Highly sensitive and selective electrochemical sensor for simultaneous determination of gallic acid, theophylline and caffeine using poly(l-proline) decorated carbon nanotubes in biological and food samples

Abstract

In this work, a novel, simple and reproducible poly(l-proline)/functionalized multi-walled carbon nanotube composite on glassy carbon electrode (poly(PRO)-MWCNTs/GCE) was developed as an electrochemical sensor for the simultaneous determination of gallic acid (GA), theophylline (TP) and caffeine (CAF) by differential pulse voltammetry (DPV). The sensing platform was optimized by experimental design and response surface methodology, using various factors affecting polymerization and detection, such as electropolymerization time and potential, and pH, respectively. As a result, the dispersion conditions were the mixing of 1.78 mg MWCNTs with 1.00 mL l-proline solution to 4.14 mg mL^-1 (in SDBS 0.5%), followed by 21 min of sonication with electropolymerization by 16 cyclic scans. In addition, the final analysis was performed at a pH of 3.00 and prior accumulation at 0.350 V for 40 s. The electrochemical behavior of GA, TP and CAF on the optimized sensor was investigated. As a result, the electrode preserves and synergistically combines the properties of each modifier. This new electrochemical sensor showed superior electrocatalytic properties for the oxidation of GA, TP and CAF, which significantly improved the sensitivity of the three compounds. Under the optimized experimental conditions, the detection limits achieved by S/N were 0.03, 0.04 and 0.11 μmol L^-1 for GA, TP and CAF, respectively. The analysis of real samples was successfully performed in human breast milk, tea, infusion of yerba mate, coffee, Coca-Cola zero and energy drink, showing good recoveries, ranged between 87 and 108%. The proposed sensor also showed good selectivity, repeatability and reproducibility, indicating feasibility and reliability. This is the first time that the l-proline monomer is used as a dispersant for MWCNTs and as a precursor for the in-situ polymerization of the proline polymer. Previously, the electropolymerizations were carried out with the monomer in solution rather than as an exfoliant of MWCNTs, where the polymer is electrosynthesized between MWCNTs rather than on them. In this way, the large specific surface area and strong adsorption ability of the nanomaterial are enhanced, and the ability to promote electron transfer reaction is increased, which provides enough effective reaction sites.

Keywords: Carbon nanotubes; Electrochemical sensors; Electropolymerization; Proline; Response surface methodology.