Improving the performance and versatility of microfluidic thread electroanalytical devices by automated injection with electronic pipettes: a new and powerful 3D-printed analytical platform.

Microfluidic cotton thread-based electroanalytical devices (µTEDs) are analytical systems with attractive features such as spontaneous passive flow, low cost, minimal waste production, and good sensitivity. Currently, sample injection in µTEDs is performed by hand using manual micropipettes, which have drawbacks such as inconstant speed and position, dependence of skilled analysts, and need of physical effort of operator during prolonged times, leading to poor reproducibility and risk of strain injury. As an alternative to these inconveniences, we propose, for the first time, the use of electronic micropipettes to carry out automated injections in µTEDs. This new approach avoids all disadvantages of manual injections, while also improving the performance, experience, and versatility of µTEDs. The platform developed here is composed by three 3D-printed electrodes (detector) attached to a 3D-printed platform containing an adjustable holder that keeps the electronic pipette in the same x/y/z position. As a proof-of-concept, both injection modes (manual and electronic) were compared using three model analytes (nitrite, paracetamol, and 5-hydroxytryptophan) on µTED with amperometric detection. As result, improved analytical performance (limits of detection between 2.5- and 5-fold lower) was obtained when using electronic injections, as well as better repeatability/reproducibility and higher analytical frequencies. In addition, the determination of paracetamol in urine samples suggested better precision and accuracy for automated injection. Thus, electronic injection is a great advance and changes the state-of-art of µTEDs, mainly considering the use of more modern and versatile electronic pipettes (wider range of pre-programmed modes), which can lead to the development of even more automated systems.

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.

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.