Development of a Novel Electrochemical Biosensor Based on Carbon Nanofibers-Gold Nanoparticles-Tyrosinase for the Detection of Ferulic Acid in Cosmetics.

The present paper deals with the electrochemical behavior of three types of sensors based on modified screen-printed electrodes (SPEs): a sensor based on carbon nanofibers (CNF/SPE), a sensor based on nanofibers of carbon modified with gold nanoparticles (CNF-GNP/SPE) and a biosensor based on nanofibers of carbon modified with gold nanoparticles and tyrosinase (CNF-GNP-Ty/SPE). To prepare the biosensor, the tyrosinase (Ty) was immobilized on the surface of the electrode already modified with carbon nanofibers and gold nanoparticles, by the drop-and-dry technique. The electrochemical properties of the three electrodes were studied by cyclic voltammetry in electroactive solutions, and the position and shape of the active redox peaks are according to the nature of the materials modifying the electrodes. In the case of ferulic acid, a series of characteristic peaks were observed, the processes being more intense for the biosensor, with the higher sensitivity and selectivity being due to the immobilization of tyrosinase, a specific enzyme for phenolic compounds. The calibration curve was subsequently created using CNF-GNP-Ty/SPE in ferulic acid solutions of various concentrations in the range 0.1-129.6 μM. This new biosensor allowed low values of the detection threshold and quantification limit, 2.89 × 10 mol·L and 9.64 × 10 mol·L, respectively, which shows that the electroanalytical method is feasible for quantifying ferulic acid in real samples. The ferulic acid was quantitatively determined in three cosmetic products by means of the CNF-GNP-Ty/SPE biosensor. The results obtained were validated by means of the spectrometric method in the infrared range, the differences between the values of the ferulic acid concentrations obtained by the two methods being under 5%.