Prospects of Application of Ultramicroelectrode Ensembles for Voltammetric Determination of Compounds with Close Standard Electrode Potentials and Different Diffusion Coefficients

Standard

Prospects of Application of Ultramicroelectrode Ensembles for Voltammetric Determination of Compounds with Close Standard Electrode Potentials and Different Diffusion Coefficients. / Arbenin, Andrey Yu; Petrov, Alexey A.; Nazarov, Denis V.; Serebryakov, Evgeny; Kirichenko, Sergey O.; Vlasov, Petr S.; Zemtsova, Elena G.; Smirnov, Vladimir M.; Danilova, Elena E.; Ermakov, Sergey S.; Vorobyov, Alexander; Mukhin, Mikhail S.; Mozharov, Alexey M.

In: Chemosensors, Vol. 10, No. 10, 433, 19.10.2022.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{4afabcdf9f7b4c35a82f3eb6924c31df,

title = "Prospects of Application of Ultramicroelectrode Ensembles for Voltammetric Determination of Compounds with Close Standard Electrode Potentials and Different Diffusion Coefficients",

abstract = "The spherical diffusion that occurs when using ultramicroelectrodes (i.e., electrodes with a characteristic size of 1–10 µm) contributes to a higher mass transfer rate. This leads to equalization of the depletion rates of the near-electrode layer due to the electrochemical reaction and to the supply of the product from the solution depth. This is the reason why, for ultramicroelectrodes, a limiting size of the spherical layer exists in which the concentration gradient is localized (diffusion layer). Thus, a stationary mass transfer mode is achieved, which is expressed in the sigmoidal CV curve{\textquoteright}s shape. In ultramicroelectrode arrays, when the diffusion hemispheres are separated, a steady-state diffusion is realized. However, with a decrease in the interelectrode distance, which leads to the diffusion spheres intersection, a mixed regime arises, which is not fully time-independent. The resulting voltammogram{\textquoteright}s shape change can serve as an analytical signal in the study of substances with differing diffusion coefficients, since the diffusion layer growth rate and, consequently, the area of intersection of neighboring spheres, depends on it. This work shows the applicability of voltammetry using ensembles of ultramicroelectrodes operating in the transient mode for the analysis of mixtures of electrochemically active compounds with close electrode reaction parameters, such as exchange currents and electrode potential. Ferrocenemethanol esters are used as an example. The applicability of cyclic voltammetry on the UME array for analysis of mixtures was illustrated by means of finite element modelling. The reliability of the modelling results was experimentally proved for ferrocenemethanol esters with glycine and triglycine.",

keywords = "diffusion mode, electrochemical sensors, peptide, peptide derivatization, ultramicroelectrode, ultramicroelectrode array, voltammetry",

author = "Arbenin, {Andrey Yu} and Petrov, {Alexey A.} and Nazarov, {Denis V.} and Evgeny Serebryakov and Kirichenko, {Sergey O.} and Vlasov, {Petr S.} and Zemtsova, {Elena G.} and Smirnov, {Vladimir M.} and Danilova, {Elena E.} and Ermakov, {Sergey S.} and Alexander Vorobyov and Mukhin, {Mikhail S.} and Mozharov, {Alexey M.}",

note = "Publisher Copyright: {\textcopyright} 2022 by the authors.",

year = "2022",

month = oct,

day = "19",

doi = "10.3390/chemosensors10100433",

language = "English",

volume = "10",

journal = "Chemosensors",

issn = "2227-9040",

publisher = "MDPI AG",

number = "10",

}

RIS

TY - JOUR

T1 - Prospects of Application of Ultramicroelectrode Ensembles for Voltammetric Determination of Compounds with Close Standard Electrode Potentials and Different Diffusion Coefficients

AU - Arbenin, Andrey Yu

AU - Petrov, Alexey A.

AU - Nazarov, Denis V.

AU - Serebryakov, Evgeny

AU - Kirichenko, Sergey O.

