Exploring the coating of 3D-printed insulating substrates with conductive composites: a simple, cheap and versatile strategy to prepare customized high-performance electrochemical sensors.

The development of 3D-printed electrochemical sensors by fused deposition modeling (FDM) has been increasing exponentially in the last five years. In this context, commercial conductive filaments composed of a blend of carbon particles (e.g., graphene or carbon black (CB)) and insulating thermoplastic polymers (e.g., polylactic acid (PLA) or acrylonitrile butadiene styrene (ABS)) have been widely used for electrode fabrication. However, such materials may be expensive and the electrodes when used "as-printed" exhibit poor electrochemical performance as a function of the low content of conductive particles in the composition (∼10 to 20 wt%), which requires one or more post-treatment steps (e.g. polishing, chemical, electrochemical, and photochemical) to reach good electrochemical performance. In this technical note a less used approach to produce "ready-to-use" electrochemical platforms based on 3D printing is explored, which consists of the coating of 3D-printed insulating substrates with homemade conductive composites. To demonstrate the potentiality of this alternative protocol, 3D-printed ABS insulating substrates at two geometries were coated in a highly loaded graphite (55 wt%) homemade composite (G-ABS) and evaluated for the detection of the ferri/ferrocyanide redox probe and model analytes in stationary and hydrodynamic 3D-printed systems (nitrite in micro-flow injection analysis/µFIA and paracetamol in batch injection analysis/BIA, respectively). The analytical parameters acquired with the coated electrodes were comparable to those obtained using conventional electrodes (glassy carbon, boron-doped diamond and carbon screen-printed) and 3D-printed sensors fabricated with commercial filaments. Moreover, the inclusion of carbon black in the fluid conductive composite was demonstrated as a perspective to obtain modified coated 3D-printed surfaces easily for the first time. This alternative "do it yourself" strategy is promising for the large-scale production of very cheap (US$ 0.08) and high-performance electrodes based on FDM 3D printing. Moreover, this approach dispenses the acquisition of commercial conductive filaments and the laborious development of homemade filaments.

Development of highly sensitive electrochemical sensor using new graphite/acrylonitrile butadiene styrene conductive composite and 3D printing-based alternative fabrication protocol.

Here, a novel electrically conductive thermoplastic material composed of graphite/acrylonitrile butadiene styrene (G/ABS) is reported for the first time. This material was explored on the production of 3D printing-based electrochemical sensors with enhanced sensitivity using a novel fabrication approach. The developed G/ABS electrodes showed lower charge transfer resistance (157 vs. 3279 Ω), higher electroactive area (0.61 vs. 0.19 cm2) and peak currents ca. 69% higher when compared with electrodes fabricated using carbon black/polylactic acid (CB/PLA) commercial filament, which has been widely explored in recent literature. Moreover, the G/ABS sensor provided satisfactory repeatability, reproducibility and stability (relative standard deviations (RSDs) were 1.14%, 6.81% and 10.62%, respectively). This improved performance can be attributed to the fabrication protocol developed here, which allows the incorporation of greater amounts of conductive material in the polymeric matrix. The G/ABS electrode also required a simpler and quicker protocol for activation when compared to CB/PLA. As proof of concept, the G/ABS sensor was employed for electroanalytical quantification of paracetamol (PAR) in pharmaceutical products. The linear concentration range was observed from 0.20 to 30 µmol L-1 and the limit of detection achieved was 54 nmol L-1, much lower than several recent studies dealing with the same analyte. The sensitivity of the G/ABS electrode regarding PAR was also far better when compared to CB/PLA sensor (0.50 µA/µmol L-1 vs. 0.12 µA/µmol L-1). Analyses in commercial pill samples showed good accuracy (recoveries ca. 108%) and precision (RSDs < 5%), suggesting great potential for use of this novel conductive thermoplastic in electroanalytical applications based on 3D printing.