The net peak splitting phenomenon in square-wave voltammetry – A simple diagnostic tool to distinguish between surface electrode mechanisms associated with different chemical reactions

Authors

DOI:

https://doi.org/10.20450/mjcce.2023.2782

Keywords:

surface CE mechanism, surface EC mechanism;, surface EC’ regenerative mechanism;, split square-wave voltammograms;

Abstract

Utilizing pulse voltammetric techniques for the electrochemical analysis of lipophilic redox systems has proven to be an effective method for studying a diverse range of redox compounds, from simple molecules to intricate proteins. To extract relevant thermodynamic and kinetic data from electrochemical analysis of redox systems exhibiting strong surface activity, there's a crucial need to decipher the underlying electrochemical mechanism in the system being examined. The "split net peak" phenomenon, a defining characteristic observed in all surface-active redox systems featuring fast electron transfer under square-wave voltammetry conditions, has been investigated in this study to establish diagnostic criteria for identifying surface electrochemical mechanisms associated with preceding, subsequent, regenerative, and reactant-inactivating chemical reactions. This understanding can be achieved by tracking the influence of the chemical reaction rate on the split square-wave voltammetric peaks in a particular electrochemical mechanism. The approach reported in the current work enables a very simple and precise differentiation between the elaborated mechanisms frequently encountered in protein-film voltammetry methodologies.

Author Biography

Rubin Gulaboski, Faculty of Medical Sciences, Goce Delčev University, Štip, Macedonia

Department of Physical Chemistry and Bioelectrochemistry

References

(1) Mirceski, V.; Komorsky-Lovric, S.; Lovric, M., Square-wave Voltammetry: Theory and Application; (Scholz, F. ed.), Springer, Berlin, Heidelberg, 2007.

(2) Molina, A.; Gonzales, J., Pulse voltammetry in physical electrochemistry and electroanalysis. In: Monographs in electrochemistry; (Scholz, F., ed.), Springer, Berlin Heidelberg, 2016.

(3) O’Dea, J. J.; Osteryoung J.; Osteryoung, R. A., Theory of square-wave voltammetry for kinetic systems. Anal. Chem. 1981, 53 (4), 695–701.

(4) A. J., Faulkner; L. R., White; H. S., Wiley, Electro-chemical Methods: Fundamentals and Applications, 3rd ed.; Bard, 2022.

(5) Armstrong F. A, Applications of voltammetric methods for probing the chemistry of redox proteins. In: Bioelectrochemistry: Principles and Practice;. (Lenaz, G., Milazz, G. eds), Birkhauser Verlag AG, Basel, 1997.

(6) Leger, C.; Bertrand, P., Direct electrochemistry of redox enzymes as a tool for mechanistic studies. Chem. Rev. 2008, 108 (7) 2379–2438. DOI: 10.1021/cr0680742

(7) Arsmstrong, F. A., Electrifying metalloenzymes. In: Metalloproteins: Theory, Calculations and Experiments; (Cho, A. E.; Goddar, III W. A., eds), CRC Press, Taylor & Francis Group, London, New York, 2015.

(8) Hirst, J., Elucidating the mechanisms of coupled electron transfer. Biochim. Biophys. Acta Bioenerg. 2006, 1757 (4), 225–239.

https://doi.org/10.1016/j.bbabio.2006.04.002

(9) Mirceski, V.; Gulaboski, R., Surface catalytic mechanism in square-wave voltammetry. Electroanalysis, 2001, 13 (16), 1326–1334. https://doi.org/10.1002/1521-4109(200111)13:16<1326::AID-ELAN1326>3.0.CO;2-S

(10) Gulaboski, R.; Mirceski, V.; Lovric, M.; Bogeski, I., Theoretical study of a surface electrode reaction preceded by a homogeneous chemical reaction under conditions of square-wave voltammetry. Electrochem. Commun. 2005, 7 (5), 515–522. DOI: 10.1016/j.elecom.2005.03.009

(11) Gulaboski, R., Theoretical contribution towards under-standing specific behaviour of "simple" protein-film reac-tions in square-wave voltammetry. Electroanalysis 2019, 31 (3), 545–553.

