Thiol functionalized carbon ceramic electrode modified with multi-walled carbon nanotubes and gold nanoparticles for simultaneous determination of purine derivatives

Abstract

In this proof-of-concept study, a thiol-functionalized sol-gel-based carbon ceramic electrode (CCE) was developed. This CCE was further modified by immobilizing gold nanoparticles (AuNP) in the thiol-functionalized ceramic matrix as well as incorporating multi-walled carbon nanotubes (MWCNT) within the pores of this ceramic sol-gel. The proposed electrode (MWCNT-AuNP-CCE) was used for the simultaneous determination of purine derivatives, uric acid (UA), xanthine (XA) and caffeine (CA). The simultaneous detection of these compounds is essential because these purine derivatives often coexist in real samples. Moreover, since these analytes have the capacity to interchange structures, developing a simultaneous detector is important. This electrode was successfully characterized using environmental scanning electron microscopy (ESEM) with secondary and back scattering electron detectors, energy dispersive X-ray (EDX) analysis, transmission electron microscopy (TEM), and Fourier-transform infrared (FT-IR) spectroscopy. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) measurements were performed in phosphate buffer solution (0.1 M PBS, pH 6) at a potential window of 0.2 to 1.1 V (vs. Ag/AgCl). The proposed modified electrode (MWCNT-AuNP-CCE) displayed three well-defined, stable and continuous oxidation peaks at 0.3, 0.7 and 1.0 V for UA, XA, and CA, respectively. The resulting catalytic current at the surfaces showed a linear dependence to the concentrations of UA, XA and CA for up to 225, 225 and 1500 μM, respectively. The limit of detection was determined to be 50, 63 and 354 nM for UA, XA and CA, respectively. The analytical performance of MWCNT-AuNP-CCE was challenged with real samples such as human serum and urine with recoveries ranging between 98.1 and 102.6%. Moreover, the selectivity of sensor was further challenged with very similar purine molecules, theobromine and theophylline, which contain one less methyl group than CA. Overall, MWCNT-AuNP-CCE exhibited a promising platform for the future development of sensitive electrochemical sensors for the detection of purine derivatives in real samples.

Keywords: Electrochemical sensor; Gold nanoparticles; Modified graphite ceramic electrode; Multi-walled carbon nanotubes; Purine derivatives.