Hydrophobic Deep Eutectic Solvents in Developing Microextraction Methods Based on Solidification of Floating Drop: Application to the Trace HPLC/FLD Determination of PAHs

Abstract

In this work, we evaluated the applicability of hydrophobic carboxylic acid-based deep eutectic solvents (DESs) as environmentally friendly alternatives to common organic solvents in microextraction methods based on solidification of floating drop (SFD). Due to the limited number of solvents that can be used in SFD, the introduction of new solvents can help in the development of these attractive methods. Deep eutectic solvents consisting of tetra-n-butyl ammonium bromide (TBAB) and carboxylic acids were prepared and used as extraction solvent. They had the desirable characteristics such as low density, suitable freezing point and proper hydrophobicity which make them suitable alternatives to conventional organic solvents for SFD. With the help of the synthesized hydrophobic DESs, a simple, fast, efficient and environmentally friendly microextraction method was developed based on solidification of deep eutectic solvent (SFDES) without using any organic solvent. The proposed organic solvent-less microextraction method based on SFDES was applied in the analysis of polycyclic aromatic hydrocarbons (PAHs) as model compounds in environmental water samples. By coupling this method with high-performance liquid chromatography–fluorescence detection, we achieved low LOD values which is a necessity in the ultra-trace analysis of PAHs in environmental water samples. Under the optimized conditions, good linearity and low limits of detection of 0.7–6.6 ng L−1 were obtained. The analysis of six PAHs in real water samples gave acceptable relative recoveries ranging from 83 to 117% with 5.4–10.5% intra-day relative standard deviations (RSD) and 4–7.1% interday RSD.