Oral Presentation 21st International Conference on Biological Inorganic Chemistry 2025

Investigating Electron Conductivity Regimes within Cytochrome Polymers from First-Principles Modeling (122075)

Sahar Sharifzadeh 1
  1. Boston University, Boston, MA, United States

In natural systems, proteins act as an electron transfer medium, facilitating long-range electronic and energy transport as part of diverse biological processes such as respiration and photosynthesis. Understanding the underlying mechanisms for conductivity is necessary for the utilization and design of these materials for synthetic bioelectronic devices. One key challenge is understanding, under biologically relevant conditions, how molecular composition, morphology, and supramolecular structure affect the electronic properties of these materials. Here, we present theoretical studies of conductivity within the microbial cytochrome wires, metalloproteins which exhibit carrier conduction over microns. We introduce an approach to extract charge carrier site information directly from Kohn-Sham density functional theory (DFT), providing input to a quantum charge carrier model that includes both coherent charge transport and the impact of decoherence. We demonstrate that low-energy, high frequency, molecular fluctuations strongly impact electron carrier diffusion lengths by allowing the system to more easily overcome static site energy barriers, improving conductivity within certain parameter regimes. We then apply this model to three naturally occurring cytochrome polymers: OmcS, OmcE and OmcZ. The differences in conductivity regimes of all three systems will be discussed. Overall, these studies provide insights into molecular and electronic determinants of long-range electronic conductivity in microbial cytochrome wires and highlight design principles for bioinspired, heme-based conductive materials.