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. 2022 Sep 6;12(39):25342-25353.
doi: 10.1039/d2ra04045j. eCollection 2022 Sep 5.

Differential pulse voltammetry and chronoamperometry as analytical tools for epinephrine detection using a tyrosinase-based electrochemical biosensor

Sylwia Baluta  1 , Francesca Meloni  2 , Kinga Halicka  1 , Adam Szyszka  3 , Antonio Zucca  2 , Maria Itria Pilo  2 , Joanna Cabaj  1
Affiliations

Differential pulse voltammetry and chronoamperometry as analytical tools for epinephrine detection using a tyrosinase-based electrochemical biosensor

Sylwia Baluta et al. RSC Adv. .

Abstract

The main goal of the presented study was to design a biosensor-based system for epinephrine (EP) detection using a poly-thiophene derivative and tyrosinase as a biorecognition element. We compared two different electroanalytical techniques to select the most prominent technique for analyzing the neurotransmitter. The prepared biosensor system exhibited good parameters; the differential pulse (DPV) technique presented a wide linear range (1-20 μM and 30-200 μM), with a low detection limit (0.18 nM and 1.03 nM). In the case of chronoamperometry (CA), a high signal-to-noise ratio and lower reproducibility were observed, causing a less broad linear range (10-200 μM) and a higher detection limit (125 nM). Therefore, the DPV technique was used for the calculation of sensitivity (0.0011 μA mM-1 cm-2), stability (49 days), and total surface coverage (4.18 × 10-12 mol cm-2). The biosensor also showed very high selectivity in the presence of common interfering species (i.e. ascorbic acid, uric acid, norepinephrine, dopamine) and was successfully applied for EP determination in a pharmaceutical sample.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Fig. 1
Fig. 1. Chemical structure of 4,4′-bis(2-methyl-3-butyn-2-ol)-2,2′-bithiophene.
Fig. 2
Fig. 2. Scheme of the bioplatform for epinephrine determination – glassy carbon electrode modified with poly-4,4′-bBT and tyrosinase.
Fig. 3
Fig. 3. (A) Representative AFM topography maps and surface 3D views of electrode surfaces modified with poly-4,4′-bis(2-methyl-3-butyn-2-ol)-2,2′-bithiophene and (B) poly-4,4′-bis(2-methyl-3-butyn-2-ol)-2,2′-bithiophene with tyrosinase; 5 × 5 μm.
Fig. 4
Fig. 4. Redox reaction of EP catalyzed by tyrosinase.
Fig. 5
Fig. 5. Representative CV scans of the bare GC electrode (blue line), GCE modified with poly-4,4′-bBT (red line), and GCE/poly-4,4′-bBT/Tyr (black line) in the presence of 200 μM EP, and GCE/poly-4,4′-bBT/Tyr (green line) in the absence of the analyte; applied potential range −0.2–0.8 V, scan rate 50 mV s−1, vs. Ag/AgCl.
Fig. 6
Fig. 6. DPV-scans for different concentrations of EP in a range of 1–200 μM.
Fig. 7
Fig. 7. Relationship between EP concentration and current (biosensor response): (A) – in a low concentration range (1–20 μM), (B) – in a high concentration range (30–200 μM), (C) – in a full concentration range (1–200 μM).
Fig. 8
Fig. 8. Current/time response of different concentrations of EP in the range of 10–200 μM.
Fig. 9
Fig. 9. Linear relationship of current and EP concentration (10–200 μM).
Fig. 10
Fig. 10. Reproducibility of the biosensor.
Fig. 11
Fig. 11. The effect of interfering substances (in excess) on epinephrine (EP) determination; DA – dopamine, NE – norepinephrine, UA – uric acid, AA – ascorbic acid.
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