The role of 3,4-dihydroxyphenylacetic acid adsorption in the oxidation of homovanillic acid at a glassy carbon rotating disc electrode

Rene Pfeifer, Priscila Tamiasso Martinhon, Celia Sousa, Josino Costa Moreira, Marco Antonio Chaer Nascimento, Jiří Barek, Vlastimil Vyskočil

Research output: Contribution to journalArticle

Abstract

Homovanillic acid (HVA) is an important biomarker for neurological disorders. Traditional methods for detection of this compound are chromatographic methods coupled with fluorescence, mass spectrometric, or electrochemical detectors. However, voltammetric methods can be useful because of their low cost, easy automation, portability, and sensitivity. 3,4-Dihydroxyphenylacetic acid (DOPAC) is formed during electrochemical oxidation of HVA. The formation of this compound could interfere with the quantification of HVA using electrochemical methods. This work aims at describing the behavior of the intermediate species generated in the oxidation of HVA using cyclic voltammetry (CV), linear staircase voltammetry (LSV), and electrochemical impedance spectroscopy (EIS) with a glassy carbon rotating disc electrode (GC RDE). The importance and desirability of detailed investigation of surface phenomena connected with electrochemical oxidation used for electroanalytical purposes are thus clearly demonstrated. The EIS measurements indicate that the intermediate DOPAC formed by the oxidation of HVA can adsorb on the surface of a glassy carbon electrode (GCE). For the static GCE, a semi-finite linear diffusion was observed and for the GC RDE, a finite-length diffusion was verified. In the case of the semi-finite linear diffusion, EIS measurements revealed that the resistance to charge transfer decreases from 100 to 50 Ω, and the capacitance of the double layer increases from 1.44 to 1.66 μF with increasing concentration of HVA. However, LSV results showed that Levich equations for electrochemical reduction of K 3 [Fe(CN) 6 ] probe in basic medium are i lim = −0.157 ω 1/2 − 0.006 (R 2 = 0.9999) in the absence of HVA (i.e. without DOPAC adsorption at GCE) and i lim = −0.154 ω 1/2 − 0.021 (R 2 = 0.9998) in the presence of HVA (i.e. with DOPAC adsorption at GCE). The small difference in these two equations proves a negligible influence of DOPAC adsorption on the quantification of HVA using stationary methods.

Original languageEnglish
Pages (from-to)129-135
Number of pages7
JournalJournal of Electroanalytical Chemistry
Volume838
DOIs
Publication statusPublished - 1 Apr 2019
Externally publishedYes

Fingerprint

3,4-Dihydroxyphenylacetic Acid
Homovanillic Acid
Glassy carbon
Rotating disks
Adsorption
Oxidation
Electrodes
Acids
Electrochemical impedance spectroscopy
Electrochemical oxidation
Voltammetry
Surface phenomena
Biomarkers
Cyclic voltammetry
Charge transfer
Capacitance
Automation
Fluorescence
Detectors

Keywords

  • 3,4-Dihydroxyphenylacetic acid
  • Electrochemical impedance spectroscopy
  • Homovanillic acid
  • Rotating disc electrode
  • Voltammetry

ASJC Scopus subject areas

  • Analytical Chemistry
  • Chemical Engineering(all)
  • Electrochemistry

Cite this

The role of 3,4-dihydroxyphenylacetic acid adsorption in the oxidation of homovanillic acid at a glassy carbon rotating disc electrode. / Pfeifer, Rene; Tamiasso Martinhon, Priscila; Sousa, Celia; Moreira, Josino Costa; Nascimento, Marco Antonio Chaer; Barek, Jiří; Vyskočil, Vlastimil.

In: Journal of Electroanalytical Chemistry, Vol. 838, 01.04.2019, p. 129-135.

Research output: Contribution to journalArticle

Pfeifer, Rene ; Tamiasso Martinhon, Priscila ; Sousa, Celia ; Moreira, Josino Costa ; Nascimento, Marco Antonio Chaer ; Barek, Jiří ; Vyskočil, Vlastimil. / The role of 3,4-dihydroxyphenylacetic acid adsorption in the oxidation of homovanillic acid at a glassy carbon rotating disc electrode. In: Journal of Electroanalytical Chemistry. 2019 ; Vol. 838. pp. 129-135.
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abstract = "Homovanillic acid (HVA) is an important biomarker for neurological disorders. Traditional methods for detection of this compound are chromatographic methods coupled with fluorescence, mass spectrometric, or electrochemical detectors. However, voltammetric methods can be useful because of their low cost, easy automation, portability, and sensitivity. 3,4-Dihydroxyphenylacetic acid (DOPAC) is formed during electrochemical oxidation of HVA. The formation of this compound could interfere with the quantification of HVA using electrochemical methods. This work aims at describing the behavior of the intermediate species generated in the oxidation of HVA using cyclic voltammetry (CV), linear staircase voltammetry (LSV), and electrochemical impedance spectroscopy (EIS) with a glassy carbon rotating disc electrode (GC RDE). The importance and desirability of detailed investigation of surface phenomena connected with electrochemical oxidation used for electroanalytical purposes are thus clearly demonstrated. The EIS measurements indicate that the intermediate DOPAC formed by the oxidation of HVA can adsorb on the surface of a glassy carbon electrode (GCE). For the static GCE, a semi-finite linear diffusion was observed and for the GC RDE, a finite-length diffusion was verified. In the case of the semi-finite linear diffusion, EIS measurements revealed that the resistance to charge transfer decreases from 100 to 50 Ω, and the capacitance of the double layer increases from 1.44 to 1.66 μF with increasing concentration of HVA. However, LSV results showed that Levich equations for electrochemical reduction of K 3 [Fe(CN) 6 ] probe in basic medium are i lim = −0.157 ω 1/2 − 0.006 (R 2 = 0.9999) in the absence of HVA (i.e. without DOPAC adsorption at GCE) and i lim = −0.154 ω 1/2 − 0.021 (R 2 = 0.9998) in the presence of HVA (i.e. with DOPAC adsorption at GCE). The small difference in these two equations proves a negligible influence of DOPAC adsorption on the quantification of HVA using stationary methods.",
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AU - Moreira, Josino Costa

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