Irreversible inactivation of initial redox form in surface electrode mechanism: Theoretical aspects in square-wave voltammetry
DOI:
https://doi.org/10.20450/mjcce.2025.3129Keywords:
surface electrode mechanism, metal surfaces, protein-film voltammetry, square-wave voltammetryAbstract
Various redox species frequently undergo irreversible inactivation under specific chemical conditions. This study explores square-wave voltammetry to examine the electrochemical behavior of lipophilic redox systems classified within the family of surface electrode mechanisms. The theoretical analysis considers an initial redox form that simultaneously undergoes an electrochemical transformation and an irreversible chemical inactivation reaction. The study presents a detailed tabulation of distinctive voltammetric patterns, assisting readers to accurately identify this electrode mechanism and distinguish it from the film loss in the square-wave voltammetry of surface-confined redox systems. The extensive collection of simulated voltammograms in this work offers insight into establishing diagnostic criteria for recognizing this mechanism. Additionally, several suitable approaches for determining the kinetics of the dual processes involved in the electrochemical mechanism are proposed. These findings are expected to help experimentalists studying metal and alloy inactivation, as well as protein-film voltammetry (PFV), to accurately characterize the considered electrode mechanism. Given the unique features of this mechanism, experimental protocols should incorporate the use of a flow-through electrochemical cell for voltammetric measurements.
References
(1) El Harrad, L., Bourais, I., Mohammadi, H., Amine, A., Recent advances in electrochemical biosensors based on enzyme inhibition for clinical and pharmaceutical applications, Sensors 2018, 18, 164.
doi:10.3390/s18010164
(2) Leger, C., Bertrand, P., Direct electrochemistry of redox enzymes as a tool for mechanistic studies, Chem. Rev. 2008, 108, 2379–2438.
https://doi.org/10.1021/cr0680742
(3) Armstrong, F. A., Electrifying metalloenzymes. In: Cho, A. E., Goddard III, W. A., Eds.; Metalloproteins: Theory, Calculations and Experiments, CRC Press, Taylor & Francis Group, London, New York, 2015.
(4) Armstrong, F. A., Applications of voltammetric meth-ods for probing the chemistry of redox proteins. In: Lenaz, G., Milazz, G., Eds., Bioelectrochemistry: Principles and Practice, Birkhäuser Verlag AG, Basel, 1997.
(5) Jenner, L. P., Butt, J. N., Electrochemistry of surface-confined enzymes: Inspiration, insight, and opportuni-ty for sustainable biotechnology, Curr. Opin. Electro-chem. 2018, 8, 81–88.
https://doi.org/10.1016/j.coelec.2018.03.021
(6) Kano, K., Biosci. Biotechnol. Biochem. 2022, 86, 141-156. https://doi.org/10.1093/bbb/zbab197
(7) Fourmond, V., Leger, C., An introduction to electro-chemical methods for the functional analysis of metal-loproteins, in: Crichton, R. R., Louro, R. O., Eds.; Practical Approaches to Biological Inorganic Chemis-try, Elsevier, 2020, pp. 325.
(8) Gulaboski, R., Mirceski, V., Bogeski, I., Hoth, M., Protein film voltammetry-electrochemical enzymatic spectroscopy. A review on recent progress. J. Solid State Electrochem. 2012, 16, 2315–2328.
https://doi.org/10.1007/s10008-011-1397-5
(9) Hirst, J., Direct measurement by protein-film voltam-metry, Biochim. Biophys. Acta Bioenerg. 2006, 1757, 225–239. https://doi.org/10.1016/j.bbabio.2006.04.002.
(10) Gulaboski, R., Kokoskarova, P., Mitrev, S., Theoreti-cal aspects of several successive two-step redox mechanisms in protein-film cyclic staircase voltamme-try, Electrochim. Acta 2012, 69, 86–96.