AU - Vlasov, Petr S.

AU - Zemtsova, Elena G.

AU - Smirnov, Vladimir M.

AU - Danilova, Elena E.

AU - Ermakov, Sergey S.

AU - Vorobyov, Alexander

AU - Mukhin, Mikhail S.

AU - Mozharov, Alexey M.

PY - 2022/10/19

Y1 - 2022/10/19

N2 - The spherical diffusion that occurs when using ultramicroelectrodes (i.e., electrodes with a characteristic size of 1–10 µm) contributes to a higher mass transfer rate. This leads to equalization of the depletion rates of the near-electrode layer due to the electrochemical reaction and to the supply of the product from the solution depth. This is the reason why, for ultramicroelectrodes, a limiting size of the spherical layer exists in which the concentration gradient is localized (diffusion layer). Thus, a stationary mass transfer mode is achieved, which is expressed in the sigmoidal CV curve’s shape. In ultramicroelectrode arrays, when the diffusion hemispheres are separated, a steady-state diffusion is realized. However, with a decrease in the interelectrode distance, which leads to the diffusion spheres intersection, a mixed regime arises, which is not fully time-independent. The resulting voltammogram’s shape change can serve as an analytical signal in the study of substances with differing diffusion coefficients, since the diffusion layer growth rate and, consequently, the area of intersection of neighboring spheres, depends on it. This work shows the applicability of voltammetry using ensembles of ultramicroelectrodes operating in the transient mode for the analysis of mixtures of electrochemically active compounds with close electrode reaction parameters, such as exchange currents and electrode potential. Ferrocenemethanol esters are used as an example. The applicability of cyclic voltammetry on the UME array for analysis of mixtures was illustrated by means of finite element modelling. The reliability of the modelling results was experimentally proved for ferrocenemethanol esters with glycine and triglycine.

AB - The spherical diffusion that occurs when using ultramicroelectrodes (i.e., electrodes with a characteristic size of 1–10 µm) contributes to a higher mass transfer rate. This leads to equalization of the depletion rates of the near-electrode layer due to the electrochemical reaction and to the supply of the product from the solution depth. This is the reason why, for ultramicroelectrodes, a limiting size of the spherical layer exists in which the concentration gradient is localized (diffusion layer). Thus, a stationary mass transfer mode is achieved, which is expressed in the sigmoidal CV curve’s shape. In ultramicroelectrode arrays, when the diffusion hemispheres are separated, a steady-state diffusion is realized. However, with a decrease in the interelectrode distance, which leads to the diffusion spheres intersection, a mixed regime arises, which is not fully time-independent. The resulting voltammogram’s shape change can serve as an analytical signal in the study of substances with differing diffusion coefficients, since the diffusion layer growth rate and, consequently, the area of intersection of neighboring spheres, depends on it. This work shows the applicability of voltammetry using ensembles of ultramicroelectrodes operating in the transient mode for the analysis of mixtures of electrochemically active compounds with close electrode reaction parameters, such as exchange currents and electrode potential. Ferrocenemethanol esters are used as an example. The applicability of cyclic voltammetry on the UME array for analysis of mixtures was illustrated by means of finite element modelling. The reliability of the modelling results was experimentally proved for ferrocenemethanol esters with glycine and triglycine.

KW - diffusion mode

KW - electrochemical sensors

KW - peptide

KW - peptide derivatization

KW - ultramicroelectrode

KW - ultramicroelectrode array

KW - voltammetry

UR - http://www.scopus.com/inward/record.url?scp=85140644974&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/799bb9ba-42ad-35e0-b04d-9aee2609152f/

U2 - 10.3390/chemosensors10100433

DO - 10.3390/chemosensors10100433

M3 - Article

AN - SCOPUS:85140644974

VL - 10

JO - Chemosensors

JF - Chemosensors

SN - 2227-9040

IS - 10

M1 - 433

ER -

ID: 100571358