redox response of the modified cyt c, hereafter PEO–cyt c, was analyzed in [emim][TFSI]. PEO modification to the surface of cyt c, which exceeded 60% of the total mass of the PEO–cyt c, was an effective method to solubilize the cyt c. In spite of the high ion density and sufficient ionic conductivity of [emim][TFSI], no redox response of pure PEO–cyt c was detected. However, a reversible redox response of PEO–cyt c was observed after adding a simple electrolyte such as KCl to [emim][TFSI]. The redox response of PEO–cyt c was sensitive to the anion radius of the added salt, and the chloride anion was found to be the best anion species to produce a redox response of PEO–cyt c in [emim][TFSI]. However, above a certain salt concentration, the resulting increase in solution viscosity would suppress the redox reaction. The results strongly indicate that the chloride anions, because of their mobility in the polypeptide matrix, compensate the charge change of heme during the electron transfer reaction. Larger anions did not show such an effect due to sterical restrictions on the migration through the protein shell to the heme pocket of cyt c.
Published Version
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