3D-printed electrodes using graphite/carbon nitride/polylactic acid composite material: A greener platform for detection of amaranth dye in food samples.

The production of sustainable materials with properties aimed at the additive manufacturing of electrochemical sensors has gained prestige in the scientific scenario. Here, a novel lab-made composite material using graphite (G) and carbon nitride (C3N4) embedded into polylactic acid (PLA) biopolymer is proposed to produce 3D-printed electrodes. PLA offers printability and mechanical stability in this composition, while G and C3N4 provide electrical properties and electrocatalytic sites, respectively. Characterizations by Raman and infrared spectroscopies and Energy Dispersive X-rays indicated that the G/C3N4/PLA composite was successfully obtained, while electron microscopy images revealed non-homogeneous rough surfaces. Better electrochemical properties were achieved when the G/C3N4/PLA proportion (35:5:60) was used. As a proof of concept, amaranth (AMR), a synthetic dye, was selected as an analyte, and a fast method using square wave voltammetry was developed. Utilizing the 3D-printed G/C3N4/PLA electrode, a more comprehensive linear range (0.2 to 4.2 µmol/L), a 5-fold increase in sensitivity (9.83 µmol-1 L µA), and better limits of detection (LOD = 0.06 µmol/L) and quantification (LOQ = 0.18 µmol/L) were achieved compared to the G/PLA electrode. Samples of jelly, popsicles, isotonic drinks, and food flavoring samples were analyzed, and similar results to those obtained by UV-vis spectrometry confirmed the method's reliability. Therefore, the described sensor is a simple, cost-effective alternative for assessing AMR in routine food analysis.

3D printed graphite-based electrode coupled with batch injection analysis: An affordable high-throughput strategy for atorvastatin determination.

This work integrated a lab-made conductive graphite/polylactic acid (Grp/PLA, 40:60% w/w) filament into a 3D pen to print customized electrodes (cylindrical design). Thermogravimetric analysis validated the incorporation of graphite into the PLA matrix, while Raman spectroscopy and scanning electron microscopy images indicated a graphitic structure with the presence of defects and highly porous, respectively. The electrochemical features of the 3D-printed Gpt/PLA electrode were systematically compared to that achieved using commercial carbon black/polylactic acid (CB/PLA, from Protopasta®) filament. The 3D printed Gpt/PLA electrode "in the native form" provided lower charge transfer resistance (Rct = 880 Ω) and a more kinetically favored reaction (K0 = 1.48 × 10-3 cm s-1) compared to the 3D printed CB/PLA electrode (chemically/electrochemically treated). Moreover, a method by batch injection analysis with amperometric detection (BIA-AD) was developed to determine atorvastatin (ATR) in pharmaceutical and water samples. Using the 3D printed Gpt/PLA electrode, a wider linear range (1-200 µmol L-1), sensitivity (3-times higher), and lower detection limit (LOD = 0.13 µmol L-1) were achieved when compared to the CB/PLA electrode. Repeatability studies (n = 15, RSD <7.3%) attested to the precision of the electrochemical measurements, and recovery percentages between 83 and 108% confirmed the accuracy of the method. Remarkably, this is the first time that ATR has been determined by the BIA-AD system and a low-cost 3D-printed device. This approach is promising to be implemented in research laboratories for quality control of pharmaceuticals and can also be useful for on-site environmental analysis.