Designed electrochemical sensor based on metallocene modified conducting polymer composite for effective determination of tramadol in real samples

Abstract

A novel composite for the electrochemical sensing of tramadol (Tr) was developed by the inclusion of a metallocene mediator between two layers of conducting poly(3,4-ethylenedioxythiophene) (PEDOT) polymer, in the presence of sodium dodecyl sulfate (SDS), i.e., P/mediator/P⋯SDS. Three charge transfer mediators were evaluated: ferrocene carboxylic acid (FC1), ferrocene (FC2), and cobaltocene (CC) for Tr electrocatalytic oxidation. The FC1 charge mediator showed a relatively higher current response that was assisted by the electronic conduction of the polymer film. Moreover, SDS presented a great impact, resulting in the enhancement of the preconcentration and (or) accumulation of Tr ions at the interface, leading to faster electron transfer. In addition, the practical application of the proposed FC1 composite for the determination of Tr in real urine and serum samples was successfully achieved with adequate recovery results. Very low detection limits of 18.6 nM and 16 nM in the linear dynamic ranges of 7–300 µM and 5–280 µM, respectively, were obtained at the proposed sensor. Furthermore, the simultaneous determination of Tr with common interfering species, paracetamol (APAP), morphine (MO), dopamine (DA), ascorbic acid (AA) and uric acid (UA), proved excellent, with good resolution and large potential peaks separation. The excellent characteristics of the proposed composite such as high reproducibility, good sensitivity, selectivity, anti-interference ability, and good stability enhanced its application for determination of other narcotic drugs.