Sensitive sensing of GLA and ISL based on highly conductivity nitrogen-doped carbon synergistic dual-template molecularly imprinted ratiometric electrochemical sensor

Abstract

A novel ratiometric Molecularly Imprinted Electrochemical sensor for the specific marker of Glycyrrhiza glabra L. was developed in this work. To achieve simultaneous detection of two analytes on one sensor, we constructed a double template molecular imprinted electrochemical sensor with glabridin (GLA) and isoliquiritin (ISL) as templates. Further, Ferrocene/ZIF-8 (Fc/ZIF-8) composites were prepared via a one-pot solvothermal reaction and coated on the surface of a glassy carbon electrode (GCE), and the oxidation of Fc was presented as the internal reference signal. Nitrogen-doped carbon (NOC) with high conductivity was further loaded on the modified GCE. Based on theoretical exploration and computer directional simulation of density functional theory (DFT), the optimal functional monomer and the best ratio of double template molecules to functional monomer were screened. Under optimal conditions, the sensor produced electrochemical curves when exposed to a solution containing GLA and ISL. As the concentration of GLA and ISL increased, the peak current intensity of GLA and ISL (I_GLA and I_ISL) also increased, while the peak current intensity of Fc (as a reference signal) remained relatively constant. The values of I_GLA/I_Fc and I_ISL/I_Fc showed excellent linear relationships with GLA and ISL concentrations in the range of 0.1-160 μM and 0.5-150 μM, respectively. The detection limits were 0.052 μM and 0.27 μM (S/N = 3), respectively. Due to the imprinting effect of MIP and the existence of a reference signal, the sensor exhibited excellent selectivity and anti-interference ability and was successfully applied to the quality evaluation of Glycyrrhiza glabra L.

Keywords: Density functional theory; Dual template imprinted polymer; Glabridin; Isoliquiritin; Ratiometric electrochemical sensor.