Polymer indicator displacement assay: electrochemical glucose monitoring based on boronic acid receptors and graphene foam competitively binding with poly-nordihydroguaiaretic acid
Simon M. Wikeley, Jakub Przybylowski, Pablo Lozano-Sánchez, Marco Caffio, Tony D. James, Steven D. Bull, Philip J. Fletcher, Frank Marken
Abstract
The concept of a reversible polymer displacement sensor mechanism for electrochemical glucose monitoring is demonstrated. A pyrene-derivatised boronic acid chemo-receptor for glucose is adsorbed onto a graphene foam electrode. Spontaneous oxidative polymerisation of nordihydroguaiaretic acid (NHG) onto the graphene foam electrode leads to a redox active film (poly-NHG) covalently attached to the boronic acid receptors. Oxidation of poly-NHG frees the boronic acid receptors to interact with glucose from the solution phase, which is detected due to competitive binding when reduced poly-NHG re-binds to the boronic acid functional groups. The sensor shows the anticipated boronic acid selectivity of fructose > glucose. The ratio of charges under the voltammetric peaks for poly-NHG unbound and bound is employed for glucose sensing with an approximately linear analytical range from 1 to 50 mM glucose in aqueous pH 7 buffer. The new methodology is shown to give apparent saccharide - boronic acid binding constants and to work in human serum. Therefore, in the future it could be developed further for glucose monitoring.