Hydrophobicity-switchable deep eutectic solvent-based effervescence-assisted dispersive liquid–liquid microextraction with solidification of floating droplets for HPLC determination of anthraquinones in fried Cassiae semen tea infusions

In this paper, a hydrophobicity-switchable deep eutectic solvent was evaluated for the first time as an efficient extractant in the effervescence-assisted dispersive liquid-liquid microextraction method combined with the solidification of floating droplets for HPLC determination of anthraquinones in fried Cassiae semen tea infusions. Prepared from choline chloride and octanoic acid, the deep eutectic solvent could be switched between hydrophobic and hydrophilic forms by pH adjustment. The dispersion of the extractant was assisted by in situ CO₂ produced from the effervescence reaction between H₂SO₄ and Na₂CO₃ without using any organic solvent or auxiliary equipment. Owing to the low melting/freezing point and low density compared with water, the extractant was solidified in an ice bath for the convenience of complete separation with the sample matrix. Some important parameters, such as species, molar ratio and volume of deep eutectic solvent, species and volume of effervescent agents were optimized to achieve the best extraction efficiency. Under the optimal conditions, extraction recoveries were obtained for four anthraquinones in the range of 91.1% to 111.9%. Relative standard deviations for intraday and interday precision were less than 3.3% and 4.0%, respectively. Greenness assessment demonstrated that the proposed method was greener than other reported methods for the determination of anthraquinones.