10.1021/jz200734a.s001 Carlo Augusto Bortolotti Carlo Augusto Bortolotti Magdalena E. Siwko Magdalena E. Siwko Elena Castellini Elena Castellini Antonio Ranieri Antonio Ranieri Marco Sola Marco Sola Stefano Corni Stefano Corni The Reorganization Energy in Cytochrome <i>c</i> is Controlled by the Accessibility of the Heme to the Solvent American Chemical Society 2015 kinetic reorganization energy λ electron transfer process cytochrome c variants reorganization energy energy transduction pathways 2015-12-16 19:31:18 Journal contribution https://acs.figshare.com/articles/journal_contribution/The_Reorganization_Energy_in_Cytochrome_i_c_i_is_Controlled_by_the_Accessibility_of_the_Heme_to_the_Solvent/2016420 Elucidation of the molecular determinants of the reorganization energy λ is central to the understanding of fundamental biological processes based on energy transduction pathways. Here, we use a combined experimental/theoretical approach to electrochemically determine the reorganization energy for a number of cytochrome <i>c</i> variants and compute structure-related properties relevant to the kinetics of the electron transfer process through molecular dynamics simulations. We find that the exposure of the heme group to solvent controls the reorganization energy of the investigated proteins. Therefore, fine-tuning of the kinetics of the electron transfer process can be achieved through modulation of the accessibility of the iron to the surrounding water. Our findings lead the way for a new strategy for the design of protein-based bioelectronic materials, requiring fast and efficient electron transfer.