Do multiheme cytochromes containing close-packed heme groups have a band structure formed from the heme π and π* orbitals?

van Wonderen, Jessica H., Morales-Florez, Alejandro, Clarke, Thomas A. ORCID: https://orcid.org/0000-0002-6234-1914, Gates, Andrew J. ORCID: https://orcid.org/0000-0002-4594-5038, Blumberger, Jochen, Futera, Zdenek, Richardson, David J. ORCID: https://orcid.org/0000-0002-6847-1832, Butt, Julea N. ORCID: https://orcid.org/0000-0002-9624-5226 and Moore, Geoffrey R. (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. ISSN 2451-9103

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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.

Item Type:	Article
Additional Information:	Data availability statement: Data will be made available on request. Funding information: UK Biotechnology and Biological Sciences Research Council for financial support through the grant BB/X011453/1 and doctoral training partnership BB/T008717/1. Computational resources were supplied by the project “e-Infrastruktura CZ” (e-INFRA LM2018140) provided within the program Projects of Large Research, Development and Innovations Infrastructures.
Faculty \ School:	Faculty of Science > School of Biological Sciences Faculty of Science Faculty of Science > School of Chemistry
UEA Research Groups:	Faculty of Science > Research Groups > Molecular Microbiology Faculty of Science > Research Centres > Centre for Molecular and Structural Biochemistry Faculty of Science > Research Groups > Centre for Photonics and Quantum Science Faculty of Science > Research Groups > Energy Materials Laboratory Faculty of Science > Research Groups > Chemistry of Light and Energy Faculty of Science > Research Groups > Chemistry of Life Processes
Depositing User:	LivePure Connector
Date Deposited:	11 Jun 2024 08:30
Last Modified:	19 Jun 2024 08:30
URI:	https://ueaeprints.uea.ac.uk/id/eprint/95535
DOI:	10.1016/j.coelec.2024.101556

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