Direct solidification of switchable-hydrophilicity salicylic acid: A design for the on-site dispersive liquid-liquid microextraction of benzoylurea insecticides in water and honey samples

Abstract

This study describes the development of a fully manual method for on-site dispersive liquid-liquid microextraction based on the direct solidification of switchable-hydrophilicity salicylic acid (on-site DLLME-DSSA) coupled with high-performance liquid chromatography with an ultraviolet detector (HPLC-UVD) and its utilization for the detection of benzoylurea insecticides (BUs) in water and honey samples. Salicylic acid (SA), a switchable hydrophilic aromatic acid, was used as an extraction solvent. It can be converted into the hydrophobic/hydrophilic forms in pH-changeable solutions, facilitating facile and effective dispersion and phase separation. Moreover, the melting point of SA (significantly higher than room temperature) enables its direct solidification without an ice-water bath, facilitating its collection by filtration. The dispersion, separation, and collection of the extraction solvent were carried out entirely in a plastic syringe without requiring special apparatus or additional energy. Univariate and response surface analyses were used to optimize various parameters of the on-site DLLME-DSSA method. Under optimal conditions, the limits of determination (LODs) were 1.50 µg L−1 and 0.03–0.09 mg kg−1 in water and honey, respectively. The relative standard deviations (RSDs) for inter-day (n = 5) and intra-day (n = 5) precision were ≤8.4%, whereas the extraction recoveries and enrichment factors for the BUs ranged from 67.0 to 97.1% and 29 to 34, respectively. Furthermore, the proposed method was used for the on-site extraction and laboratory detection of BUs from real water and honey samples. Theoretical analyses indicated non-covalent interactions (such as hydrogen bonds, electrostatic interactions, van der Waals forces, and π-π interactions) to be the main driving force for extraction. This study introduces a switchable hydrophilic aromatic acid capable of direct solidification into on-site DLLME for the first time, opening new frontiers in the development of on-site sample pretreatment methods.