Challenges faced with 3D-printed electrochemical sensors in analytical applications.

Prototyping analytical devices with three-dimensional (3D) printing techniques is becoming common in research laboratories. The attractiveness is associated with printers' price reduction and the possibility of creating customized objects that could form complete analytical systems. Even though 3D printing enables the rapid fabrication of electrochemical sensors, its wider adoption by research laboratories is hindered by the lack of reference material and the high "entry barrier" to the field, manifested by the need to learn how to use 3D design software and operate the printers. This review article provides insights into fused deposition modeling 3D printing, discussing key challenges in producing electrochemical sensors using currently available extrusion tools, which include desktop 3D printers and 3D printing pens. Further, we discuss the electrode processing steps, including designing, printing conditions, and post-treatment steps. Finally, this work shed some light on the current applications of such electrochemical devices that can be a reference material for new research involving 3D printing.

A novel 3D-printed graphite/polylactic acid sensor for the electrochemical determination of 2,4,6-trinitrotoluene residues in environmental waters.

Here, lab-made graphite and polylactic acid (Gpt-PLA) biocomposite materials were used to additively manufacture electrodes via the fused deposition modeling (FDM) technique for subsequent determination of the explosive 2,4,6-trinitrotoluene (TNT, considered a persistent organic pollutant). The surface of the 3D-printed material was characterized by SEM and Raman, which revealed high roughness and the presence of defects in the graphite structure, which enhanced the electrochemical response of TNT. The 3D-printed Gpt-PLA electrode coupled to square wave voltammetry (SWV) showed suitable performance for fastly determining the explosive residues (around 7 s). Two reduction processes at around -0.22 V and -0.36 V were selected for TNT detection, with linear ranges between 1.0 and 10.0 µM. Moreover, detection limits of 0.52 and 0.66 µM were achieved for both reduction steps. The proposed method was applied to determine TNT in different environmental water samples (tap water, river water, and seawater) without a dilution step (direct analysis). Recovery values between 98 and 106% confirmed the accuracy of the analyses. Additionally, adequate selectivity was achieved even in the presence of other explosives commonly used by military agencies, metallic ions commonly found in water, and also some electroactive camouflage species. Such results indicate that the proposed device is promising to quantify TNT residues in environmental samples, a viable on-site analysis strategy.

Lab-made 3D-printed electrochemical sensors for tetracycline determination.

Antibiotics such as tetracycline (TC) are widely prescribed to treat humans or dairy animals. Therefore, it is important to establish affordable devices in laboratories with minimal infrastructure. 3D printing has proven to be a powerful and cost-effective tool that revolutionizes many applications in electrochemical sensing. In this work, we employ a conductive filament based on graphite (Gr) and polylactic acid (PLA) (40:60; w/w; synthesized in our lab) to manufacture 3D-printed electrodes. This electrode was used "as printed" and coupled to batch injection analysis with amperometric detection (BIA-AD) for TC sensing. Preliminary studies by cyclic voltammetry and differential pulse voltammetry revealed a mass transport governed by adsorption of the species and consequent fouling of the redox products on the 3D printed surface. Thus, a simple strategy (solution stirring and application of successive potentials, +0.95 V followed by +1.2 V) was associated with the BIA-AD system to solve this effect. The proposed electrode showed analytical performance comparable to costly conventional electrodes with linear response ranging from 0.5 to 50 µmol L-1 and a detection limit of 0.19 µmol L-1. Additionally, the developed method was applied to pharmaceutical, tap water, and milk samples, which required minimal sample preparation (simple dilution). Recovery values of 92-117% were obtained for tap water and milk samples, while the content found of TC in the capsule was close to the value reported by the manufacturer. These results indicate the feasibility of the method for routine analysis involving environmental, pharmaceutical, and food samples.

Paper-based analytical devices for point-of-need applications.

