The role of intramolecular interactions in the functional control of multiheme cytochromes c

► In this paper we review the detailed redox characterization of multiheme cytochromes. ► Close proximity between the hemes allow redox interactions to modulate the potentials in a significant way. ► The interplay between intrinsic potentials and interactions establishes selection of specific populations. ► Interactions between hemes play a key role in establishing the biological function.