Journal of Electrochemical Science and Technology

The Korean Electrochemical Society (한국전기화학회)
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Electrochemical Determination of Capsaicin by Ionic Liquid Composite-Modified Electrode

  • Received : 2018.11.04
  • Accepted : 2018.12.05
  • Published : 2019.06.30

Abstract

An electrochemical detection method for capsaicin has been developed using ionic liquid (IL) doped graphene-titania-Nafion composite-modified electrode. The combination of IL (1-hexyl-3-methylimidazolium with hexafluorophosphate counter ion) in the composite-modified electrode resulted in a significantly increased electrochemical response for capsaicin compared to that obtained at the corresponding electrode without IL. The increased electrochemical signal could be ascribed to the decreased electron transfer resistance through the composite film and also to the effective accumulation of capsaicin on the electrode surface due to ${\pi}-{\pi}$ interaction of the imidazole groups of IL with the aromatic rings of capsaicin. The present IL composite-modified electrode can detect capsaicin with a concentration range from $3.0{\times}10^{-8}M$ to $1.0{\times}10^{-5}M$ with a detection limit of $3.17{\times}10^{-9}M$ (S/N = 3). The present sensor showed good reproducibility (RSD = 3.2%).

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Fig. 1. Scanning electron microscopy image of the ionic liquid-graphene-titania-Nafion composite film. Scale bar: 500 nm.

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Fig. 2. Energy-dispersive X-ray spectroscopy mapping image of the ionic liquid-graphene-titania-Nafion composite. (A) Fluorine (B) Titanium.

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Fig. 3. Nyquist plots for the impedance measurements in the presence of 5.0 mM K3Fe(CN)6/K4Fe(CN)6 in 0.05 M phosphate buffer (pH 7.0) at a bare GCE (□), titania-Nafion (○), ionic liquid-titania-Nafion (◆), ionic liquid-graphenetitania-Nafion (▲) composite modified glassy carbon electrode.

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Fig. 4. Linear sweep voltammograms of 0.5 μM capsaicin at a titania-Nafion (a), ionic liquid-titania-Nafion (b), graphene-titania-Nafion (c) and ionic liquid-graphenetitania-Nafion (d) composite modified glassy carbon electrode in 0.04 M Britton-Robinson buffer (pH 1.0) at a scan rate of 100 mV/s.

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Fig. 5. Oxidation current of 10 μM capsaicin obtained at glassy carbon electrodes modified with titania-Nafion composites incorporated with 1-butyl-3-methylimidazolium (A), 1-hexyl-3-methylimidazolium (B), 1-ethyl-3-methylimidazolium (C), 1,3-dimethoxy-2-methylimidazolium (D) and 1-benzyl-3-methylimidazolium (E) hexafluorophosphate in 0.05 M pH 7.0 phosphate buffer at a scan rate was 100 mV/s.

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Scheme 1. Reaction mechanism of the oxidation of capsaicin, and the chemical structures of the ionic liquids used: 1-butyl-3-methylimidazolium (A), 1-hexyl-3-methylimidazolium (B), 1-ethyl-3-methylimidazolium (C), 1,3-dimethoxy-2-methylimidazolium (D) and 1-benzyl-3-methylimidazolium (E) hexafluorophosphate.

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Fig. 6. Effect of the accumulation time on the oxidation peak current of 0.1 μM capsaicin at the graphene-titania-Nafion (dashed line) and ionic liquid-graphene-titania-Nafion (solid line) composite-modified electrode in 0.04 M Britton- Robinson buffer (pH 1.0) at a scan rate of 100 mV/s.

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Fig. 7. Effect of concentration of ionic liquid on the oxidation peak current of 100 μM capsaicin at the composite-modified electrode in 0.04 M Britton-Robinson buffer (pH 1.0) at a scan rate of 100 mV/s.

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Fig. 8. Effect of amount of graphene on the oxidation peak current of 100 μM capsaicin at the composite-modified electrode in 0.04 M Britton-Robinson buffer (pH 1.0) at a scan rate of 100 mV/s.

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Fig. 9. Calibration curves for capsaicin obtained at the composite-modified electrode in the concentration of 10 μM, 1 μM, 0.5 μM, 0.1 μM, 0.05 μM, and 0.03 μM. Insert (A): calibration curves for capsaicin obtained at ionic liquidgraphene-titania-Nafion (solid line) and graphene-titania-Nafion (dashed line) composite-modified electrode in the concentration range from 0.03 μM to 1.0 μM. (B): Linear sweep voltammograms of buffer (solid line) and 0.03 μM capsaicin (dotted line) at ionic liquid-graphene-titania-Nafion composite.

Table 1. Comparison of the present capsaicin sensor with different reported methods.

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Table 2. Recovery of capsaicin spiked in Korean hot pepper (Chungyang pepper) solution.

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Acknowledgement

Supported by : National Research Foundation of Korea (NRF)

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