van Wonderen, Jessica H;
Morales-Florez, Alejandro;
Clarke, Thomas A;
Gates, Andrew J;
Blumberger, Jochen;
Futera, Zdenek;
Richardson, David J;
... Moore, Geoffrey R; + view all
(2024)
Do multiheme cytochromes containing close-packed heme groups have a band structure formed from the heme π and π* orbitals?
Current Opinion in Electrochemistry
, 47
, Article 101556. 10.1016/j.coelec.2024.101556.
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Abstract
Multiheme cytochromes (MHCs) are bacterial electron-transfer proteins. We show from optical spectra and calculations that some of these cytochromes probably contain occupied and unoccupied bands formed from heme π and π∗ orbitals that span the protein. In the fully oxidised proteins, the unoccupied π∗-bands are energetically above the redox-active frontier orbitals, which according to NMR data and calculations, are formed of Fe3+ t2g and porphyrin π-orbitals. These orbitals on different hemes are electronically coupled according to EPR data and calculations, but only weakly so. We suggest a role for the heme bands in the electronic conductivity of single MHCs in bioelectronic junctions that is distinct from the role of the redox-active Fe3+ t2g and porphyrin π-orbitals in physiological electron transfer.
| Type: | Article |
|---|---|
| Title: | Do multiheme cytochromes containing close-packed heme groups have a band structure formed from the heme π and π* orbitals? |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1016/j.coelec.2024.101556 |
| Publisher version: | http://dx.doi.org/10.1016/j.coelec.2024.101556 |
| Language: | English |
| Additional information: | © 2024 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/) |
| Keywords: | Cytochromes, Heme, Molecular orbitals, Band structure, Spectroscopy, Electron transfer, Electronic conductivity, Bioelectronics |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Physics and Astronomy |
| URI: | https://discovery-pp.ucl.ac.uk/id/eprint/10195462 |
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