Electrochemical, EIS and AFM characterisation of biosensors: Trioxysilane sol–gel encapsulated glucose oxidase with two different redox mediators

Sol–gel encapsulated glucose oxidase (GOx) enzyme electrodes based on carbon film resistors with chemically deposited copper hexacyanoferrate (CuHCF) or poly(neutral red) (PNR), made by electrochemical polymerisation, as redox mediator have been developed and characterised using cyclic voltammetry, electrochemical impedance spectroscopy and atomic force microscopy. The sol–gel was prepared using three different trioxysilanes: 3-aminopropyl-triethoxysilane (APTOS), 3-glycidoxypropyl-trimethoxysilane (GOPMOS) and methyltrimethoxysilane (MTMOS), without alcohol addition, and alcohol formed during the hydrolysis of the precursor compounds was removed. The best sensitivity, ∼60 nA mM−1, for glucose and limit of detection (2–40 μM, depending on the sol–gel precursor) were obtained when PNR was used as a mediator, but the linear range (50–600 μM) was two to four times lower than that at CuHCF mediated biosensors, using an operating potential of +0.05 V at CuHCF or −0.25 V versus saturated calomel electrode (SCE) at PNR mediated electrodes. The stability of the sensor depended on the sol–gel morphology and was 2 months testing the biosensor every day, while the storability was at least 4 months in the case of GOPMOS, the sensors being kept in buffer at +4 °C.