Long-Range Electron Transport Rates Depend on Wire Dimensions in Cytochrome Nanowires

The ability to redirect electron transport to new reactions in living systems opens possibilities to store energy, generate new products, or probe physiological processes. Recent work by Huang et al. showed that 3D crystals of small tetraheme cytochromes (STC) can transport electrons over nanoscopic to mesoscopic distances by an electron hopping mechanism, making them promising materials for nanowires. However, fluctuations at room temperature may distort the nanostructure, hindering efficient electron transport. Classical molecular dynamics simulations of these fluctuations at the nano- and mesoscopic scales allowed us to develop a graph network representation to estimate maximum electron flow that can be driven through STC wires. In longer nanowires, transient structural fluctuations at protein-protein interfaces tended to obstruct efficient electron transfer, but these blockages are ameliorated in thicker crystals where alternative electron transfer pathways become more efficient. The model implies that more flexible proteinprotein interfaces limit the required minimum diameter to carry currents commensurate with conventional electronics. A close-up view of a small tetraheme cytochrome nanocrystal with heavy atoms represented as spheres. Thermal motions within the chain are sampled with molecular dynamics simulations to estimate heme-to-heme (glowing orange) electron transfer rates, finding that thermal motion induced electron transport bottlenecks limit the current, most apparent in longer and thinner protein nanowires.image