https://doi.org/10.1002/elan.201800739

(12) Gulaboski, R.; Janeva, M.; Maksimova, V., New aspects of protein-film voltammetry of redox enzymes coupled to follow up chemical reaction in square-wave voltammetry, Electroanalysis. 2019, 31 (5), 946–956.

https://doi.org/10.1002/elan.201900028

(13) Gulaboski, R.; Mirceski, V.; Lovric, M. Square-wave protein-film voltammetry: new insights in the enzymatic electrode processes coupled with chemical reactions, J. Solid State Electrochem. 2019, 23 (8), 2493–2506. https://doi.org/10.1007/s10008-019-04320-7

(14) Mirceski, V.; Lovric, M., Split square-wave voltammo-grams of surface redox reactions, Electroanalysis, 1997, 9 (16), 1283–1287.

https://doi.org/10.1002/elan.1140091613

(15) Gulaboski, R.; Mirceski, V., New aspects of the electro-chemical-catalytic (EC’) mechanism in square-wave volt-ammetry. Electrochim. Acta, 2015, 167, 219–225. https://doi.org/10.1016/j.electacta.2015.03.175

(16) Gulaboski, R., Distinction between film loss and enzyme inactivation in protein-film voltammetry: A theoretical study in cyclic square-wave voltammetry. Monatsh. Chem. 2023, 254, 141–149.

DOI: 10.1007/s00706-022-02999-5

(17) Jenner, L. P.; Butt J. N., Electrochemistry of surface-confined enzymes: Inspiration, insight and opportunity for sustainable biotechnology. Curr. Opin. Electrochem. 2018, 8, 81-88.

https://doi.org/10.1016/j.coelec.2018.03.021

(18) Stevenson, G. P.; Lee, C-Y.; Kennedy, G. F.; Parkin, A.; Baker, R. E.; Gillow, K.; Armstrong, F. A.; Gavaghan, D. J.; Bond, A. M., Theoretical analysis of two-electron transfer reaction and experimental studies with surface-confined cytochrome c peroxidase using large-amplitude Fourier transformed AC voltammetry. Langmuir, 2012, 28 (25), 9864–9877.

https://doi.org/10.1021/la205037e

(19) Mann, M. A.; Bottomley, L. A., Cyclic square-wave volt-ammetry of surface-confined quasireversible electron transfer reactions. Langmuir 2015, 31 (34), 9511–9520. https://doi.org/10.1021/acs.langmuir.5b01684

(20) Zhang, H. N.; Guo, Z. Y.; Gai, P. P., Research progress in protein-film voltammetry. Chin. J. Anal. Chem. 2009, 37 (3), 461–465.

https://doi.org/10.1016/S1872-2040(08)60093-6

(21) Lisdat, F., Coupling biology to electrochemistry-future trends and needs, J. Solid State Electrochem. 2020, 24 (8), 2125–2127.

https://doi.org/10.1007/s10008-020-04714-y

(22) Bollella, P.; Gorton, L., Enzyme based amperometric bio-sensors. Curr. Opin. Electrochem. 2018, 10, 157–173. https://doi.org/10.1016/j.coelec.2018.06.003

(23) Gulaboski, R.; Mirceski, V., Application of voltammetry in biomedicine – Recent achievements in enzymatic volt-ammetry. Maced. J. Chem. Chem. Eng. 2020, 39 (2), 153–166. https://doi.org/10.20450/mjcce.2020.2152

(24) Gulaboski, R., The future of voltammetry. Maced. J. Chem. Chem. Eng. 2022, 41 (2), 151–162.

DOI: 10.20450/mjcce.2022.2555

Downloads

Published

2023-12-01 — Updated on 2023-12-24

Versions

How to Cite

Gulaboski, R. (2023). The net peak splitting phenomenon in square-wave voltammetry – A simple diagnostic tool to distinguish between surface electrode mechanisms associated with different chemical reactions. Macedonian Journal of Chemistry and Chemical Engineering, 42(2), 237–247. https://doi.org/10.20450/mjcce.2023.2782 (Original work published December 1, 2023)

Issue

Section

Electrochemistry

Most read articles by the same author(s)