Natural deep eutectic solvent-based hollow polymer inclusion membrane doped with TiO2 nanoparticles: A new design of polymer inclusion membrane for on-chip electromembrane extraction of fluoroquinolones from food samples prior to liquid chromatography tandem mass analysis

Abstract

A new design of polymer inclusion membrane has been proposed with the aim of addressing issues with using common forms of liquid membranes. To do so, a natural deep eutectic solvent (NADES) was employed as an extractant in the structure of the hollow polymer inclusion membrane (HPIM). Besides polyvinyl chloride (PVC) as a base polymer, titanium dioxide nanoparticles (TiO₂) as well as polyethylene glycol polymer (PEG) were incorporated into the HPIM structure to achieve a nanocomposite form with a desirable hydrophilicity. The optimal HPIM was composed of 12.5 v/w% of thymol-coumarin NADES, 3.0 w/w% of TiO₂ and 40.0 v/w% of PEG based on PVC content. Aiming to compare the applicability, HPIMs with other types of extractants, such as bis(2-ethylhexyl) phthalate (DEHP), and the mixture of DEHP-NADES were also fabricated. To confirm the successful fabrication of the HPIM, containing the aforementioned extractant doped with TiO₂ nanoparticles various characterization techniques were employed. The resultant HPIM was employed as a liquid membrane in an on-chip electromembrane extraction (EME) of fluoroquinolones (FQs) from various samples, followed by LC-MS/MS analysis. The parameters influencing extraction performance were analyzed, and the proposed method was validated under ideal conditions. All the samples provided excellent performance concerning limits of detection (0.01–0.08 ng mL⁻¹), and quantification (0.03–0.25 ng mL⁻¹) together with an excellent linearity (R² ≥ 0.9978). The method indicates the desirable RSDs% in the range of 3.2–7.0 % (intra-day, n = 3 × 3) and 3.8–6.1 % (inter-day, n = 3 × 3) for three spiked levels. The satisfactory relative recoveries fell within the 92.0–115.0 % range.