An innovative approach for selective and robust screening of NBOHs, NBOMes, and LSD in forensic samples using a 3D-Printed electrochemical double cell.

Lysergic acid diethylamide (LSD) and two phenethylamine classes (NBOHs and NBOMes) are the main illicit drugs found in seized blotter papers. The preliminary identification of these substances is of great interest for forensic analysis. In this context, this work constitutes the inaugural demonstration of an efficient methodology for the selective detection of LSD, NBOHs, and NBOMes, utilizing a fully 3D-printed electrochemical double cell (3D-EDC). This novel 3D-EDC enables the use of two working electrodes and/or two supporting electrolytes (at different pHs) in the same detection system, with the possibility of shared or individual auxiliary and pseudo-reference electrodes. Thus, the selective voltammetric detection of these substances is proposed using two elegant strategies: (i) utilizing the same 3D-EDC platform with two working electrodes (boron-doped diamond (BDD) and 3D-printed graphite), and (ii) employing two pH levels (4.0 and 12.0) with 3D-printed graphite electrode. This comprehensive framework facilitates a fast, robust, and uncomplicated electrochemical analysis. Moreover, this configuration enables a rapid and sensitive detection of LSD, NBOHs, and NBOMes in seized samples, and can also provide quantitative analysis. The proposed method showed good stability of the electrochemical response with RSD <9 % for Ip and <5 % for Ep, evaluating all oxidation processes observed for studied analytes (n = 7) at two pH levels, using the same and different (n = 3) working electrodes. It demonstrates a broad linear range (20-100 and 20-70 µmol L-1) and a low LOD (1.0 µmol L-1) for quantification of a model molecule (LSD) at the two pHs studied. Hence, the 3D-EDC combined with voltammetric techniques using BDD and 3D-printed graphite electrodes on the same platform, or only with this last sensor at two pH values, provide a practical and robust avenue for preliminary identification of NBOHs, NBOMes, and LSD. This method embodies ease, swiftness, cost-efficiency, robustness, and selectivity as an on-site screening tool for forensic analysis.

Electrochemical platform produced by 3D printing for analysis of small volumes using different electrode materials.

Fused deposition modeling (FDM) 3D printing is a promising additive manufacturing technique to produce low-cost disposable electrochemical devices. However, the print of devices like well-known screen-printed electrodes (all electrodes on the same device) is difficult using the available technology (few materials available for production of working electrodes). In this paper we present a procedure to produce disposable and robust electrochemical devices by FDM 3D printing that allows reproducible analysis of small volumes (50-2000 µL). The device consists of just two printed parts that allow easy coupling of different conductive materials for using as disposable or non-disposable working electrodes with reproducible geometric area. Printed counter and pseudo-reference electrodes can also be easily fitted into the microcell. Moreover, conventional counter (platinum wire) and mini reference electrodes can also be used. As a proof of concept, paracetamol, cocaine and uric acid were used as model analytes using different materials as working electrodes. Linear calibration curves (r > 0.99) with similar slopes (0.29 ± 0.01 µA µmol L-1; RSD = 3.4%) were obtained by square wave voltammetry (SWV) using a complete printed system and different volumes of standard solutions of paracetamol (50, 100, and 200 µL). For uric acid, a linear range of 10-125 µmol L-1 (r > 0.99), was obtained using differential pulse voltammetry as the electrochemical technique and a disposable laser-induced graphene base as the working electrode. With the coupling of boron-doped diamond working electrode, screening tests were successfully performed in seized cocaine samples with selective detection of cocaine in the presence of its most common adulterants. The production cost per unit of a complete electrochemical system is around US 5.00. In large-scale production, only the working electrode needs to be replaced while the microcell and counter/pseudo reference electrodes do not need to be discarded.

A simple, fast, portable and selective system using carbon nanotubes films and a 3D-printed device for monitoring hydroxychloroquine in environmental samples.

In this work, an electrochemical method was developed for rapid and sensitive detection of hydroxychloroquine (HCQ), an ineffective candidate drug for COVID-19 treatment however widely consumed during the pandemic, in aqueous samples using a multi-walled carbon nanotubes (MWCNT) film produced through the interfacial method on the indium tin oxide electrode (ITO). According to Raman spectroscopy, X-ray diffraction, UV-vis spectroscopy, Energy-dispersive X-ray spectroscopy, scanning electron microscopy, and atomic force microscopy, the interfacial method produces homogeneous thin films of carbon nanotubes on the substrate surface, which keep connected to the surface forming a three-dimensional microporous structure. The electrochemical behavior and oxidation kinetics of HCQ were also investigated in the MWCNT film. The sensor showed a 7 times higher oxidation current for (69.88 µA) for HCQ than the ITO electrode (9.33 µA) due to the electrocatalytic properties MWCNTs. The ITO-modified electrode was assembled on a portable 3D-printed batch-injection cell for the amperometric detection of HCQ. The oxidation peak current of HCQ is linearly proportional to the concentrations of HCQ ranging from 1.0 to 100.0 µmol L-1, with a limit of detection of 0.27 µmol L-1. Water samples (river and tap water) were spiked with HCQ, without the need for dispendious pretreatment (except filtration), and analyzed by the portable system, revealing the detection of HCQ with the recovery of 92.0%-99.8%, which suggested the great potential for real environmental monitoring application.