Natural Deep Eutectic Solvent-Based Dispersive Liquid–Liquid Microextraction Coupled with Direct Analysis in Real Time Mass Spectrometry: A Green Temperature-Mediated Analytical Strategy

Green analytical chemistry (GAC) represents a rapidly growing research field that aims at developing novel analytical approaches with minimal consumption of hazardous reagents and solvents. The current study reports on a GAC methodology exploiting the unique physicochemical properties of natural deep eutectic solvents (NADESs), a supposedly environmentally friendly class of solvents. Based on a temperature-mediated strategy, the NADESs were manipulated to undergo multiple phase transitions for favorable functionality and performance. As proof-of-concept demonstrations, both hydrophobic and hydrophilic NADESs were prepared for the extraction and analysis of eight phthalate esters in aqueous samples (food simulants) and three aflatoxins in oily samples (edible oils), respectively. NADES-based dispersive liquid-liquid microextraction (DLLME) was employed to achieve high-efficiency sample pretreatment. Afterward, the NADESs were transformed from liquids into solids by tuning the peripheral temperature for a convenient phase separation from the sample matrices. The solidified NADES extracts were melted and vaporized at elevated temperatures by transmission-mode direct analysis in real time (DART) for further quadrupole-Orbitrap high-resolution mass spectrometry (Q-Orbitrap HRMS) analysis. The developed protocol was validated, achieving good repeatability with relative standard deviations (RSDs) of less than 9% and satisfactory sensitivity with limits of detection (LODs) and quantitation (LOQs) ranging from 0.1 to 0.8 and 0.2 to 2.0 μg/kg, respectively. The greenness of the analytical methodology was assessed with the calculated scores of 0.66 and 0.57 for the hydrophobic and hydrophilic NADES-based protocols, respectively. The method was applied to marketed samples, highlighting the great potential for green chemical analysis.