Fast and green methodology based on miniaturised liquid–liquid extraction with a hydrophobic natural deep eutectic solvent of opium alkaloids from poppy seed beverages

• Green and fast analytical method to quantify opium alkaloids in poppy seed beverage. • Thymol:Camphor 1:1 was the best HNADES to extract opium alkaloids in aqueous media. • Efficient miniaturized liquid–liquid extraction achieved in only 2 min. • The poppy seed beverage is safer since the legislation entry into force. Currently, the development of environmentally friendly analytical methodologies is a challenge for analytical chemistry. Therefore, the search for solvents to extract analytes of interest from complex matrices has progressed considerably in recent years. In the present work, 15 hydrophobic natural deep eutectic solvents (HNADES) consisting of a mixture of different donors and acceptors in different ratios have been prepared and compared to evaluate the most efficient extraction of opium alkaloids (OA) from fortified water samples. After selecting the most effective one consisting in a mixture of thymol and camphor in the ratio 1:1 ([Thy]:[Cam] 1:1), a rapid analytical methodology to determine OA in poppy seed beverages was optimised and validated for the first time. It was based on a miniaturised liquid–liquid extraction (m-LLE) with 0.5 mL of sample and 0.5 mL of HNADES by vortexing for 1 min, followed by 1 min centrifugation and subsequent analysis by high-performance liquid chromatography with diode array detector (HPLC-DAD). The validation was successful, showing extraction efficiencies between 91 and 107 % for all analytes, low limits of quantification (0.1 µg/mL for all analytes, except for morphine, 0.4 µg/mL) and precision values below 15 %. In addition, the greenness of the method was evaluated, obtaining a 0.79 on the AGREEprep metric scale. Therefore, it was demonstrated that the methodology developed to analyse OAs in poppy seed beverage was efficient, fast, simple and environmentally friendly.