Fluorescence-Based Detection of Picric Acid Using Vortex-Assisted Liquid–Liquid Microextraction: An Innovative Analytical Approach

A novel design for vortex-assisted liquid–liquid microextraction (VALLME), combined with spectrofluorimetric determination (FLD), was proposed and successfully tested for determining picric acid (PA) in water samples. This fluorescence method is based on the formation of an ion associate (IA) through electrostatic interactions, which serves as the analytical species for fluorescence measurement in the presence of the basic polymethine dye Astrafloksin (AF). The approach aims to minimize the volume of the extraction phase, aligning with the principles of green analytical chemistry. The calibration curve was linear from 0.92 to 11.45 µg L−1, with an R2 of 0.9930. LOD was 0.40 µg L−1. Density functional theory (DFT) calculations, supported by analysis of van der Waals and electrostatic interionic attraction, helped explain the experimentally observed selectivity of the AF cation for picrate compared to other selected phenols. Theoretical solubility descriptors of the proposed IA provided insight into the extraction of IA from water to the n-amyl acetate phase. This VALLME-FLD method represents a significant advancement in PA determination, characterized by high sensitivity, selectivity, and procedural simplicity. It minimizes the use of organic solvents, facilitates direct sample preparation, and shortens analysis time. The developed method was successfully applied to real samples.