Ultrasound assisted upper critical solution temperature type switchable deep eutectic solvent based liquid-liquid microextraction for the determination of triazole in water

Anal Chim Acta. 2024 Nov 1:1328:343172. doi: 10.1016/j.aca.2024.343172. Epub 2024 Aug 28.

Abstract

Background: The use of pesticides to protect crops has long been an important measure to provide healthy and safe agricultural products, but excess pesticides flow into fields and rivers, causing environmental pollution. Earlier methods utilizing organic solvent liquid-liquid microextraction for pesticide residue detection were not environmentally friendly. Therefore, it is significant to find a greener and more convenient detection method to determine pesticide residues.

Results: A new method was established to detect three triazole fungicides (TFs), including myclobutanil, epoxiconazole and tebuconazole, in environmental water samples. And the determination was conducted using a high-performance liquid chromatography with the ultraviolet detector (HPLC-UV). The switchable deep eutectic solvent (SDES) can be reversibly switched between hydrophilic and hydrophobic states through temperature modulation. Additionally, the method exhibited excellent linearity for all target analytes within the concentration range of 10-2000 μg L-1, with satisfactory R2 values (≥0.9975). The limits of detection (LODs) ranged from 2.3 to 2.6 μg L-1, and the limits of quantification (LOQs) ranged from 7.8 to 8.7 μg L-1. The accuracy of the method was assessed through intra-day and inter-day precision tests, yielding relative standard deviations (RSDs) in the ranges of 2.8%-6.7% and 2.2%-7.5%, respectively. Density functional theory (DFT) results indicated that hydrogen bonding is a significant factor affecting the binding of DES with triazoles. Three different green assessment tools were used to prove that the SDES-HLLME method had good greenness and broad applicability.

Significance: This is a homogeneous liquid-liquid microextraction (HLLME) method based on the upper critical solution temperature (UCST) type switchable deep eutectic solvent program, which can complete the extraction within a few minutes without dispersant. In terms of pesticide detection, the analytical method is simple and more conducive to environmental protection.

Keywords: Environmental analysis; High performance liquid chromatography; Homogeneous liquid-liquid microextraction; Reversible phase transition; Temperature switchable deep eutectic solvent; Triazole fungicides.