DOI: 10.1016/j.electacta.2012.02.086
(11) Lopez-Tenes, M., Gonzalez, J., Molina, A., Two elec-tron transfer reactions in electrochemistry for solution-soluble and surface-confined molecules: A common approach, J. Phys. Chem. C 2014, 118, 12312–12324. DOI:10.1021/jp5025763
(12) Zhang, H. N., Guo, Z. Y., Gai, P. P., Research progress in protein film voltammetry, Chin. J. Anal. Chem. 2009, 37, 461–465.
https://doi.org/10.1016/S1872-2040(08)60093-6
(13) Gonzalez, J., Lopez-Tenes, M., Molina, A., Voltam-metry of electrochemically reversible systems at elec-trodes at any geometry: A general, explicit, analytical characterization, J. Phys. Chem. C 2013, 117, 5208–5220. https://doi.org/10.1021/jp109587b
(14) Mann, M. A., Bottomley, L. A., Cyclic square-wave voltammetry of surface-confined quasireversible elec-tron transfer reactions, Langmuir 2015, 31, 9511–9520. https://doi.org/10.1021/acs.langmuir.5b01684
(15) Stevenson, G. P.; Lee, C.-Y.; Kennedy, G. F.; Parkin, A.; Baker, R. E.; Gillow, K.; Armstrong, F. A.; Ga-vaghan, D. J.; Bond, A. M., Theoretical analysis of the two-electron transfer reaction and experimental studies with surface-confined cytochrome c peroxidase using large-amplitude Fourier transformed AC voltammetry. Langmuir 2012, 28, 9864– 9877.
DOI: 10.1021/la205037e
(16) Fourmond, V., Wiedner, E. S., Shaw, W. J., Léger, C., Understanding and design of bidirectional and reversi-ble catalysts of multielectron, multistep reactions, J. Am. Chem. Soc. 2019, 141, 11269–11285.
https://doi.org/10.1021/jacs.9b04854
(17) Gonzalez, J., Sequí, J.-A., Analysis of the electro-chemical response of surface-confined bidirectional molecular electrocatalysts in the presence of intermo-lecular interactions, ChemCatChem. 2021, 13, 747–762.
https://doi.org/10.1002/cctc.202001599
(18) Mirceski, V., Guziejewski, D., Gulaboski, R. Differen-tial square-wave voltammetry, Anal. Chem. 2019, 91, 14904–14910. DOI: 10.1021/acs.analchem.9b03035
(19) Léger, C., Elliott, S. J., Hoke, K. R., Jeuken, L. J. C., Jones, A. K., Armstrong, F. A., Enzyme electrokinet-ics: using protein film voltammetry to investigate re-dox enzymes and their mechanisms, Biochemistry 2003, 42, 8653–8662. https://doi.org/10.1021/bi034789c
(20) Gulaboski, R., Mirceski, V., Lovric, M., Critical as-pects in exploring time analysis for the voltammetric estimation of kinetic parameters of surface electrode mechanisms coupled with chemical reactions, Maced. J. Chem. Chem. Eng. 2021, 40, 1–9.
https://doi.org/10.20450/mjcce.2021.2270
(21) Janeva, M., Kokoskarova, P., Maksimova, V., Gula-boski, R., Square-wave voltammetry of two-step sur-face electrode mechanisms coupled with chemical re-actions – A theoretical overview, Electroanalysis 2019, 31, 2488–2506. https://doi.org/10.1002/elan.201900416
(22) Gulaboski, R., Mirceski, V., Application of voltamme-try in biomedicine – Recent achievements in enzymat-ic voltammetry. Maced. J. Chem. Chem. Eng. 2020, 39, 153–166. https://doi.org/10.20450/mjcce.2020.2152
(23) Del Barrio, M., Fourmond, V., Redox (in)activation of metalloenzymes: A protein film voltammetry ap-proach, ChemElectroChem. 2019, 6, 4949–4962.
https://doi.org/10.1002/celc.201901028
(24) Olmstead, M. L., Hamilton, R. G., Nicholson, R. S., Theory of cyclic voltammetry for a dimerization reac-tion initiated electrochemically, Anal. Chem. 1969, 41, 260–267. https://doi.org/10.1021/ac60271a032
(25) Molina, A., González, J., Pulse Voltammetry in Physi-cal Electrochemistry and Electroanalysis. In: Scholz, F., Ed., Monographs in Electrochemistry, Springer, Berlin Heidelberg, 2016.
(26) Mirceski, V., Komorsky-Lovric, S., Lovric, M., Square-Wave Voltammetry: Theory and Application. Scholz, F., Ed., Springer, Berlin, Heidelberg, 2007.
