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Metalloprotein electron transfer reactions: Analysis of reactivity of horse heart cytochrome c with inorganic complexes

Wherland, Scot and Gray, Harry B. (1976) Metalloprotein electron transfer reactions: Analysis of reactivity of horse heart cytochrome c with inorganic complexes. Proceedings of the National Academy of Sciences of the United States of America, 73 (9). pp. 2950-2954. ISSN 0027-8424. http://resolver.caltech.edu/CaltechAUTHORS:WHEpnas76

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Abstract

The reactions of horse heart cytochrome c with Fe(ethylenediaminetetraacetate)2-, Co(1,10-phenanthroline)3{}3+, Ru(NH3)6{}2+, and Fe(CN)6{}3- have been analyzed within the formalism of the Marcus theory of outer-sphere electron transfer, including compensation for electrostatic interactions. Calculated protein self-exchange rate constants based on crossreactions are found to vary over three orders of magnitude, decreasing according to Fe(CN)6{}3- > Co(phen)3{}3+ > Ru(NH3)6{}2+ > Fe(EDTA)2-. The reactivity order suggests that the mechanism of electron transfer involves attack by the small molecule reagents near the most nearly exposed region of the heme; this attack is affected by electrostatic interactions with the positively charged protein, by hydrophobic interactions that permit reagent penetration of the protein surface, and by the availability of pi symmetry ligand (or extended metal) orbitals that can overlap with the pi redox orbitals of the heme group.


Item Type:Article
Additional Information:Copyright © 1976 by The National Academy of Sciences. Contributed by Harry B. Gray, June 1, 1976. This research was supported by the National Science Foundation. S.W. acknowledges a National Science Foundation Graduate Fellowship (1973-76). This is Contribution no. 5347 from the Arthur Amos Noyes Laboratory.
Record Number:CaltechAUTHORS:WHEpnas76
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:WHEpnas76
Alternative URL:http://www.pnas.org/cgi/content/abstract/73/9/2950
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:606
Collection:CaltechAUTHORS
Deposited By: Archive Administrator
Deposited On:01 Sep 2005
Last Modified:14 Nov 2014 19:18

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