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. 2023 Feb 20;23(4):2348.
doi: 10.3390/s23042348.

Voltammetric Sensor Based on the Poly(p-aminobenzoic Acid) for the Simultaneous Quantification of Aromatic Aldehydes as Markers of Cognac and Brandy Quality

Guzel Ziyatdinova  1 , Tatyana Antonova  1 , Rustam Davletshin  2
Affiliations

Voltammetric Sensor Based on the Poly(p-aminobenzoic Acid) for the Simultaneous Quantification of Aromatic Aldehydes as Markers of Cognac and Brandy Quality

Guzel Ziyatdinova et al. Sensors (Basel). .

Abstract

Cognac and brandy quality control is an actual topic in food analysis. Aromatic aldehydes, particularly syringaldehyde and vanillin, are one of the markers used for these purposes. Therefore, simple and express methods for their simultaneous determination are required. The voltammetric sensor based on the layer-by-layer combination of multi-walled carbon nanotubes (MWCNTs) and electropolymerized p-aminobenzoic acid (p-ABA) provides full resolution of the syringaldehyde and vanillin oxidation peaks. Optimized conditions of p-ABA electropolymerization (100 µM monomer in Britton-Robinson buffer pH 2.0, twenty cycles in the polarization window of -0.5 to 2.0 V with a potential scan rate of 100 mV·s-1) were found. The poly(p-ABA)-based electrode was characterized by scanning electron microscopy (SEM), cyclic voltammetry, and electrochemical impedance spectroscopy (EIS). Electrooxidation of syringaldehyde and vanillin is an irreversible two-electron diffusion-controlled process. In the differential pulse mode, the sensor allows quantification of aromatic aldehydes in the ranges of 0.075-7.5 and 7.5-100 µM for syringaldehyde and 0.50-7.5 and 7.5-100 µM for vanillin with the detection limits of 0.018 and 0.19 µM, respectively. The sensor was applied to cognac and brandy samples and compared to chromatography.

Keywords: aminobenzoic acid; carbon nanotubes; chemically modified electrodes; cognac and brandy; electropolymerization; food quality; syringaldehyde; vanillin; voltammetric sensors.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Baseline-corrected differential pulse voltammograms of 10 µM syringaldehyde, vanillin, and their mixture: (a) at the bare GCE; (b) at the MWCNTs/GCE. The supporting electrolyte is Britton–Robinson buffer pH 2.0. Pulse amplitude is 50 mV, pulse time is 50 ms, and potential scan rate is 10 mV·s−1.
Figure 2
Figure 2
Electropolymerization of 100 µM p-ABA at the MWCNTs/GCE in Britton–Robinson buffer pH 2.0: (a) First cycle of electropolymerization; (b) Twenty cycles of electropolymerization. The inset is the enlarged scale of voltammograms in the potential range of 0.1–1.2 V. Potential scan rate is 100 mV·s−1.
Scheme 1
Scheme 1
Electropolymerization of p-ABA in acidic medium.
Figure 3
Figure 3
Changes in the oxidation currents of 10 µM mixture of syringaldehyde and vanillin at the polymer-modified electrode depending on the: (a) number of cycles at υ = 100 mV·s−1; (b) number of cycles at υ = 150 mV·s−1; (c) supporting electrolyte pH; (d) monomer concentration; (e) polarization window used for the poly(p-ABA) layer electrodeposition. The response of aromatic aldehydes is recorded in Britton–Robinson buffer pH 2.0 using cyclic voltammetry at a potential scan rate of 100 mV·s−1.
Figure 4
Figure 4
SEM images of: (a) bare GCE; (b) MWCNTs/GCE; (c) Poly(p-ABA)/MWCNTs/GCE.
Figure 5
Figure 5
(a) Cyclic voltammograms of 1.0 mM ferrocyanide ions in 0.1 M KCl at the bare GCE, MWCNTs/GCE, and poly(p-ABA)/MWCNTs/GCE. The potential scan rate is 100 mV·s−1; (b) Nyquist plot (experimental (points) and fitted (lines)) for bare GCE, MWCNTs/GCE, and poly(p-ABA)/MWCNTs/GCE in the presence of 1.0 mM mixture of ferro-/ferricyanide ions in 0.1 M KCl. Polarization potential is 0.21 V, frequency range is 10 kHz—0.04 Hz, amplitude is 5 mV.
Figure 6
Figure 6
Baseline-corrected differential pulse voltammograms of 10 µM mixture of syringaldehyde and vanillin at the MWCNTs/GCE and poly(p-ABA)/MWCNTs/GCE in Britton–Robinson buffer pH 2.0. Pulse amplitude is 50 mV, pulse time is 50 ms, and potential scan rate is 10 mV·s−1.
Figure 7
Figure 7
Voltammetric characteristics of 100 µM aromatic aldehydes at the poly(p-ABA)-modified electrode depending on the Britton–Robinson buffer pH: (a) Oxidation potentials of syringaldehyde; (b) Oxidation currents of syringaldehyde; (c) Oxidation potentials of vanillin; (d) Oxidation currents of vanillin.
Figure 8
Figure 8
Cyclic voltammograms of aromatic aldehydes at the poly(p-ABA)-modified electrode in the Britton–Robinson buffer pH 2.0 at various potential scan rates: (a) 100 µM of syringaldehyde; (b) 100 µM of vanillin.
Scheme 2
Scheme 2
Electrooxidation of aromatic aldehydes.
Figure 9
Figure 9
Baseline-corrected differential pulse voltammograms of the aromatic aldehydes equimolar mixtures of various concentrations at the poly(p-ABA)-modified electrode in the Britton–Robinson buffer pH 2.0: (a) concentration range of 0.075–7.5 µM; (b) concentration range of 7.5–100 µM. Pulse amplitude is 50 mV, pulse time is 25 ms, potential scan rate is 10 mV·s−1.
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