Electromembrane extraction using deep eutectic solvent-supported liquid membranes in a 3D-printed multi-compartment...

This study presents a novel approach for the simultaneous microextraction of six pharmaceutical products based on the use of three different deep eutectic solvents (DES) as supported liquid membranes (SLM), exploiting a custom-designed 3D-printed multi-compartment device for the electromembrane extraction (EME) and subsequent ultra-high-performance liquid chromatography-diode array detector (UHPLC-DAD) analysis. Three DES were synthesized and characterized, combining menthol with aliphatic acids in a 2:1 molar ratio. Thus, menthol:heptanoic acid was used for the extraction of tetracycline (TET) and ampicillin (AMP), menthol:octanoic acid for ciprofloxacin (CIP) and sulfamethoxazole (SMX), while menthol:decanoic acid was used for the extraction of diclofenac (DIC) and ibuprofen (IBU). The simultaneous extraction was optimized by evaluating key parameters such as extraction time, applied voltage, agitation speed, DES volume, buffer composition, and pH in both the donor and acceptor phases. Under optimal conditions, the method achieved limits of detection ranging from 0.05 to 0.4 μg L^-1, with enrichment factors between 10.7 and 13.1. The proposed methodology was satisfactorily applied to wastewater samples, obtaining high relative recoveries (83-102 %) and good reproducibility (precision <9 % RSD). The study demonstrates that the combination of 3D-printed devices, DES-SLM, and EME constitutes a robust, reproducible, and environmentally friendly analytical strategy for monitoring pharmaceutical pollutants in water matrices.