Paper-based analytical devices (PADs) are powerful platforms for point-of-need testing since they are inexpensive devices fabricated in different shapes and miniaturized sizes, ensuring better portability. Additionally, the readout and detection systems can be accomplished with portable devices, allying with the features of both systems. These devices have been introduced as promising analytical platforms to meet critical demands involving rapid, reliable, and simple testing. They have been applied to monitor species related to environmental, health, and food issues. Herein, an outline of chronological events involving PADs is first reported. This work also introduces insights into fundamental parameters to engineer new analytical platforms, including the paper type and device operation. The discussions involve the main analytical techniques used as detection systems, such as colorimetry, fluorescence, and electrochemistry. It also showed recent advances involving PADs, especially combining optical and electrochemical detection into a single device. Dual/combined detection systems can overcome individual barriers of the analytical techniques, making possible simultaneous determinations, or enhancing the devices' sensitivity and/or selectivity. In addition, this review reports on distance-based detection, which is also considered a trend in analytical chemistry. Distance-based detection offers instrument-free analyses and avoids user interpretation errors, which are outstanding features for analyses at the point of need, especially for resource-limited regions. Finally, this review provides a critical overview of the practical specifications of the recent analytical platforms involving PADs, demonstrating their challenges. Therefore, this work can be a highly useful reference for new research and innovation.

A novel miniaturized electroanalytical device integrated with gas extraction for the voltammetric determination of sulfite in beverages.

Voltammetry and amperometry are inexpensive and high-performance analytical techniques. However, their lack of selectivity limits their use in complex matrices such as biological, environmental, and food samples. Therefore, voltammetric and amperometric analyses of these samples usually require time-consuming and laborious sample pretreatments. In this study, we present a simple and cost-effective approach to fabricate a miniaturized electrochemical cell that can be easily coupled to a head space-like gas extraction procedure in such a way the sample pretreatment and voltammetric detection are performed in a single step. As a proof of concept, we have used the proposed system to quantify sulfite in beverage samples after its conversion to SO2(g). Despite the simplicity and low cost of the proposed system, it provided good analytical performance and a limit of detection of 4.0 µmol L-1 was achieved after only 10 min of extraction. The proposed system is quite versatile since it can be applied to quantify any volatile electroactive species. Also, the proposed system provides a unique way to assess real-time extraction curves, which are essential to study and optimize new gas extraction procedures. Therefore, the approach described in this study could contribute to both applied and fundamental Analytical Chemistry.

Thermoplastic electrodes as a new electrochemical platform coupled to microfluidic devices for tryptamine determination.

This study reports a new electrochemical method for tryptamine determination using a paper-based microfluidic device and a thermoplastic electrode (TPE) as an amperometric detector. Tryptamine (Tryp) is a biogenic amine present in drinks and foods. Even though this compound has some beneficial effects on human health, the ingestion of foods with high concentrations of Tryp may be detrimental, which justifies the need for monitoring the Tryp levels. The TPEs were made from 50% carbon black and 50% polycaprolactone and characterized by cyclic voltammetry, demonstrating enhancement in the analytical response compared to other carbon composites. TPEs also showed a better antifouling effect for Tryp compared to conventional glassy carbon electrodes. Once characterized, the electrodes were incorporated into the microfluidic device to determine Tryp in water and cheese samples using amperometry. A linear range was achieved from 10 to 75 µmol L-1 with limits of detection and quantification of 3.2 and 10.5 µmol L-1, respectively. Therefore, this work shows promising findings of the electrochemical determination of Tryp, bringing valuable results regarding the electrochemical properties of thermoplastic composites.

Rapid Analysis in Continuous-Flow Electrochemical Paper-Based Analytical Devices.

A simple and low-cost continuous-flow (CF) electrochemical paper-based analytical device (ePAD) coupled with thermoplastic electrodes (TPEs) was developed. The fast, continuous flow combined with flow injection analysis was made possible by adding two inlet reservoirs to the same paper-based hollow channel flowing over detection electrodes, terminating in a fan-shaped pumping reservoir. The upstream inlet reservoir was filled with buffer and provided constant flow through the device. Sample injections were performed by adding 2 µL of the sample to the downstream sample inlet. Differences in flow resistance resulted in sample plugs displacing buffer as the solution flowed over the working electrodes. The electrodes were fabricated by mixing carbon black and polycaprolactone (50% w/w). CF-TPE-ePADs were characterized with chronoamperometry using ferrocenylmethyl trimethylammonium as the electrochemical probe. Optimized flow rates and injection volumes gave analysis times roughly an order of magnitude faster than those of previously reported flow injection analysis ePADs. To demonstrate applicability, the CF-TPE-ePADs were used to quantify caffeic acid in three different tea samples. The proposed method had a linear range from 10 to 500 µmol L-1 and limits of detection and quantification of 2.5 and 8.3 µmol L-1, respectively. Our approach is promising for fabricating simple, inexpensive, yet high-performance, flow injection analysis devices using paper substrates and easy-to-make electrodes that do not require external mechanical pumping systems or complicated valves.