Amperometric biosensors based on carbon paste electrodes modified with nanostructured mixed-valence manganese oxides and glucose oxidase

Abstract

Nanostructured, multivalent, manganese-oxide octahedral molecular sieves (OMS), including cryptomelane-type manganese oxides and todorokite-type manganese oxides, were synthesized and evaluated for chemical sensing and biosensing at low operating potential. Both cryptomelane-type manganese oxides and todorokite-type manganese oxides are nanofibrous crystals with subnanometer open tunnels that provide a unique property for sensing applications. The electrochemical and electrocatalytic performance of OMS for the oxidation of H 2O 2 have been compared. Both cryptomelane-type manganese oxides and todorokite-type manganese oxides can be used to fabricate sensitive H 2O 2 sensors. With glucose oxidase (GOx) as an enzyme model, amperometric glucose biosensors are constructed by bulk modification of carbon paste electrodes with GOx as a biocomponent and nanostructured OMS as a mediator. A Nafion thin film was applied as an immobilization/encapsulation and protective layer. The biosensors were evaluated as an amperometric glucose detector at phosphate buffer solution with a pH 7.4 at an operating potential of 0.3 V (vs Ag/AgCl). The biosensor is characterized by a well-reproducible amperometric response, linear signal-to-glucose concentration range up to 3.5 mmol/L and 1.75 mmol/L, and detection limits (S/N = 3) of 0.1 mmol/L and 0.05 mmol/L for todorokite-type manganese oxide and cryptomelane-type manganese oxide–modified electrodes, respectively. The biosensors based on OMS exhibit considerable good reproducibility and stability, and the construction and renewal are simple and inexpensive.