Theoretical aspects of several successive two-step redox mechanisms in protein-film cyclic staircase voltammetry

Gulaboski, Rubin; Kokoškarova, Pavlinka; Mitrev, Saša

doi:10.1016/j.electacta.2012.02.086

Cited by 44 publications

(48 citation statements)

References 36 publications

(121 reference statements)

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“…A plethora of intriguing studies has been conducted in relation to the kinetics of charge transfer processes at liquid/liquid interfaces [18][19][20][21][22][23], electrochemistry of immobilized proteins [24,25], and catalytic mechanisms [26][27][28], revealing that SWV is highly suited for both mechanistic and kinetic characterization of electrode reactions, besides its excellent analytical performances [29][30][31][32][33][34] and its appropriateness for bioanalytical applications [35][36][37][38][39][40][41].…”

Section: Introductionmentioning

confidence: 99%

Measuring the Electrode Kinetics of Surface Confined Electrode Reactions at a Constant Scan Rate

2014

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The kinetics of surface confined electrode reactions of alizarin, vitamin B12, and vitamin K2 is measured with square‐wave voltammetry over a wide pH interval, by applying the recent methodology for kinetic analysis at a constant scan rate [V. Mirceski, D. Guziejewski, K. Lisichkov, Electrochim. Acta 2013, 114, 667–673]. The reliability and the simplicity of the recent methodology is confirmed. The methodology requires analysis of the peak potential separation of the forward and backward component of the response as a function of the pulse height (SW amplitude), for a given frequency (i.e. constant scan rate) of the potential modulation.

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Section: Introductionmentioning

confidence: 99%

Measuring the Electrode Kinetics of Surface Confined Electrode Reactions at a Constant Scan Rate

2014

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“…A lot of theoretical features of the EC (electrochemicalchemical), CE (chemical-electrochemical), ECE (electrochemicalchemical-electrochemical), EC' (electrochemical-catalytic) systems under voltammetric conditions at various electrodes are appropriately elaborated in several excellent books [1][2][3][4][5][6], theoretical studies and reviews [7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26]. The so-called electrocatalytic regenerative mechanism (often referred to as EC' or ECat mechanism) is one of the most intriguing from a theoretical point of view, since it differs in many aspects from the other three mechanisms (EC, CE, and ECE) [1,[5][6][7][8]11,13,16,[18][19][20][21][22][23][24][25][26]. The EC' electrode mechanism comprises regeneration of the initial electroactive species involved in the electrode reaction via homogeneous redox reaction of the electrochemically generated product with other redox species present in the electrolyte solution.…”

Section: Introductionmentioning

confidence: 99%

New aspects of the electrochemical-catalytic (EC’) mechanism in square-wave voltammetry

Gulaboski

Mirčeski

2015

Electrochimica Acta

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Keywords:EC' catalytic mechanism electrode reaction kinetics standard rate constant enzymatic biosensors protein-film voltammetry A B S T R A C T Several new theoretical aspects of the electrocatalytic (regenerative) EC' mechanism under conditions of square-wave (SWV) and staircase cyclic voltammetry (SCV) are presented. Elaborating the effect of the rate of the catalytic reaction in the diffusion-controlled catalytic mechanism (diffusional EC' mechanism) and surface catalytic mechanism (surface EC' mechanism), we refer to several phenomena related to the shift of the position and the half-peak width of the net peak in square-wave voltammetry (SWV). If the rate of the catalytic reaction is much higher than the kinetics of the electrode reaction, a linear dependence between the peak potential of the simulated net SWV peaks and the logarithm of the catalytic parameter can be observed. The intercept of that linear dependence is a function of the kinetics of the electrode reaction. Based on this finding, we propose a new methodology to determine the electrode kinetics rate constant. The proposed approach relies on the variation of the concentration of the regenerative reagent. To the best of our knowledge, this is one of very few voltammetric approaches for electrode kinetic measurements not based on the time or potential variation in the experimental analyzes. In addition, we present a brief analysis of the catalytic mechanism under conditions of staircase cyclic voltammetry in order to emphasize the main differences between SCV and SWV.

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“…In the last few years, several groups worked on the development of mathematical models of coupled redox reactions under conditions of cyclic and square-wave voltammetry. The theoretical results relevant to the voltammetric behavior of the so-called EE (electrochemical-electrochemical), ECE (electrochemical-chemical-electrochemical), and EECat (electrochemical-electrochemical-catalytic) redox mechanisms under conditions of cyclic staircase voltammetry are comprehensively elaborated in the recent work of Gulaboski et al [55]. Moreover, the voltammetric features of EEcat [56], CE (chemical-electrochemical) [57], ECE [58], and EC [54] redox mechanisms have also been studied under conditions of square-wave voltammetry by Gulaboski et al Mirceski et al [59][60][61], Lovric and Komorsky-Lovric et al [62][63][64][65][66][67][68][69][70][71], and Molina et al [72][73][74][75][76] also made several great contributions towards theoretical understanding of the complex voltammetric behavior of coenzyme Qs under various conditions.…”

Section: Theoretical Studies Relevant To the Coenzyme Q's Redox Chemimentioning

confidence: 99%

Redox chemistry of coenzyme Q—a short overview of the voltammetric features

Gulaboski

Markovski

Zhu

2016

J Solid State Electrochem

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Quinones constitute a big family of organic redox active compounds that are overwhelmingly involved in important physiological processes. The most important members in the class of quinones are, indeed, the plastoquinones and the coenzyme Q (CoQ) derivatives. Voltammetry of coenzyme Q family members attracts significant attention since 50 years ago. In this work, we refer to some of the most important voltammetric features of coenzyme Qs studied in aprotic and in aqueous media. While the redox chemistry of coenzyme Q members in non-aqueous aprotic organic solvents can be described by two consecutive one-electron transfer steps, more complex situation exists in the voltammetry of coenzyme Qs performed in aqueous media. Although it has been claimed for a while that the voltammetric processes of coenzyme Qs in aqueous solutions proceed via formation of semiquinone radical intermediate species, it has been recently proven that this can be not completely true. Intensive voltammetric and spectroscopic studies of coenzyme Q systems in buffered and non-buffered aqueous media revealed that hydrogen bonding between electrochemically created CoQ species and the water molecules plays an important role in stabilizing electrochemically generated species of these systems. We also pay attention to the amazing redox chemistry of coenzyme Qs in strong alkaline media, while we refer to the chemical features of novel coenzyme Q derivatives obtained under such conditions. Hints are presented about the antioxidant capacity of some of the novel hydroxylated coenzyme Q systems. Also, the possibility of these systems to bind and transfer earth-alkaline cations across biomimetic membranes is shortly elaborated. In the end, we refer to some relevant theoretical works that describe closely the voltammetric behavior of various coenzyme Q systems. We believe that this short review will contribute towards better understanding of the amazing chemistry of coenzyme Q derivatives.

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Theoretical aspects of several successive two-step redox mechanisms in protein-film cyclic staircase voltammetry

Cited by 44 publications

References 36 publications

Measuring the Electrode Kinetics of Surface Confined Electrode Reactions at a Constant Scan Rate

Measuring the Electrode Kinetics of Surface Confined Electrode Reactions at a Constant Scan Rate

New aspects of the electrochemical-catalytic (EC’) mechanism in square-wave voltammetry

Redox chemistry of coenzyme Q—a short overview of the voltammetric features

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