Electrochemical Characterization of Biomolecular Electron Transfer at Conductive Polymer Interfaces
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 holistical...
| Main Authors: | , , , , |
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| Format: | Article |
| Language: | English |
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The Electrochemical Society
2025
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| Online Access: | https://hdl.handle.net/1721.1/158306 |
| _version_ | 1826204879802073088 |
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| author | Agee, Alec Gill, Thomas Mark Pace, Gordon Segalman, Rachel Furst, Ariel |
| author2 | Massachusetts Institute of Technology. Department of Chemical Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Chemical Engineering Agee, Alec Gill, Thomas Mark Pace, Gordon Segalman, Rachel Furst, Ariel |
| author_sort | Agee, Alec |
| collection | MIT |
| description | 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. |
| first_indexed | 2025-03-10T11:04:50Z |
| format | Article |
| id | mit-1721.1/158306 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2025-03-10T11:04:50Z |
| publishDate | 2025 |
| publisher | The Electrochemical Society |
| record_format | dspace |
| spelling | mit-1721.1/1583062025-03-04T21:51:22Z Electrochemical Characterization of Biomolecular Electron Transfer at Conductive Polymer Interfaces Agee, Alec Gill, Thomas Mark Pace, Gordon Segalman, Rachel Furst, Ariel Massachusetts Institute of Technology. Department of Chemical Engineering 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. 2025-03-04T21:51:21Z 2025-03-04T21:51:21Z 2023-01-01 2025-03-04T21:37:36Z Article http://purl.org/eprint/type/JournalArticle https://hdl.handle.net/1721.1/158306 Alec Agee et al 2023 J. Electrochem. Soc. 170 016509 en 10.1149/1945-7111/acb239 Journal of The Electrochemical Society Creative Commons Attribution-NonCommercial-NoDerivatives https://creativecommons.org/licenses/by-nc-nd/4.0/ application/pdf The Electrochemical Society The Electrochemical Society |
| spellingShingle | Agee, Alec Gill, Thomas Mark Pace, Gordon Segalman, Rachel Furst, Ariel Electrochemical Characterization of Biomolecular Electron Transfer at Conductive Polymer Interfaces |
| title | Electrochemical Characterization of Biomolecular Electron Transfer at Conductive Polymer Interfaces |
| title_full | Electrochemical Characterization of Biomolecular Electron Transfer at Conductive Polymer Interfaces |
| title_fullStr | Electrochemical Characterization of Biomolecular Electron Transfer at Conductive Polymer Interfaces |
| title_full_unstemmed | Electrochemical Characterization of Biomolecular Electron Transfer at Conductive Polymer Interfaces |
| title_short | Electrochemical Characterization of Biomolecular Electron Transfer at Conductive Polymer Interfaces |
| title_sort | electrochemical characterization of biomolecular electron transfer at conductive polymer interfaces |
| url | https://hdl.handle.net/1721.1/158306 |
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