Development and characterization of a gold nanoparticles glassy carbon modified electrode for dithiotreitol (DTT) detection suitable to be applied for determination of atmospheric particulate oxidative potential

Abstract

A gold nanostructured electrochemical sensor based on modified GC electrode for thiols' detection is described and characterized. This sensor is a suitable device for the measurement of the oxidative potential (OP) of the atmospheric particulate matter (PM), considered a global indicator of adverse health effects of PM, as an alternative to the classic spectrophotometric methods. The operating principle is the determination of the OP, through the measurement of the consumption of DTT content. The DTT-based chemical reactivity is indeed a quantitative acellular probe for assessment of the capacity of the atmospheric PM to catalyze reactive oxygen species generation which contributes to the induction of oxidative stress in living organisms and in turn to the outcome of adverse health effects. To make the sensors, glassy carbon electrodes, traditional (GC) and screen printed (SPE) electrodes, have been electrochemically modified with well-shaped rounded gold nanoparticles (AuNPs) by using a deposition method that allows obtaining a stable and efficient modified surface in a very simple and reproducible modality. The chemical and morphological characterization of the nano-hybrid material has been performed by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy coupled with electron dispersive spectroscopy analysis (SEM/EDS). The electrochemical properties have been evaluated by cyclic voltammetry (CV) and chrono-amperometry (CA) in phosphate buffer at neutral pH as requested in DTT assay for OP measurements. The electroanalytical performances of the sensor in DTT detection are strongly encouraging showing low LODs (0.750 μM and 1.5 μM), high sensitivity (0.0622 μA cm^-2 μM^-1 and 0.0281 μA cm^-2 μM^-1), wide linear and dynamic ranges extending over 2-4 orders of magnitude and high selectivity. FIA preliminary results obtained on measuring the DTT rate consumption in six PM aqueous extracts samples showed a good correlation with measurements obtained in parallel on the same set of samples by using the classic spectrophotometric method based on the Ellman's reactive use. These results confirm the high selectivity of the method and its suitability for application to be applied in PM oxidative potential measurements.

Keywords: Atmospheric particulate matter (PM); BIA and FIA analysis; DTT electrochemical sensor; Gold NPs electro-synthesis; Oxidative potential (OP) measurement.