Development of an Electrochemical Sensor Based on Molecularly Imprinted Polymer Using Functionalized Gold Nanoparticles for Caffeine Quantification.

Abstract

Caffeine is a natural alkaloid consumed primarily for its stimulant and metabolic effects. Some everyday products, such as coffee, tea, soft drinks, sports supplements, and even pain relievers, contain caffeine. However, excessive caffeine consumption, greater than 400 mg per day, can cause adverse effects. Therefore, this work presents an electrochemical sensor based on a molecularly imprinted polymer (MIP) electropolymerized on gold nanoparticles functionalized with p-aminothiophenol (AuNPs-pATP) for caffeine quantification. AuNPs-pATP synthesized show a spherical morphology with an average diameter of 2.54 nm. Stages of MIP formation were monitored by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) using a potassium ferrocyanide redox probe, where the following were observed: (i) an increase in conductivity upon modification of the GCE with AuNPs-pATP, (ii) the blocking of active sites during the electropolymerization step, and (iii) the release of specific cavities upon template removal, revealing consistent differences between the MIP and the control polymer (NIP). SEM images revealed three-dimensional spherical cavities on MIP surface, while the NIP showed a more compact rough surface. Caffeine quantification was performed using square wave voltammetry (SWV) with LOD of 0.195 µmol L^-1 and LOQ of 0.592 µmol L^-1. Interference studies indicated high selectivity and a high density of caffeine-specific binding sites in the MIP. Additionally, MIP sensor demonstrated reusability, good reproducibility, and stability, as well as promising results for analysis in soft drink and sports supplement samples.