Electrochemical sensor based on 3D-printed substrate by masked stereolithography (MSLA): a new, cheap, robust and sustainable approach for simple production of analytical platforms.

The development of miniaturized, sustainable and eco-friendly analytical sensors with low production cost is a current trend worldwide. Within this idea, this work presents  the innovative use of masked stereolithography (MSLA) 3D-printed substrates for the easy fabrication of pencil-drawn electrochemical sensors (MSLA-3D-PDE). The use of a non-toxic material such as pencil (electrodes) together with a biodegradable 3D printing resin (substrate) allowed the production of devices that are quite cheap (ca. US$ 0.11 per sensor) and with low environmental impact. Compared to paper, which is the most used substrate for manufacturing pencil-drawn electrodes, the MSLA-3D-printed substrate has the advantages of not absorbing water (hydrophobicity) or becoming crinkled and weakened when in contact with solutions. These features provide more reproducible, reliable, stable, and long-lasting sensors. The MSLA-3D-PDE, in conjunction with the custom cell developed, showed excellent robustness and electrochemical performance similar to that observed of the glassy carbon electrode, without the need of any activation procedure. The analytical applicability of this platform was explored through the quantification of omeprazole in pharmaceuticals. A limit of detection (LOD) of 0.72 µmol L-1 was achieved, with a linear range of 10 to 200 µmol L-1. Analysis of real samples provided results that were highly concordant with those obtained by UV-Vis spectrophotometry (relative error ≤ 1.50%). In addition, the greenness of this approach was evaluated and confirmed by a quantitative methodology (Eco-Scale index). Thus, the MSLA-3D-PDE appears as a new and sustainable tool with great potential of use in analytical electrochemistry.

Electrochemical study and forensic electroanalysis of fungicide benzovindiflupyr using disposable graphite pencil electrode.

Nowadays, the use of pesticides in world agriculture is fundamental. However, it leads to an increase in the illegal sale and smuggling of these products in various parts of the world, mainly in Brazil. Therefore, the development of new analytical methods for screening and analysis of these kind of substances is a relevant issue. We present in this work, for the first time, an electrochemical study and a novel electroanalytical method for determination of fungicide benzovindiflupyr (BENZO). According to our knowledge, the electrochemical behavior of BENZO, as well as its voltammetric determination, have never been reported before. The sensors used here consisted of disposable pencil graphite electrodes (PGEs). On this electrode surface and at optimal pH, BENZO behaved according to a quasi-reversible system and showed two voltammetric peaks, one anodic at Ep = +0.59 V and another cathodic at Ep = +0.43 V. The analytical studies utilized BENZO anodic sweep and square-wave adsorptive stripping voltammetry (SWAdSV). All experimental and instrumental parameters were fully investigated and optimized. Under the best conditions, a calibration plot was obtained in the concentration range from 0.10 to 12.5 µmol L-1. The limits of detection (LOD) and quantification (LOQ) achieved were 0.023 and 0.076 µmol L-1, respectively. An electrochemical mechanism for BENZO oxidation was also proposed. The method developed here was successfully employed for the qualitative and quantitative forensic analysis of BENZO in smuggled products, showing good accuracy (recoveries ca. 104%) and precision (relative standard deviation < 5%). These data attest the potential for use of this method in forensic area.