Electrochemical Characterization of Biomolecular Electron Transfer at Conductive Polymer Interfaces
Name
Agee_2023_J._Electrochem._Soc._170_016509.pdf
Description
Published version
Size
774.04 KB
Format
Adobe PDF
Checksum (MD5)
497921f86c2124dba1f465a82a10eead
Author(s)
Agee, Alec
Gill, Thomas Mark
Pace, Gordon
Segalman, Rachel
Furst, Ariel
Date Issued
January 1, 2023
Journal
Journal of The Electrochemical Society
Publisher
The Electrochemical Society
Citation
Alec Agee et al 2023 J. Electrochem. Soc. 170 016509
Version
Final published version
Abstract
Bio-electrochemical systems (BESs) are promising for renewable energy generation but remain hindered by inefficient electron transfer at electrode surfaces. As the toolbox of bio-anode materials increases, rigorous electrochemical characterization of emerging materials is needed. Here, we holistically characterize the electrochemical interaction of flavin mononucleotide (FMN), an electron shuttle in biological systems and a cofactor for oxidoreductase enzymes, with the bio-inspired mixed conducting polymer poly{3-[6'-(N-methylimidazolium)hexyl]thiophene} (P3HT-Im+). The behavior of this polymer is compared to the equivalent polymer without the histidine-like imidazolium. We find improved conductivity and charge storage in imidazolium-containing polymers beyond what is explained by differences in the electroactive area. The P3HT-Im+ further shows internal charge storage but with negligible faradaic contribution, indicating that charge storage capacity may translate to improved biocatalysis non-intuitive ways. Finally, one-electron transfer is observed between FMN and glassy carbon, while a bio-similar two-electron transfer is observed for the P3HT-Im+. To our knowledge, this is the first example of a concerted two-electron transfer between FMN and an electrode interface, which we attribute to the bio-inspired, histidine-like imidazolium functional groups in the polymer. These studies demonstrate the importance of bio-relevant materials characterization when such materials are deployed in BESs.
MIT Department
Massachusetts Institute of Technology. Department of Chemical Engineering
Terms of Use
Creative Commons Attribution-NonCommercial-NoDerivatives
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DOI of Published Version
https://doi.org/10.1149/1945-7111/acb239
