Improved electrochemical detection of metals in biological samples using 3D-printed electrode: Chemical/electrochemical treatment exposes carbon-black conductive sites

This work shows that the electrochemical activity of a 3D-printed electrode fabricated using a conductive composite of polylactic acid (PLA) containing carbon black (CB) can be substantially improved through a simple and fast chemical/electrochemical pretreatment in 0.5 mol L-1 NaOH. Scanning electron microscopy and infrared spectroscopy data showed that the pretreatment process promotes the removal of the non-conductive PLA material, providing greater exposure of the conductive particles. Cyclic voltammetry of the redox probe ferricyanide/ferrocyanide indicated faster electron transfer on the treated 3D-printed surface and increase in electroactive area. Moreover, electrochemical impedance spectroscopic results also confirmed faster electron transfer after surface pretreatment. As a proof-of-concept, a low-cost and sensitive method for the determination of cadmium and lead in real urine and saliva samples by square-wave anodic stripping voltammetry was developed. The chemical/electrochemical treatment provided an impressive 30-fold current increase in the detection of both metals. Acceptable limits of detection (2.9 mu g L-1 for Cd2+ and 2.6 mu g L-1 for Pb2+), wide linear ranges for both metals (30 mu g L-1 to 270 mu g L-1; R = 0.997), high stability (RSD lower than 4.5%; n = 10), and adequate recovery values (between 93% and 112%) for the analysis of spiked samples were achieved. Additionally, interday (n = 3), intra-day (n = 3), inter-electrode (n = 2) and inter-treatment (n = 2) experiments revealed RSD values lower than 6.5%, which indicates high reproducibility of the proposed treated 3D-printed electrode. The strategy here proposed opens up new applications for 3D-printed electrode in analytical electrochemistry with improved electrochemical sensing properties in comparison to screen-printed electrodes. (C) 2020 Elsevier Ltd. All rights reserved.