Surface catalytic mechanism-theoretical study under conditions of differential square-wave voltammetry




differential square-wave voltammetry, surface catalytic mechanism, enzyme-substrate interactions, quasireversible maximum, protein-film voltammetry


Differential square-wave voltammetry (DSWV) is the most recent modification of square-wave voltammetry (SWV) developed for advancing the performances of the technique for both analytical and kinetics applications. The differential current-measuring protocol in DSWV leads to improved voltammetric features of the forward and backward current components, in particular when slow i.e., quasireversible or irreversible electrode reactions are studied. In the present theoretical work catalytic electrode mechanism of surface bounded redox species (surface EC’ mechanism) is studied under conditions of the new technique, where E denotes the electrode reaction and C’ refers to the irreversible follow-up regenerative chemical reaction. Presented theoretical data provides a general overview of the EC’ reaction scheme, implying some specific voltammetric features which can be exploited for estimation of relevant physical parameters of the electrode reaction E and the regenerative chemical reaction C’.

Author Biography

Rubin Gulaboski, Faculty of Medical Sciences, Goce Delcev University, Stip

Department of Physical Chemistry and Bioelectrochemistry


Electrochemical methods. Fundamentals and applica-tions, 3rd edition.; Faulkner, A. J., John, L. R., Bard, Wiley & Sons, Inc. 2004.

Electrifying metalloenzymes in: Metalloproteins: Theo-ry, calculations and experiments; Armstrong, F. A., (Cho, A. E., Goddar, W.A eds.), CRC Press, Tay-lor&Francis Group, London, New York, 2015

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

Leger, C.; Bertrand, P. Direct electrochemistry of re-dox enzymes as a tool for mechanistic studies, Chem. Rev., 2008, 108, 2379.


Gulaboski, R.; Mirceski, V. Application of voltamme-try in biomedicine-recent achievements in enzymatic voltammetry, Maced. J. Chem. Chem. Eng. 2020, 39, 153. DOI:

Armstrong, F. A..; Heering, H. A.; Hirst, J., Reactions of complex metalloproteins studied by protein-film voltammetry, Chem. Soc. Rev., 1997, 26, 169.

Voltammetry of proteins, In: Encyclopedia of electro-chemistry; Armstrong, F. A. (Bard, A. J.; Stratmann, M.; Wilson G. S. eds.), vol. 9, Wiley VCH, Weinheim, 2002.

Pulse voltammetry in physical electrochemistry and electroanalysis, in Monographs in electrochemistry; Molina, A.; Gonzales, J., (Scholz, F. ed.), Berlin Hei-delberg, Springer, 2016.

Understanding voltammetry, 2nd ed.; Compton, R. G.; Banks, C. E., Imperial College Press, London, UK, 2011.

Elements of molecular and biomolecular electrochem-istry: An electrochemical approach to electron trans-fer chemistry, Saveant, J. M., John Wiley & Sons, 2006. DOI:

Square-Wave Voltammetry, Electroanalytical chemis-try: a series of advances, Osteryoung, J. G.; O'Dea, J. J. Marcel Dekker, Inc: New York,1986.

Square-wave voltammetry: Theory and application, Mirceski, V.; Komorsky-Lovric, S.; Lovric, M., (Scholz F. ed.) Springer, Berlin, 2007.

Gulaboski, R.; Mirceski, V.; Lovric, M. Square-wave protein-film voltammetry: new insights in the enzy-matic electrode processes coupled with chemical reac-tions, J. Solid State Electrochem. 2019, 23, 2493.


Gulaboski, R.; Mirceski, V. New aspects of the elec-trochemical-catalytic (EC’) mechanism in square-wave voltammetry, Electrochim. Acta, 2015, 167, 219. doi: DOI:

Mirceski, V.; Guziejewski, D.; Stojanov, L.; Gula-boski, R. Differential square-wave voltammetry, Anal. Chem., 2019, 91, 14904.


Mirceski, V.; Gulaboski, R. Surface catalytic mecha-nism in square-wave voltammetry. Electroanalysis, 2001, 13, 1326.

Mirceski, V.; Stojanov, L.; Gulaboski, R. Double-sampled differential square-wave voltammetry. J. Electroanal. Chem. 2020, 872, 114384. DOI:

Mirceski, V.; Lovric, M. Split square-wave voltammo-grams of surface redox reactions. Electroanalysis, 1997, 9, 1283.


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How to Cite

Gulaboski, R., & Mirceski, V. (2022). Surface catalytic mechanism-theoretical study under conditions of differential square-wave voltammetry. Macedonian Journal of Chemistry and Chemical Engineering, 41(1).