Novel functionalized magnetic ionic liquid green separation technology coupled with high performance liquid chromatography: A rapid approach for determination of estrogens in milk and cosmetics.

Several magnetic ionic liquids (MILs), [P6,6,6,14+][FeCl4-], [P6,6,6,14+]2[MnCl42-], [P6,6,6,14+]2[CoCl42-] and [P6,6,6,14+]2[NiCl42-] were synthesized and applied for the extraction of six estrogens (estrone, estradiol, 17-α-hydroxyprogesterone, chloromadinone 17-acetate, megestrol 17-acetate and medroxyprogesterone 17-acetate) in dispersive liquid-liquid microextraction (DLLME). The [CoCl42-]-based MIL was selected as extraction solvent for the separation and concentration of estrogens from milk and cosmetics due to its visual recognition, no sign of hydrolysis, solution acquisition easier and the highest extraction capacity. In addition, the [CoCl42-]-based MIL with low UV absorbance allows direct analysis of the extraction solvent by HPLC-UV. The influence of the mass of MIL, extraction time, salt concentration, and the pH of the sample solution was investigated to obtain optimized extraction efficiency. Besides, extraction conditions including salt concentration, mass of MIL and extraction time were further optimized by the Box-Behnken design through the response surface method. Under optimized conditions, the limits of detection (LODs) of all estrogens were ranged from 5 ng mL-1 to 15 ng mL-1. The recoveries ranging from 98.5% to 109.3% in milk and from 96.3% to 111.4% in cosmetics were also studied, respectively. Furthermore, the proposed method were statistically compared with the reported conventional IL-DLLME method and the National standard methods of food safety and cosmetics. The experimental results showed that the functionalized MIL could successfully applied for extraction, separation and pretreatment of estrogens in milk and cosmetics.