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Amperometric glucose biosensor based on single-walled carbon nanohorns

https://doi.org/10.1016/j.bios.2008.02.016Get rights and content

Abstract

The biosensing application of single-walled carbon nanohorns (SWCNHs) was demonstrated through fabrication of an amperometric glucose biosensor. The biosensor was constructed by encapsulating glucose oxidase in the Nafion–SWCNHs composite film. The cyclic voltammograms for glucose oxidase immobilized on the composite film displayed a pair of well-defined and nearly symmetric redox peaks with a formal potential of −0.453 V. The biosensor had good electrocatalytic activity toward oxidation of glucose. To decrease detection potential, ferrocene monocarboxylic acid was used as a redox mediator. The mediated glucose biosensor shows a linear range from 0 to 6.0 mM. The biosensor shows high sensitivity (1.06 μA/mM) and stability, and can avoid the commonly coexisted interference. Because of impressive properties of SWCNHs, such as high purity and high surface area, SWCNHs and their composites are expected to be promising material for biomolecular immobilization and biosensing applications.

Introduction

Carbon nanotubes (CNTs) has been extensively used in electrochemical and biosensing studies (Sotiropoulou et al., 2003, Katz and Willner, 2004, Poh et al., 2004, Lin et al., 2005, Merkoçi et al., 2005, Wang, 2005, Balasubramanian and Burghard, 2006). For example, CNTs have been used for electrocatalysis (Chen et al., 2005, Liu et al., 2005a, Musameh et al., 2002), immobilization of proteins (Zhao et al., 2002, Davis et al., 2003, Wang et al., 2003, Hrapovic et al., 2004, Zhang et al., 2004, Tsai et al., 2005, Yan et al., 2005), and promotion of direct electrochemistry of redox proteins (Gooding et al., 2003, Patolsky et al., 2004), and so on. However, most CNT synthesis methods inevitably introduce some impurities. Tedious purification is necessary, and metal catalyst residues still existed in CNTs even after purification. The impurities resulted in conflicting reports (Shvedova et al., 2003, Banks et al., 2006, Sljukic et al., 2006, Jones et al., 2007).

Single-walled carbon nanohorns (SWCNHs) are cost-effectively produced by laser ablation of pure graphite with unparalleled purity without using any metal catalyst (Iijima et al., 1999). It is essentially metal-free and can be used directly for electrochemical and biosensing study. Typically, horn-shaped SWCNHs assemble and form dahlia-like or bud-like aggregates (Yang et al., 2005), ensuring extremely large surface area and fast mass transport. Its unique properties rapidly promote various applications (Ohba et al., 2001, Yoshitake et al., 2002, Bekyarova et al., 2003, Murakami et al., 2004).

In this study, the biosensing application of SWCNHs was exploited using glucose biosensor as a model (Heller, 1999, Wang, 2001, Newman and Turner, 2005, Wilson and Gifford, 2005). The biosensor was constructed by immobilizing glucose oxidase in Nafion–SWCNHs film. It showed high sensitivity, good selectivity, and comparable results with spectrophotometry method.

Section snippets

Reagents

The glucose oxidase (GOx, from Aspergillus niger, E.C. 1.1.3.4), ferrocene monocarboxylic acid (FMCA, 97%), Nafion (20 wt.% of lower aliphatic alcohols/water mixture), lithium l-lactate, l-cysteine, glutathione, l-ascorbate acid and p-aminophenol were purchased from Sigma and used without further purification. β-d-Glucose (>99.8%) was purchased from Amresco and the glucose stock solutions were stored overnight at room temperature before use. Professor S. Iijima generously offers SWCNHs. Other

Morphology and voltammetric characterization of Nafion–SWCNHs modified glassy carbon electrode

A typical SEM image of Nafion–SWCNHs modified glassy carbon electrode is shown in Fig. S1. Spherical SWCNHs aggregates are packed densely and homogeneously on the electrode surface. The conductivity and the inherent purity of SWCNHs make them excellent candidates for electrochemical application. Cyclic voltammetry is a useful tool for electrochemical evaluation of the transducers. K3Fe(CN)6 was used as a probe to investigate performance of Nafion–SWCNHs film (Fig. S2). A pair of well-defined

Conclusions

In summary, we utilized SWCNHs for the first time to fabricate glucose biosensor. The glucose biosensor based on the Nafion–SWCNHs nanocomposite possessed high sensitivity, low detection limit, and good selectivity. The attractive electrochemical and structural properties of SWCNHs suggest potential application of SWCNHs for electrocatalysis and biosensor.

Acknowledgements

We are very grateful to Professor S. Iijima (Solution Oriented Research for Science and Technology in Japan Science and Technology Agency) for generous offer of SWCNHs. This work was kindly supported by the National Natural Science Foundation of China (No. 20505016), Department of Sciences & Technology of Jilin Province (20070108), and Hundred Talents Program of Chinese Academy of Sciences.

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