Abstract
The electrochemical surface plasmon resonance (ESPR) technique was used to investigate the electrodeposition of the charge-transfer complex (CTC) generated during electrooxidation of o-tolidine ( o-TD) in pH 4.5 Britton–Robinson buffers and the effects of coexisting dermatan sulfate (DS). The peak-type surface plasmon resonance (SPR) responses (versus time) observed in the cyclic voltammetric experiments indicated the precipitation and dissolution of a poorly soluble CTC, an oxidation intermediate, formed during the redox switching of o-TD in a weakly acidic medium. The effects of potential scan rate and solution pH were examined. The height of the peak-type SPR response to the redox switching of the o-TD/CTC “couple” was notably enhanced by the introduction of DS, due to the formation of a mass-enhanced CTC-DS adduct, as also supported by UV–vis spectroelectrochemistry. The SPR signal responded linearly to the DS concentration up to 14 μmol L −1, with a limit of detection (LOD) down to 8 nmol L −1 ( S/ N = 3). The analytical performance of the ESPR technique was found to be better than that of the quartz crystal microbalance technique with an LOD value of 70 nmol L −1. The CTC-based ESPR assay is recommended as a new, highly sensitive and dynamically surface-regenerated biosensing technology for other species.
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