A Surfactant-Based Quasi-Hydrophobic Deep Eutectic Solvent for Dispersive Liquid-Liquid Microextraction of Gliflozins from Environmental Water Samples Using UHPLC/Fluorescence Detection

Abstract

Despite the anticipated exceptional properties of deep eutectic solvents (DES) in microextraction techniques, their self-aggregation behaviour has only been sporadically studied in the previous literature. In the presented study, a novel surfactant-based quasi-hydrophobic deep eutectic solvent (DES) is synthesized and utilized in dispersive liquid-liquid microextraction (DLLME) of three gliflozins in environmental water samples as a proof-of-concept examples. The synthesized DES is composed of benzalkonium chloride (BZKCl) as a hydrogen bond acceptor and octanol (Oct) as a hydrogen bond donor. A full optimization of the extraction conditions was carried out including molar ratio and composition of DES, volume of DES, volume of water samples, extraction time and type of diluting solvent. Moreover, the extraction mechanism was thoroughly investigated, and it was established that the extraction of the target analytes is attributed to the analytes' incorporation into the micelles' cores that facilitates mass transfer from the aqueous layer into DES layer. Furthermore, micelles formed by surfactant-based DES will provide adequate dispersion of extractant phase within water samples, which consequently improves the extraction efficiency. Micelles formation was confirmed by transmission electron microscopy (TEM). Furthermore, 1 H NMR spectra verifies that the synthesized DES keeps its integrity even after extraction, which excludes any decomposition of DES after DLLME procedure. The extraction recovery is in an excellent agreement with the hydrophobicity of the investigated drugs, being the highest for the most hydrophobic one. The extracted analytes were separated by UHPLC coupled with fluorescence detection. Under the optimized experimental conditions, the method exhibits excellent linearity and a high detection sensitivity with a limit of detection of 0.5, 2.0 and 0.1 ng mL-1 for EMP (empagliflozin), DAP (dapagliflozin) and CAN (canagliflozin), respectively. The greenness of the developed microextraction approach was assessed by different greenness metrics such as Complex GAPI and AGREE tools. The developed method shows excellent greenness of synthetic procedure for preparation of DES, the environmentally benign nature of DLLME procedure as well as the greenness of the developed UHPLC approach.