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

Guziejewski, Dariusz; Mirčeski, Valentin; Jadreško, Dijana

doi:10.1002/elan.201400349

Cited by 31 publications

(40 citation statements)

References 65 publications

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“…While the experimental set‐up in PFV is quite simple to be designed, the results of theoretical models developed to study these systems under conditions of pulse voltammetric techniques are not always easy for interpretation. The theoretical models in protein‐film voltammetry give mainly mechanistic, thermodynamic and kinetic insights into the chemistry of considered redox enzymes . If a given enzyme is firmly adsorbed on a working electrode surface forming a monolayer of non‐interacting redox molecules, then its chemical features can be explored by developing theoretical models of so‐called “surface redox reactions” .…”

Section: Introductionmentioning

confidence: 99%

New Aspects of Protein‐film Voltammetry of Redox Enzymes Coupled to Follow‐up Reversible Chemical Reaction in Square‐wave Voltammetry

2019

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Protein‐film square‐wave voltammetry of uniformly adsorbed molecules of redox lipophilic enzymes is applied to study their electrochemical properties, when a reversible follow‐up chemical reaction is coupled to the electrochemically generated product of enzyme's electrode reaction. Theoretical consideration of this so‐called “surface ECrev mechanism” under conditions of square‐wave voltammetry has revealed several new aspects, especially by enzymatic electrode reactions featuring fast electron transfer. We show that the rate of chemical removal/resupply of electrochemically generated Red(ads) enzymatic species, shows quite specific features to all current components of calculated square‐wave voltammograms and affects the electrode kinetics. The effects observed are specific for this particular redox mechanism (surface ECrev mechanism), and they got more pronounced at high electrode kinetics of enzymatic reaction. The features of phenomena of “split net‐SWV peak” and “quasireversible maximum”, which are typical for surface redox reactions studied in square‐wave voltammetry, are strongly affected by kinetics and thermodynamics of follow‐up chemical reaction. While we present plenty of relevant voltammetric situations useful for recognizing this particular mechanism in square‐wave voltammetry, we also propose a new approach to get access to kinetics and thermodynamics of follow‐up chemical reaction. Most of the results in this work throw new insight into the features of protein‐film systems that are coupled with chemical reactions.

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Section: Introductionmentioning

confidence: 99%

New Aspects of Protein‐film Voltammetry of Redox Enzymes Coupled to Follow‐up Reversible Chemical Reaction in Square‐wave Voltammetry

2019

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“…At the same time the peak potential remains almost constant with negligible shift toward more negative values (9 mV in SWV). Following the foregoing basic voltammetric characterization of the electrode reaction, a detailed kinetic analysis has been performed by varying the SW amplitude (over the interval from 20 to 250 mV) and measuring the peak potential separation between the forward to backward SW voltammetric components [3, 35,36] and amplitude-based quasireversible maximum [2]. A careful inspection of the amplitude normalized net peak currents reveals the presence of an amplitude-based quasireversible maxima for the measurements conducted at 8, 25, 50 and 100 Hz (data not shown) implying that electrode reaction is kinetically controlled at all used frequencies [2].…”

Section: Experimental Datamentioning

confidence: 99%

“…k s, sur = 30 and 25 s À1 , the splitting is observed at sampling time of t s = 42 and 48 ms, respectively. Thus, an analogous methodology to the previously reported one [2,3,21,35,36] can be developed for kinetic and mechanistic characterization of the electrode reaction by recording a single experiment only. …”

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confidence: 99%

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Characterizing electrode reactions by multisampling the current in square-wave voltammetry

Mirčeski

Guziejewski

Bozem

et al. 2016

Electrochimica Acta

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A B S T R A C TA novel and simple methodology for characterization of electrode processes by square-wave voltammetry (SWV), considered as a complex repetitive double-step chronoamperometric experiment, is proposed. Specifically, the sampling of the current at the very end of each potential pulse, as common in conventional SWV, is replaced with a multisampling protocol during each potential pulse, resulting in generation of a series of corresponding multisampled SW voltammograms constructed out of a single measurement. The evolution of such voltammograms reflects the chronoamperometric properties of the current in the course of each potential pulse, thus being specific to electrode mechanism and electrode kinetics. The proposed methodology could serve as a basis for modification of common SWV mode in commercially available instrumentation for the purpose of an advanced characterization of electrode processes. The methodology is theoretically illustrated by the analysis of three kinetically controlled common electrode mechanisms, such as the electrode reaction of a solution resident and surface confined redox couples, as well as the regenerative catalytic electrode mechanism (EC'), while the experimental verification is done with the electrode reaction of Eu 3+ /Eu 2+ and azobenzene/ hydrazobenzene redox couples.

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“…Electrochemical assay often offers selectivity and sensitivity due to the selective detection of electroactive species among the complex samples. Among electrochemical methods voltammetry , especially square wave voltammetry (SWV) , is the one which offers broad mechanistic, kinetic and analytical studies. In the present work the quantitative determination of PFL is studied for the first time under SW conditions.…”

Section: Introductionmentioning

confidence: 99%

First Electroanalytical Studies of Profluralin with Square Wave Voltammetry Using Glassy Carbon Electrode

et al. 2016

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The electrochemical behaviour of profluralin (PFL) was investigated with square wave voltammetry (SWV) and cyclic voltammetry at bare and modified with graphene, graphene oxide, reduced graphene oxide, carbon nanotubes glassy carbon electrode. The influence of various factors such as pH, buffer composition, ionic surfactants and voltammetric parameters was studied. The best results in terms of signal shape and intensity were recorded in 0.04 M Britton‐Robinson buffer at pH 2.0 at −0.43 V versus Ag/AgCl. In acidic medium profluralin produces single cathodic signal of an irreversible nature. Observed peak (two superimposed signals from two nitro groups) is a result of PFL reduction controlled by diffusion processes. Linearity of peak currents (Ip) vs. concentrations of profluralin was found in the range of 1.0×10−7 to 1.0×10−6 M with a detection limit of 2.6×10−8 M using fast and sensitive SWV. The developed method has been applied for the quantitative analysis of profluralin in spiked environmental samples with very good average recoveries in the range from 98.6 to 99.9 % with a mean relative standard deviation of 4.0 %.

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

Cited by 31 publications

References 65 publications

New Aspects of Protein‐film Voltammetry of Redox Enzymes Coupled to Follow‐up Reversible Chemical Reaction in Square‐wave Voltammetry

New Aspects of Protein‐film Voltammetry of Redox Enzymes Coupled to Follow‐up Reversible Chemical Reaction in Square‐wave Voltammetry

Characterizing electrode reactions by multisampling the current in square-wave voltammetry

First Electroanalytical Studies of Profluralin with Square Wave Voltammetry Using Glassy Carbon Electrode

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