Multiheme cytochromes (MHCs) are the building blocks of highly conductive micrometre-long supramolecular wires found in so-called electrical bacteria. Recent studies have revealed that these proteins possess a long supramolecular array of closely packed heme cofactors along the main molecular axis alternating between perpendicular and stacking configurations (TST = T-shaped, stacked, T-shaped). While TST arrays have been identified as the likely electron conduit, the mechanisms of outstanding long-range charge transport observed in these structures remain unknown. Here we study charge transport on individual small tetraheme cytochromes (STCs) containing a single TST heme array. Individual STCs are trapped in a controllable nanoscale tunnelling gap. By modulating the tunnelling gap separation, we are able to selectively probe four different electron pathways involving 1, 2, 3 and 4 heme cofactors, respectively, leading to the determination of the electron tunnelling decay constant along the TST heme motif. Conductance calculations of selected single-STC junctions are in excellent agreement with experiments and suggest a mechanism of electron tunnelling with shallow length decay constant through an individual STC. These results demonstrate that an individual TST motif supporting electron tunnelling might contribute to a tunnelling-assisted charge transport diffusion mechanism in larger TST associations.

Departament de Ciència de Materials i Química Física Universitat de Barcelona Institut de Química Teòrica i Computacional Marti i Franquès 1 08028 Barcelona Spain

Department of Chemistry Faculty of Natural Mathematical and Engineering Sciences King's College London Britannia House 7 Trinity Street London SE1 1DB UK

Department of Physics and Astronomy Thomas Young Centre University College London Gower Street London WC1E 6BT UK

Faculty of Science University of South Bohemia Branisovska 1760 370 05 Ceske Budejovice Czech Republic

School of Chemistry School of Biological Sciences University of East Anglia Norwich Research Park Norwich NR4 7TJ UK

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