Chrysantus Onyinye Chikere
Electrochemical determination of gallic acid in food matrices using novel materials.
Chikere, Chrysantus Onyinye
Doctor Nadimul Faisal N.H.Faisal@rgu.ac.uk
Gallic acid (GA), as an endogenous polyphenol, has shown many different important properties that have influenced its use in the food and pharmaceutical industry. These properties include its antioxidant, anti-cancer, anti-tumor, anti-HIV and anti-ulcerogenic activities. The most commonly used GA determination techniques have been the spectrophotometric and chromatographic techniques. However, these techniques have shown some drawbacks; they are expensive, labour intensive, time-consuming and are not suitable for in-situ measurements. Electrochemical methods using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) at inert glassy carbon electrode (GCE) or carbon paste electrodes (CPE) have also been used in the determination of GA. However, despite their easy application and fast result generation, their sensitivity and selectivity have been relatively inadequate for the analysis of GA found in beverages and pharmaceutical products. The aim of this study is therefore to investigate and develop novel nanomaterials-based electrochemical sensors for determination and analysis of GA that is fast, sensitive, cost-effective and selective. In this study, the detection of GA in red and white wines was achieved using CV, through the development of carbon-based working electrodes modified with graphene oxide nanoparticles and other metal oxide nanoparticles. The synthesised metal oxide nanoparticles were characterised using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy and Zetasizer (for particle size analysis). Meanwhile, characterisation of the developed electrodes was carried out using CV, DPV and electrochemical impedance spectroscopy. The electrochemical effects of the electrodes were analysed. This thesis presents the results of a novel graphene oxide nanocolloids-SiO2 nanoparticles combination used for the electrochemical determination of GA. The results show enhanced peak currents, with high sensitivity and selectivity. The anodic peak current was enhanced from 241 µA (for the bare GCE) to 411 µA (for the modified GCE) - with a limit of detection (LOD) of 2.09 x 10-6 mol L-1, within a concentration range of 6.25 x 10-6 to 1.0 x 10-3 mol L-1. The thesis also proposes that there is a synergistic effect between SiO2 nanoparticles and graphene oxide nanocolloids in the determination of GA. Synthesised amorphous zirconium oxide nanoparticles were used for the modification of a carbon paste electrode and used for the determination of GA. The electrode modification enhanced the electrochemical activity of GA, with increased sensitivity and selectivity. The modified electrode produced an enhanced anodic peak from 260 µA (for the bare electrode) to 451 µA (for the modified electrode) - with an LOD of 1.24 x 10-7 mol L-1, within a range of 1 x 10-6 to 1.0 x 1 x 10-3 mol L-1. The thesis additionally makes a novel proposal for the interaction and effect of the amorphous zirconia nanoparticles on the graphite in the CPE. Zinc oxide nanoparticles and cobalt oxide nanoparticles were also used individually for the modification of carbon paste electrodes. The modified electrodes showed an enhanced effect on GA oxidation. This enhanced effect was an increase in anodic peak current from 261 µA to 414 µA, when the CPE was modified. The LOD produced by the ZnO nanoparticles-modified CPE was 1.86 x 10-7 mol L-1, within a concentration range of 1 x 10-3 to 5 x 10-2 mmol L-1. Meanwhile, the effect of scan rate and the effect of pH show that the electrodes were more effective in acidic pH, and that the GA-electrode interaction was an adsorption-controlled process. Cobalt oxide nanoparticles were also synthesised, characterised and used for the modification of CPE. The modified electrode produced an enhanced anodic peak current from 302 µA (for the bare CPE) to 404 µA (for the modified electrode). The LOD of the modified electrode was studied and found to be 1.52 x 10-6 mol L-1, at a concentration range of 1 x 10-4 to 1 x 10-3 mol L-1. The modified electrodes were successfully used for the determination of GA in real samples of red and white wine. Based on the electrochemical activities of the different electrodes made, the Zirconium dioxide nanoparticles-modified carbon paste electrode seems to have produced the best results. The zirconium dioxide-modified CPE showed increased sensitivity and better limit of detection for GA.
|Institution Citation||CHIKERE, C.O. 2020. Electrochemical determination of gallic acid in food matrices using novel materials. Robert Gordon University [online], PhD thesis. Available from: https://openair.rgu.ac.uk|
|Keywords||Gallic acid; Wine; Electrochemical analysis; Electrochemical determination; Carbon-based electrodes; Metal oxide nanoparticles|
CHIKERE 2020 Electrochemical determination of gallic acid
Copyright: the author and Robert Gordon University