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A novel flow injection amperometric method for sensitive determination of total antioxidant capacity at cupric-neocuproine complex modified MWCNT glassy carbon electrode

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Abstract

A novel amperometric method is presented for the determination of total antioxidant capacity in flow injection analysis (FIA) system using copper(II)-neocuproine complex modified on Nafion-functionalized multi-walled carbon nanotube-glassy carbon electrode ([Cu(Ncp)22+]/Nf@f-MWCNT/GCE). Cyclic voltammetric studies showed that the modified electrode exhibits a very well-formed reversible redox couple for Cu(II)-/Cu(I)-complex. In addition, the [Cu(Ncp)22+]/[Cu(Ncp)2+] redox pair shows very good electrocatalytic activity towards the oxidation of polyphenolic compounds (PPhCs) such as trolox, catechin, and quercetin due to the enhancement of the anodic peak current of the redox couple in the presence of these analytes. This electrocatalytic oxidation current at the [Cu(Ncp)22+]/Nf@f-MWCNT/GCE was used for flow injection (FI) amperometric determination of PPhCs. FI amperometric-time curves recorded under optimized conditions (applied potential: + 0.6 V vs. Ag/AgCl/KCl(0.10 M), flow rate: 2 mL/min) showed that the proposed electrode had a wide linear range (LR) with a very low detection limit (LOD) for PPhCs. LR and LOD were 0.5–800 and 0.2 µM for trolox, respectively and 0.50–250 and 0.14 µM, respectively, for both quercetin and catechin. This sensitive method was successfully applied to the amperometric measurement of total antioxidant capacity (TAC) of some herbal teas, giving compatible results with the spectrophotometric CUPRAC method. The proposed method gave higher rank to fast-reacting antioxidants; it was equally precise but had a wider linear range and lower LOD than the spectrophotometric CUPRAC assay (e.g., LOD for ascorbic acid and gallic acid were 0.07 and 0.08 μM, respectively), and similar electroanalytical methods using the CUPRAC reagent.

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Acknowledgements

This publication has been produced within the scope of the priority field of biotechnology determined and announced by The Turkish Council of Higher Education (YÖK). This study has also been produced from a part of PhD thesis of Selen Ayaz carried out under supervisions of Prof. Dr. Yusuf Dilgin and Prof. Dr. Reşat Apak. PhD Student Selen Ayaz would like to thank YÖK (supported by 100/2000 program) and The Scientific and Technological Research Council of Turkey (TÜBİTAK) (supported by 2211-A program) for the scholarship.

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Authors and Affiliations

  1. Department of Chemistry, Faculty of Art and Science, Çanakkale Onsekiz Mart University, 17100, Çanakkale, Turkey

    Selen Ayaz & Yusuf Dilgin

  2. Department of Chemistry, Faculty of Engineering, Istanbul University-Cerrahpasa, Avcilar, 34320, Istanbul, Turkey

    Ayşem Üzer & Reşat Apak

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  1. Selen Ayaz
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  2. Ayşem Üzer
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Contributions

Selen Ayaz: conceptualization, methodology, investigation and writing—original draft. Ayşem Arda: investigation, visualization, and results and discussion. Yusuf Dilgin: supervision, writing and funding acquisition. Reşat Apak: supervision, writing—interpreting and editing.

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Correspondence to Yusuf Dilgin or Reşat Apak.

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Ayaz, S., Üzer, A., Dilgin, Y. et al. A novel flow injection amperometric method for sensitive determination of total antioxidant capacity at cupric-neocuproine complex modified MWCNT glassy carbon electrode. Microchim Acta 189, 167 (2022). https://doi.org/10.1007/s00604-022-05271-z

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