A simple non-enzymatic hydrogen peroxide sensor using gold nanoparticles-graphene-chitosan modified electrode

https://doi.org/10.1016/j.snb.2014.01.043Get rights and content

Highlights

  • GNPs were electrochemically deposited on the GN and CS modified electrode.

  • The direct electrochemical reduction of H2O2 was achieved in the presence of GNPs.

  • A simple and effective H2O2 sensor with many advantages was developed.

Abstract

Gold nanoparticles (GNPs) were electrochemically deposited on the graphene and chitosan modified glassy carbon electrode and characterized by scanning electron microscope and cyclic voltammetry, respectively. A simple non-enzymatic H2O2 sensor was developed based on the direct electrochemistry of H2O2 in the presence of GNPs. Under the optimized conditions, the fabricated electrode displayed a linear response in the H2O2 concentration range from 5.0 μM to 35 mM with a detection limit of 1.6 μM estimated at a signal-to-noise ratio of 3. The proposed sensor presented some advantages including simple operation procedure, wide linear range, low detection limit, fast response time as well as good anti-interference performance, stability and reproducibility, which indicate it can act as a promising electrochemical platform for H2O2 detection.

Introduction

Hydrogen peroxide has found its wide application in many fields including food, industry, environment and medicine. Biological researches reveal that H2O2 has a close relationship with human metabolism and accumulation of H2O2 can cause grievous injury to cells through base modifications and strand breakage in genomic DNA [1], damage to lysosomal membranes [2], and induction of apoptosis [3]. In addition, H2O2 can play an important role in tumor incidence [4]. So developing H2O2 sensor with low cost, high sensitivity and good biocompatibility is of greatly practical importance. Many detection techniques including fluorescence [5], spectrometry [6], chemiluminescence [7], chromatography [8] and electrochemistry [9], [10], [11], [12], [13] have been reported. Some electrochemical sensors have been prepared based on catalysis of immobilized biomacromolecules, for example, horse radish peroxidase [14], haemoglobin [15] and myosin [16], towards H2O2 reduction. However, their uses have been limited owing to some disadvantages of biomaterials including high cost, instability and critical demand on the environmental condition. Therefore, many researchers devote themselves to development and manufacturing of new-style non-enzymatic sensor. Recent studies have shown that electrodes modified with noble metal nanoparticles [17], carbon nanotubes [18], metal alloys [19], metal oxides [20] exhibit good catalytic activity for direct electrochemistry of H2O2.

Geim and coworkers [21] first reported graphene sheets prepared by mechanical exfoliation (repeated peeling) of highly oriented pyrolytic graphite in 2004. Graphene is a two-dimensional single layer of graphite in which sp2 bonded carbon atoms are arranged into a honeycomb structure. It has attracted tremendous scientific and technological attention because of its unique properties including high surface area, strong mechanical strength, excellent thermal conductivity and electric conductivity. This new-style nanomaterial exhibits a lower charge-transfer resistance than graphite and glassy carbon electrodes and a comparable wide electrochemical potential window [22]. In recent years, graphene has been widely employed in the construction of electrochemical sensors and biosensors [23], [24]. Chitosan is the deacetylated derivative of chitin and contains 2-acetamido-2-deoxy-β-d-glucopyranose and 2-amino-2-deoxy-β-d-glucopyranose residues. It has drawn particular attentions as a biocompatible polymeric matrix based on its excellent film-forming ability, high water permeability and susceptibility to chemical modifications. Many researches using the modified electrodes with nanomatericals including gold nanoparticles, carbon nanotubes and graphene in the presence of chitosan have been reported [25], [26], [27].

In this paper, an electrode modified with electrochemically deposited gold nanoparticles, graphene and chitosan was prepared. A simple method for the detection of H2O2 was developed based on the direct electrochemical reduction of H2O2. Several factors affecting the electroanalytical performances of the proposed sensor were further optimized. The linear range, detection limit, anti-interference performance, stability and reproducibility of the fabricated non-enzymatic sensor were evaluated, respectively.

Section snippets

Reagents and apparatus

Graphene (GN) was purchased from Nanjing CJNANO Tech Co., Ltd., (China). Chitosan (CS, from crab shells, >90% deacetylation) was obtained from Shanghai Biochemical Reagents Co., Ltd. (Shanghai, China). HAuCl4 was obtained from Sinopharm Chemical Reagent Co., Ltd. (China). Hydrogen peroxide, Ascorbic acid (AA, Z99.0%, Fluka), dopamine (DA, Aldrich) and uric acid (UA, Aldrich) were used as received. The hydrogen peroxide stock solution was prepared daily to avoid its excessive decomposition to

Characterization of GNPs/GN-CS/GCE

Fig. 1A–C shows the SEM images of GCE, GN-CS/GCE and GNPs/GN-CS/GCE, respectively. One can find an even and smooth surface of bare glass carbon electrode (Fig. 1A). Graphene was stably immobilized on the GCE surface in the presence of chitosan, exhibiting typical crumpled and wrinkled sheet structure (Fig. 1B). It can be observed from Fig. 1C that gold nanoparticles with the average size of 100 nm were presented with uniform distribution on the graphene-chitosan modified GCE surface. Some GNPs

Conclusions

This work presents a simple and effective non-enzymatic sensor for detection of H2O2 using some biocompatible materials. The direct electrochemical reduction of H2O2 was achieved on the modified glassy carbon electrode with electrochemically deposited gold nanoparticles, which exerted the excellent catalytic activity, graphene and chitosan. Compared with bare GCE, the high specific area and good conductivity of GN-CS/GCE was more beneficial to the electrochemical deposition of gold

Acknowledgments

This work was supported by the National Natural Science Foundation of China (20905025), Hunan Provincial Natural Science Foundation of China (12JJ3015), the Program for Excellent Talents in Hunan Normal University (ET12203) and Aid Program for Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Province.

Ningming Jia is pursuing her M.D. in the Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education, China), College of Chemistry and Chemical Engineering, Hunan Normal University. Her research interests include electrochemical sensing and cell-based detection.

References (36)

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    Notably, the obtained LOD of 1.87 × 10−9 mol L−1 for the sensor was considerably less than those of previous non-enzymatic H2O2 sensors summarized in Table 1. Furthermore, the linear response range (0.001–1.0 mM) and applied potential (around −0.30 V) of the sensor were comparable to those of recently reported H2O2 sensors [17–20]. Hence, the Cu/ERGO nanocomposite-modified electrode can be used as a sensitive electrode material for H2O2 quantification.

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Ningming Jia is pursuing her M.D. in the Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education, China), College of Chemistry and Chemical Engineering, Hunan Normal University. Her research interests include electrochemical sensing and cell-based detection.

Baozhen Huang is pursuing her M.D. in the Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education, China), College of Chemistry and Chemical Engineering, Hunan Normal University. Her research interests include electrochemical sensing and cell-based detection.

Lina Chen is pursuing her M.D. in the Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education, China), College of Chemistry and Chemical Engineering, Hunan Normal University. Her research interests include electrochemical sensing and cell-based detection.

Liang Tan is a professor in the Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education, China), College of Chemistry and Chemical Engineering, Hunan Normal University. His research interests cover electrochemistry analysis, biosensing and cell-based detection.

Shouzhuo Yao is a professor in the Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education, China), College of Chemistry and Chemical Engineering, Hunan Normal University. He has been appointed as an academician of Chinese Academy of Science in analytical chemistry.

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