ELECTROCHEMICAL ANALYSIS SUPPORTED BY MACRO AND MICROELECTRODE ARRAY

The purpose of this project was to investigate cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) analytical techniques for enantioselective sensing at both a macroelectrode and a microelectrode array. The scale of the electrochemical cell was reduced from macro to micro dimensions to improve both the electroanalytical detection and the efficient use of chemicals. A microdevice was fabricated using photolithography and plasma bonding and consisting of a microelectrode array (MEA) of 306 microelectrodes, each with a diameter of 45 µm supported by a polydimethylsiloxane (PDMS) slab engraved with microfluidic channels. The electroanalytical performances of the microdevice were characterised using cyclic voltammetry and it was established that the metallisation process influenced the surface roughness of the electrode, and also affected the final response of the array. The microdevice was used for flow injection analysis using chronoamperometry and provided the capability to detect small changes of analyte concentration. The selective electro-oxidation of phenylethanol catalysed by TEMPO and (-)-sparteine at a macroelectrode and MEA was investigated. The CV analysis showed a reproducible selective oxidation in favour of the (-)-phenylethanol enantiomer. The performances of the electrodes were enhanced to improve their enantioselective capability, and to extend their application to biosensors by functionalising their surface with Self-Assembled Monolayers (SAM). The electrodes were modified with glutathione and cysteine chiral molecules to investigate their ability to recognise the proline enantiomers using EIS analysis. The electron transfer rate of the ferricyanide analyte at the cysteine monolayer was less in the presence of D proline than it was in the presence of L-proline, indicating the selective penetration of the enantiomer through the monolayer. The properties of the macroelectrode and MEA were extended to biological applications by modifying their surfaces with thiolated single stranded DNA.