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.

Multi sensor compatible 3D-printed electrochemical cell for voltammetric drug screening.

3D printing is a hot topic in electroanalytical chemistry, allowing the construction of custom cells and sensors at affordable prices. In this work, we describe a novel small and practical 3D-printed electrochemical cell. The cell's body, manufactured in ABS on a 3D printer, is composed by three parts easily screwed: solution vessel, stick and cover with two embedded 3D-pen-printed carbon black-polylactic acid (CB-PLA) electrodes (counter and pseudo-reference). The cell is compatible with any planar working electrode, in which boron-doped diamond, graphite sheet (GS) and 3D-printed CB-PLA were shown as examples. A new alternative protocol to quickly produce 3D-printed sensors using a 3D pen and other low-cost apparatus is also proposed. The voltammetric performance of each evaluated sensor was carried out in the presence of redox probe ferricyanide and paracetamol as model analyte, and the surfaces were characterized by electrochemical impedance spectroscopy and scanning electrochemical microscopy. To present an analytical application of the 3D-printed cell, low-cost flexible sensors (GS and CB-PLA) were used as integrated platforms for sampling and detection of solid drugs. As a proof-of-concept, traces of drugs with a historic of counterfeit or adulteration (sildenafil citrate, tadalafil, losartan and 17α-ethinylestradiol) were abrasively sampled over the sensor and assembled on 3D-printed cell to perform a fast voltammetric scan in the presence of only 500 µL of electrolyte. This protocol is attractive for pharmaceutical and forensic sciences as a simple preliminary screening method which could identify the presence or absence of the suspicious drug as well as impurities or adulterants. The 3D-printed cell was also used for the determination of 17α-ethinylestradiol in a contraceptive pill to demonstrate a quantitative analysis. The cell is quickly printed (90 min), cheap (US$ 0.30) and requires low electrolyte volumes (0.5-3.0 mL), being suitable to be used in several other electroanalyses, especially for on-site applications.