Reduced graphene oxide doping with nanometer-sized ferrocene moieties - New active material for glucose redox sensors.

Herein, we present that the reduced graphene oxide (rGO) doped with nanometer-sized ferrocene moieties is a new, excellent active material for redox sensors. Two distinct approaches were utilized for the modification of rGO. The first method was based on the covalent decoration of rGO via the addition of azomethine ylide generated from the ferrocenecarboxaldehyde oxime. The second approach utilized the adsorption of 1,1'-ferrocenedicarboxylic acid on the graphene sheet via the π-π stacking. The morphology of the synthesized graphene materials was studied by application of microscopic techniques, whereas the Raman data allowed the characteristics of the tested materials in terms of their structural properties. The tested graphene materials doped with ferrocene moieties were used as a bioactive platform for glucose oxidase (GOx) immobilization. The enzyme was immobilized onto the rGO materials in two ways: (i) using a crosslinking agent - glutaraldehyde (GA) and (ii) by formation of the amide bonds between carboxylic groups of rGO-Fc(COOH)2 and amine groups from enzyme. Ferrocene moieties present at the graphene surface play the role of mediator in the electron transfer between the redox center of GOx and the electrode surface. The functionality of the constructed biosensors has been tested on real samples. The results of the recovery rates showed a satisfying degree of accuracy toward determination of glucose concentration. Examination of the potential interfering species has demonstrated favorable sensitivity and selectivity of the designed biosensor for the detection of glucose.