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. 2020 Jun 26;13(12):2874.
doi: 10.3390/ma13122874.

A Nonenzymatic Glucose Sensor Platform Based on Specific Recognition and Conductive Polymer-Decorated CuCo2O4 Carbon Nanofibers

Yongling Ding  1   2   3   4 , Huadong Sun  1 , Chunrong Ren  1 , Mingchen Zhang  3 , Kangning Sun  4
Affiliations

A Nonenzymatic Glucose Sensor Platform Based on Specific Recognition and Conductive Polymer-Decorated CuCo2O4 Carbon Nanofibers

Yongling Ding et al. Materials (Basel). .

Abstract

CuCo2O4 decoration carbon nanofibers (CNFs) as an enzyme-free glucose sensor were fabricated via electrospinning technology and carbonization treatment. The CNFs with advantages of abundant nitrogen amounts, porosity, large surface area, and superior electrical conductivity were used as an ideal matrix for CuCo2O4 decoration. The resultant CuCo2O4-CNF hybrids possessed favorable properties of unique three-dimensional architecture and good crystallinity, accompanied by the CuCo2O4 nanoparticles uniformly growing on the CNF skeleton. To further enhance the selective molecular recognition capacity of the developed sensor, a conductive film was synthesized through the electropolymerization of thiophene and thiophene-3-boronic acid (TBA). Based on the synergistic effects of the performances of CNFs, CuCo2O4 nanoparticles, and boronic acid-decorated polythiophene layer, the obtained poly(thiophene-3-boronic acid) (PTBA)/CuCo2O4-CNF-modified electrodes (PTBA/CuCo2O4-CNFs/glassy carbon electrode (GCE)) displayed prominent electrocatalytic activity toward electro-oxidation of glucose. The fabricated sensor presented an outstanding performance in the two linear ranges of 0.01-0.5 mM and 0.5-1.5 mM, with high selectivity of 2932 and 708 μA·mM-1·cm-2, respectively. The composite nanofibers also possessed good stability, repeatability, and excellent anti-interference selectivity toward the common interferences. All these results demonstrate that the proposed composite nanofibers hold great potential in the application of constructing an enzyme-free glucose sensing platform.

Keywords: CuCo2O4; electrocatalytic activity; electrospinning; glucose sensor; thiophene-3-boronic acid.

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Conflict of interest statement

The authors declare no conflicts of interest.

Figures

Scheme 1
Scheme 1
(a) Schematic diagram for the preparation of CuCo2O4–carbon nanofibers (CNFs) and (b) the representation of the proposed mechanism for electrocatalytic oxidation of glucose based on poly(thiophene-3-boronic acid) (PTBA)/CuCo2O4–CNFs/glassy carbon electrode (GCE).
Figure 1
Figure 1
SEM images of (a) polyacrylonitrile (PAN) nanofibers (NFs), (b) CNFs, (c) PAN@CuCo2O4 NFs, and (d) CuCo2O4–CNFs; insets are the enlarged SEM images of the corresponding samples. Panels (e) and (f) correspond to the EDX spectrum of (b) and (d).
Figure 2
Figure 2
X-ray diffraction (XRD) (a) and Raman spectra (b) of CNFs (black) and CuCo2O4–CNFs (red).
Figure 3
Figure 3
Wide-scan (a) and high-resolution X-ray photoelectron spectroscopy (XPS) spectra of CuCo2O4–CNFs at binding energies corresponding to (b) C 1s, (c) N 1s, (d) O 1s, (e) Co 2p, and (f) Cu 2p.
Figure 4
Figure 4
CV of bare GCE, CNFs/GCE, CuCo2O4–CNFs/GCE, and PTBA/CuCo2O4-CNFs/GCE in (a) 1.0 mM [Fe(CN)6]3−/4− and (b) after accumulation of 2 mM glucose in 0.1 M NaOH at a scan rate of 50 mV/s.
Figure 5
Figure 5
(a) CVs of PTBA/CuCo2O4–CNFs/GCE in 0.1 M NaOH with 1 mM glucose at scan rates ranging from 25 to 200 mV·s−1; (b) the linear regression of scan rate versus current signal; (c) the plots of peak potential with respect to ln ν.
Figure 6
Figure 6
(a) Differential pulse voltammetry (DPV) measurements of PTBA/CuCo2O4–CNFs/GCE in 0.1 M NaOH after accumulation in different concentrations of glucose in the range of 0.01–1.5 mM; (b) the linear plots of current versus glucose concentration.
Figure 7
Figure 7
The stability of PTBA/CuCo2O4–CNFs/GCE sensor in the presence of 1 mM glucose after storage for more than two weeks.
See this image and copyright information in PMC

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