Hexafluoroisopropanol-alkanol based high-density supramolecular solvents: Fabrication, characterization and application potential as restricted access extractants.

Hexafluoroisopropanol-alkanol (C-C) supramolecular solvents were proposed and their application potential as restricted access extraction solvents was assessed. Hexafluoroisopropanol acts as alkanol reverse micelle-forming agent and density-regulating agent for the supramolecular solvent synthesis. The formation of supramolecular solvent only needs a small percentage of hexafluoroisopropanol (<10% v/v for alkanol <5% v/v) and is almost not affected by the pH (2-11) and low ionic strength (NaCl <3%, w/v) of aqueous medium. The supramolecular solvents have higher density than water and consist of reversed micellar aggregates with irregular mesh structures and hydrophilic inner cavities, and the hydrophilic cavity size is obviously dependent on the hexafluoroisopropanol amount in the bulk system but almost not relevant to the alkanol amount. The hydrogen-bond and hydrophobic interactions of hexafluoroisopropanol with alkanol and the hydrogen-bond force between hexafluoroisopropanol and water play crucial roles in the formation of supramolecular solvent. The supramolecular solvents not only do not or slightly dissolve macromolecules (proteins, polysaccharides, and humic acid sodium), but also can effectively exclude them in extraction procedure; meanwhile, they can extract small molecules from complex samples with high extraction rate (even near 100% through optimization). The extraction mechanism involves the hydrophilic inner cavity size of supramolecular aggregates and the interactions (hydrogen-bond, hydrophobic) between supramolecular solvent and analytes. The suitability of supramolecular solvents as extractants was evaluated by extracting and determining chlorophenols in real water samples, coupled with high performance liquid chromatography-ultraviolet detector. The enrichment factors of 72-147 were obtained. Limits of detection were from 0.38 to 0.57 ng mL. The recoveries ranged from 96.0 to 107.9%, and intra-day and inter-day precisions were less than 4.0%. The novel hexafluoroisopropanol-alkanol supramolecular solvents have promising potential as restricted access extractants.