Supramolecular solvents based on hydrophobic natural deep eutectic solvents and primary amines for preconcentration and determination of enrofloxacin in milk

• Published in: Talanta (Oxford) 2024-11, Vol.279, p.126666, Article 126666
• Main Authors: Kurashov, Yaroslav, Pochivalov, Aleksei, Petrova, Anna, Safonova, Evgenia, Garmonov, Sergey, Bulatov, Andrey
• Format: Article
• Language: English
• Subjects: Amines - analysis; Amines - chemistry; Animals; Anti-Bacterial Agents - analysis; Anti-Bacterial Agents - chemistry; Caproates; Caprylates - analysis; Caprylates - chemistry; Chromatography, High Pressure Liquid - methods; Deep Eutectic Solvents - chemistry; Enrofloxacin - analysis; Fatty acid; Fluoroquinolone; Food analysis; Food Contamination - analysis; High performance liquid chromatography with fluorescence detection; Hydrophobic and Hydrophilic Interactions; Limit of Detection; Liquid Phase Microextraction - methods; Menthol - analysis; Menthol - chemistry; Microextraction; Milk - chemistry; Solvents - chemistry; Terpenoid
• ISSN: 0039-9140; 1873-3573; 1873-3573
• DOI: 10.1016/j.talanta.2024.126666

In this work, coacervation in primary amines solutions with hydrophobic natural deep eutectic solvents based on terpenoids and carboxylic acids was demonstrated for the first time. A liquid-phase microextraction approach was developed based on supramolecular solvent formation with primary amine acting as amphiphile and hydrophobic deep eutectic solvent making up mixed vesicles and serving as coacervation agent. Such supramolecular solvents could be used to separate wide range of substances from different aqueous media, such as food products, biological liquids and wastewaters. It is important that both hydrophobic and ionic interactions with supramolecular aggregates take place ensuring synergetic effect and better extraction ability, which is significant in separating relatively polar analytes. Different primary amines and deep eutectic solvents were investigated for liquid-phase microextraction of proof-of-concept amphoteric analyte (enrofloxacin, widely used veterinary fluoroquinolone antibiotic) and its determination by high-performance liquid chromatography with fluorescence detection using Shimadzu LC-20 Prominence chromatograph and RF-20A fluorescence detector. It was found that the supramolecular solvent based on 1-nonylamine, formed after addition of a deep eutectic solvent based on menthol and hexanoic acid (molar ratio of 1:1), provided maximum extraction recovery (85 %) and maximum enrichment factor (34). To characterize the extraction system, the composition of the phases was investigated, and cryo-transmission electron microscopy images were obtained. Vesicular aggregates were observed in the supramolecular solvent. The extraction mechanism was proposed in terms of formation of mixed aggregates to capture the analyte. Limit of detection was found to be 7 μg kg−1, while linear range of 20–250 μg kg−1 was established. Relative standard deviation values were lower than 7 %. Relative bias did not exceed 12 %. [Display omitted] •DESs based on terpenoids and fatty alcohols/fatty acids as coacervation agents.•Microvolume of coacervation agent was needed to induce phase separation.•Structure of primary amine-based SUPRAS was found to be vesicular.•Fast microextraction of enrofloxacin from milk after protein precipitation.