A ratiometric electrochemical sensing platform based on multifunctional molecularly imprinted polymer with catalytic activity for the detection of psychoactive substances

Abstract

Molecularly imprinted polymers (MIPs) are widely used as artificial recognition element in sensing field, but their electrochemical sensing performances are generally affected by their poor catalytic activity and unruly condition change. In this work, an MIP film with catalysis (Fe-DMMIP) is constructed by electrodeposition of Fe-coordinated aminophenanthroline and 3,4-ethylenedioxythiophene on N, S doped C material, using cannabinoid (CBD) as template molecule. Due to the presence of Fe–N active sites, the obtained Fe-DMMIP possesses enzyme-like catalytic activity besides conventional recognition capability. Accordingly, the sensor exhibits high electrocatalytic activity and selectivity. Moreover, the Fe-DMMIP can produce a stable and well-defined signal as an internal reference around 0 V (vs. Ag/AgCl) for ratiometric sensing. Under the optimal conditions, the ratiometric signal is linear to CBD concentration in the range of 0.004–0.8 μmol L−1 (R2 = 0.9946) with a detection limit of 2.9 nmol L−1. The ratiometric sensor shows high reproducibility, stability and applicability. In addition, through replacing the template molecule, the resulting biomimetic sensor also exhibits good performance in sensing other psychoactive substances such as melatonin and 5-hydroxytryptophan, with LODs of 19 nmol L−1 and 8 nmol L−1for them, respectively. Therefore, the developed sensing platform has good prospects, and this work provides a new way for developing ratiometric electrochemical sensors with high sensitivity, reproducibility and anti-interference ability.