Ultrasound-Assisted Extraction Using a 3D-Printed Device Functionalized With SPE Sorbent for UHPLC-DAD Analysis of...

The presence of pesticide residues in honey represents a significant concern for food safety and public health, underscoring the need for advanced analytical techniques capable of ensuring accurate detection and effective food control. In this study, a stereolithographically 3D-printed device coated with the solid-phase extraction (SPE) sorbent Oasis MCX was developed for the ultrasound-assisted extraction (UAE) of pesticide residues in honey, followed by ultra-high performance liquid chromatography with diode array detection (UHPLC-DAD) analysis. Variables that affect the performance of the 3D-printed extraction (i.e., design and fabrication of 3D-printed device, SPE resin, elution solution, pH, and ultrasonic conditions) and the chromatographic analysis were systematically evaluated. The optimized methodology allowed the simultaneous determination of five pesticides: azoxystrobin (AZO), carbaryl (CAR), pirimicarb (PIR), thiacloprid (THC), and thiamethoxam (THI). Chromatographic separation was completed in less than 15 min using a KinetexXB-C18 column (2.6 µm, 100 Å, 100 × 3 mm), with a mobile phase consisting of methanol and 0.1% formic acid (pH 3.35). The proposed methodology showed satisfactory agreement compared with commercial QuEChERS dispersive SPE kits. The developed method demonstrated good linearity up to 100 mg L^-1 (R² > 0.99), low detection limits (0.002-0.5 mg kg^-1), good precision (< 5.1 % RSD), and satisfactory recoveries (90-109 %). Its successful application to real honey samples demonstrates the method's potential for reliable multi-residue pesticide analysis in complex food matrices. The sample preparation stage was evaluated with the AGREEprep tool, yielding a greenness score of 0.43, which indicates a moderately green performance.