Cyclic voltammetry, square wave voltammetry or electrochemical impedance spectroscopy? Interrogating electrochemical approaches for the determination of electron transfer rates of immobilized redox proteins
In this article, we cross-examine three well-established electrochemical approaches, namely cyclic voltammetry (CV), cyclic square-wave voltammetry (SWV) and electrochemical impedance spectroscopy (EIS) to dissect the electron transfer (ET) rate of electrostatically immobilized cytochrome c on Ag el...
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| Format: | Article |
| Language: | English |
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Elsevier
2023-01-01
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| Series: | BBA Advances |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S2667160323000248 |
| _version_ | 1827596295330594816 |
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| author | F.H. Pilz P. Kielb |
| author_facet | F.H. Pilz P. Kielb |
| author_sort | F.H. Pilz |
| collection | DOAJ |
| description | In this article, we cross-examine three well-established electrochemical approaches, namely cyclic voltammetry (CV), cyclic square-wave voltammetry (SWV) and electrochemical impedance spectroscopy (EIS) to dissect the electron transfer (ET) rate of electrostatically immobilized cytochrome c on Ag electrodes. A detailed analysis supported by simulations of redox transition provided three distinct values for the heterogeneous electron transfer (HET) rate constant of cyt c interfaced on COOH-terminated C10-long alkanethiol, i.e., kHET= 47.8 (±2,91) s−1 in CV, kHET= 64.8 (±1,27) s−1 in SWV, and kHET= 26.5 s−1 in EIS. We discuss the obtained discrepancies obtained from electrochemical methods and compare them with the data from spectro-electrochemical experiments. A comprehensive selection list is created from which the most applicable approach can be chosen for studying proteins of interest. CV is most applicable to study the interfaced proteins exhibiting kHET of ca. 0.5 - 70 s−1, SWV is suitable for a broader range of kHET of 5 – 120 s−1 and EIS for kHET of 0.5 to 5 s−1 if alkanethiols are used as immobilization strategy. |
| first_indexed | 2024-03-09T03:08:34Z |
| format | Article |
| id | doaj.art-f6f01d50513341198dfb183037c6400e |
| institution | Directory Open Access Journal |
| issn | 2667-1603 |
| language | English |
| last_indexed | 2024-03-09T03:08:34Z |
| publishDate | 2023-01-01 |
| publisher | Elsevier |
| record_format | Article |
| series | BBA Advances |
| spelling | doaj.art-f6f01d50513341198dfb183037c6400e2023-12-04T05:24:55ZengElsevierBBA Advances2667-16032023-01-014100095Cyclic voltammetry, square wave voltammetry or electrochemical impedance spectroscopy? Interrogating electrochemical approaches for the determination of electron transfer rates of immobilized redox proteinsF.H. Pilz0P. Kielb1Transdisciplinary Research Area ‘Building Blocks of Matter and Fundamental Interactions (TRA Matter)’, University of Bonn, Bonn, Germany; Clausius Institute of Physical and Theoretical Chemistry, University of Bonn, Wegelerstr. 12, Bonn 53115, GermanyTransdisciplinary Research Area ‘Building Blocks of Matter and Fundamental Interactions (TRA Matter)’, University of Bonn, Bonn, Germany; Clausius Institute of Physical and Theoretical Chemistry, University of Bonn, Wegelerstr. 12, Bonn 53115, Germany; Corresponding author at: Transdisciplinary Research Area ‘Building Blocks of Matter and Fundamental Interactions (TRA Matter)’, University of Bonn, Bonn, Germany.In this article, we cross-examine three well-established electrochemical approaches, namely cyclic voltammetry (CV), cyclic square-wave voltammetry (SWV) and electrochemical impedance spectroscopy (EIS) to dissect the electron transfer (ET) rate of electrostatically immobilized cytochrome c on Ag electrodes. A detailed analysis supported by simulations of redox transition provided three distinct values for the heterogeneous electron transfer (HET) rate constant of cyt c interfaced on COOH-terminated C10-long alkanethiol, i.e., kHET= 47.8 (±2,91) s−1 in CV, kHET= 64.8 (±1,27) s−1 in SWV, and kHET= 26.5 s−1 in EIS. We discuss the obtained discrepancies obtained from electrochemical methods and compare them with the data from spectro-electrochemical experiments. A comprehensive selection list is created from which the most applicable approach can be chosen for studying proteins of interest. CV is most applicable to study the interfaced proteins exhibiting kHET of ca. 0.5 - 70 s−1, SWV is suitable for a broader range of kHET of 5 – 120 s−1 and EIS for kHET of 0.5 to 5 s−1 if alkanethiols are used as immobilization strategy.http://www.sciencedirect.com/science/article/pii/S2667160323000248BioelectrochemistryElectron transferRedox proteinCyclic voltammetrySquare-wave voltammetryElectrochemical impedance spectroscopy |
| spellingShingle | F.H. Pilz P. Kielb Cyclic voltammetry, square wave voltammetry or electrochemical impedance spectroscopy? Interrogating electrochemical approaches for the determination of electron transfer rates of immobilized redox proteins BBA Advances Bioelectrochemistry Electron transfer Redox protein Cyclic voltammetry Square-wave voltammetry Electrochemical impedance spectroscopy |
| title | Cyclic voltammetry, square wave voltammetry or electrochemical impedance spectroscopy? Interrogating electrochemical approaches for the determination of electron transfer rates of immobilized redox proteins |
| title_full | Cyclic voltammetry, square wave voltammetry or electrochemical impedance spectroscopy? Interrogating electrochemical approaches for the determination of electron transfer rates of immobilized redox proteins |
| title_fullStr | Cyclic voltammetry, square wave voltammetry or electrochemical impedance spectroscopy? Interrogating electrochemical approaches for the determination of electron transfer rates of immobilized redox proteins |
| title_full_unstemmed | Cyclic voltammetry, square wave voltammetry or electrochemical impedance spectroscopy? Interrogating electrochemical approaches for the determination of electron transfer rates of immobilized redox proteins |
| title_short | Cyclic voltammetry, square wave voltammetry or electrochemical impedance spectroscopy? Interrogating electrochemical approaches for the determination of electron transfer rates of immobilized redox proteins |
| title_sort | cyclic voltammetry square wave voltammetry or electrochemical impedance spectroscopy interrogating electrochemical approaches for the determination of electron transfer rates of immobilized redox proteins |
| topic | Bioelectrochemistry Electron transfer Redox protein Cyclic voltammetry Square-wave voltammetry Electrochemical impedance spectroscopy |
| url | http://www.sciencedirect.com/science/article/pii/S2667160323000248 |
| work_keys_str_mv | AT fhpilz cyclicvoltammetrysquarewavevoltammetryorelectrochemicalimpedancespectroscopyinterrogatingelectrochemicalapproachesforthedeterminationofelectrontransferratesofimmobilizedredoxproteins AT pkielb cyclicvoltammetrysquarewavevoltammetryorelectrochemicalimpedancespectroscopyinterrogatingelectrochemicalapproachesforthedeterminationofelectrontransferratesofimmobilizedredoxproteins |