(27) Gulaboski, R., Mirceski, V., New aspects of electro-chemical-catalytic (EC’) mechanism in square-wave voltammetry, Electrochim. Acta 2015, 167, 219–225. https://doi.org/10.1016/j.electacta.2015.03.175
(28) Mirceski, V., Gulaboski, R., Surface catalytic mecha-nism in square-wave voltammetry, Electroanalysis 2001, 13, 1326–1334. https://doi.org/10.1002/1521-4109(200111)13:16<1326::AID-ELAN1326>3.0.CO;2-S
(29) Waskasi, M. M., Martin, D. R., Matyushov, D. V., Wetting of the protein active site leads to non-Marcusian reaction kinetics, J. Phys. Chem. B 2018, 122, 10490-10495. DOI: 10.1021/acs.jpcb.8b10376
(30) Mirčeski, V., Lovrić, M., Split square-wave voltam-mograms of surface redox reactions, Electroanalysis 1997, 9, 1283–1287. https://doi.org/10.1002/elan.1140091613
(31) Blumberger, J., Recent advances in theory and molec-ular simulation of biological electron transfer reac-tions, Chem. Rev. 2015, 115, 11191–11238.
https://doi.org/10.1021/acs.chemrev.5b00298
(32) Gulaboski, R., Mirčeski, V., Lovrić, M., Bogeski, I., Theoretical study of a surface electrode reaction pre-ceded by a homogeneous chemical reaction under conditions of square-wave voltammetry, Electrochem. Commun. 2005, 7, 515-522.
https://doi.org/10.1016/j.elecom.2005.03.009
(33) Mirčeski, V., Lovrić, M., Gulaboski, R., Theoretical and experimental study of the surface redox reaction involving interactions between the adsorbed particles under conditions of square-wave voltammetry, J. Electroanal. Chem. 2001, 515, 91–100.
(34) Gulaboski, R., Theoretical contribution towards under-standing specific behavior of “simple” protein-film re-actions in square-wave voltammetry, Electroanalysis 2019, 31, 545–553. DOI:10.1002/elan.201800739
(35) Gulaboski, R., Janeva, M., Maksimova, V., New as-pects of protein-film voltammetry of redox enzymes coupled to follow up reversible chemical reaction in square-wave voltammetry, Electroanalysis 2019, 31, 946–956. https://doi.org/10.1002/elan.201900028
(36) Gulaboski, R., Distinction between film loss and enzyme inactivation in protein film voltammetry: a theoretical study in cyclic staircase voltammetry, Monatsh. Chem. 2023, 154, 141–149. DOI: 10.1007/s00706-022-02999-5
(37) Guziejewski, D., Mirceski, V., Jadresko, D., Measur-ing the electrode kinetics of surface confined elec-trode reactions at constant scan rate, Electroanalysis 2015, 27, 67–73. https://doi.org/10.1002/elan.201400349
(38) Jadreško, D., Guziejewski, D., Mirčeski, V., Electro-chemical Faradaic spectroscopy, ChemElectroChem. 2018, 5, 187–194.
https://doi.org/10.1002/celc.201700784
(39) Mirceski, V., Laborda, E., Guziejewski, D.; Compton, R. G. New approach to electrode kinetic measure-ments in square-wave voltammetry: Amplitude-based quasireversible maximum, Anal. Chem. 2013, 85, 5586–5594. https://doi.org/10.1021/ac4008573
(40) Gulaboski, R., Lovrić, M., Mirceski, V., Bogeski, I. Hoth, M., A new rapid and simple method to deter-mine the kinetics of electrode reactions of biologically relevant compounds from the half-peak width of the square-wave voltammograms, Biophys. Chem. 2008, 138, 130–137. http://hdl.handle.net/20.500.12188/13892
(41) Rial-Rodriguez, E., Williams, J. D., Eggenweiler, H-M., Fuchss, T., Sommer, A., Kappe, C. O., Cantillo, D., Development of an open-source flow-through cy-clic voltammetry cell for real-time inline reaction ana-lytics, Reac. Chem. Eng. 2024, 9, 26–30.
https://doi.org/10.1039/D3RE00535F
(42) Gunasingham, H.; Fleet, B., Hydrodynamic voltamme-try in continuous-flow analysis. In: Electroanalytical Chemistry: A series of advances, Vol. 16, Marcel Dekker, New York, 1990, pp. 89–180.
(43) Butt, J. N., Jeuken, L. J. C., Zhang, C., Burton, J. A. J., Sutton-Cook, A. L., Protein film electrochemistry, Nat. Rev. Methods Primers, 2023, 3.
Downloads
Additional Files
Published
Versions
- 2025-06-29 (3)
- 2025-06-24 (2)
- 2025-06-22 (1)
How to Cite
Issue
Section
License
Copyright (c) 2025 Rubin Gulaboski, pavle Apostoloski
This work is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License.
