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.

An improved drop casting electrochemical strategy for furosemide quantification in natural waters exploiting chemically reduced graphene oxide on glassy carbon electrodes.

This work exploits the applicability of a chemically reduced graphene oxide (CRGO) modification on the electrochemical response of a glassy carbon electrode (GCE) for the first-time sensitive determination of furosemide in natural waters. The batch injection analysis (BIA) is proposed as an analytical method, where CRGO-GCE is coupled to a BIA cell for amperometric measurements. Acetate buffer (0.1 µmol L-1, pH 5.2) was used as the background electrolyte. The modification provided an increase in sensitivity (0.024 µA/µmol L-1), low limit of detection (0.7 µmol L-1), RSD (< 4%), and broad linear range (1-600 µmol L-1). Recovery tests performed in two different concentration ranges resulted in values between 89 and 99%. Recovery tests were performed and compared with high-performance liquid chromatography (HPLC) with UV-Vis detection using Student's t test at a 95% significance level, and no significant differences were found, confirming the accuracy of the method. The developed method is proven faster (169 h-1) compared with the HPLC analysis (5 h-1), also comparable with other flow procedures hereby described, offering a low-cost strategy suitable to quantify an emerging pharmaceutical pollutant. Graphical abstract.

Electrodeposition of 4-Benzenesulfonic Acid onto a Graphite-Epoxy Composite Electrode for the Enhanced Voltammetric Determination of Caffeine in Beverages.

Caffeine is widely present in food and drinks, such as teas and coffees, being also part of some currently commercialized medicines, but despite its enhancement on several functions of human body, its exceeding use can promote many health problems. In order to develop new fast approaches for the caffeine sensing, graphite-epoxy composite electrodes (GECE) were used as substrate, being modified by different diazonium salts, synthetized as their tetraflouroborate salts. An analytical method for caffeine quantification was developed, using sware wave voltammetry (SWV) in Britton-Robinson buffer pH 2.0. Detection limits for bare electrode and 4-benzenesulfonic modified electrode were observed circa 145 µmol·L-1 and 1.3 µmol·L-1, respectively. The results have shown that the modification shifts the oxidation peaks to lower potential. Kinetics of the reaction limited by diffusion was more expressive when caffeine was added to the solution, resulting in decreases of impedance, characterized by lower R ct. All results for caffeine determination were compared to a reference chromatographic procedure (HPLC), showing no statistical difference. Analytical parameters for validation were suitably determined according to local legislation, leading to a linear behaviour from 5 to 150 µmol·L-1; precision of 4.09% was evaluated based on the RDC 166/17, and accuracy was evaluated in comparison with the reference method, with recovery of 98.37 ± 2.58%.