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Bioelectrochemistry 2013.

Electrochemical and Solid Phase Chemical Modification of Carbon Electrodes for Biosensor Applications
Mohamed A. Ghanema, Izzet Kocakb, Abdullah Al-Mayoufa, Mansour AlHoshanc, Philip N. Bartlettb
b

Chemistry Dept., Science College, King Saud University, KSA School of Chemistry, University of Southampton, Southampton, UK c Chemical Eng. Dept., Eng. College, King Saud University, KSA Email: mghanem@ksu.edu.sa

The surface modification of carbon based electrodes (CNTs, porous carbon, glassy carbon, edge and basal plan carbon) with monolayer of specific chemical functional groups has received great interest for potential applications in molecular electronics, biosensors, surface adhesion and electrocatalysts. In this work, a general electrochemical and solid phase synthesis methods have been developed to covalently bond an organic monolayer linker and redox probe to the surfaces of carbon electrodes [1]. The linker layer was covalently attached either by chemically or electrochemical reduction of PhCH2NHBoc diazonium salt or oxidation of Boc-EDA. After the Boc group deprotection, a selection of organic redox probes such as anthraquinone (Fig.1), nitrobenzene and dihydroxy benzene are attached to the spacer layer by amid coupling reaction using solid-phase synthesis. The surface coverage, stability, electron transfer coefficient and rate of the tethered probe have been investigated by electrochemical techniques. The resulting antheraquinone and dihydroxy benzene modified carbon electrodes were evaluated as mediators for oxygen reduction and the oxidation of NADH respectively. Novel high-throughput methodology for modification of carbon electrodes with 13 dihydroxy benzene member is also developed. The combination of chemical or electrochemical attachment of protected linkers and subsequent modifications using solid-phase synthesis provides a very versatile approach for attaching a wide range of organic moieties onto different types of carbon surface.
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Current/ A

O
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NH O
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Potential vs. SCE/ V

Fig.1. Cyclic voltammograms at scan rate of 50 mV s1 in 0.1 M PBS, pH 7, for CNTs modified by AQ through PhCH2NH spacer layer. Acknowledgment: This project is funded by National Plan for Science and Technology (NPST), King Saud University, Project no: 10-NAN101402 and funded by the EPSRC (EP/D038588/1). [1] M. A. Ghanem, J.M. Chrtien, J. D. Kilburn, P. N. Bartlett, J. Mater. Chem., 18 (2008) 4917; Chemistry Eur. J., 14 (2008) 2548; Bioelectrochemistry, 76, (2009) 115; Chemistry Eur. J., 15, (2009) 11928.