Tailoring supramolecular solvents with phosphoryl groups for highly efficient extraction of chlorophenols in natural waters

Lourdes Algar; María Dolores Sicilia; Soledad Rubio

doi:10.1016/j.aca.2024.342688

Tailoring supramolecular solvents with phosphoryl groups for highly efficient extraction of chlorophenols in natural waters

Anal Chim Acta. 2024 Jun 22:1309:342688. doi: 10.1016/j.aca.2024.342688. Epub 2024 May 3.

Authors

Lourdes Algar¹, María Dolores Sicilia², Soledad Rubio¹

Affiliations

¹ Department of Analytical Chemistry, Institute of Chemistry for Energy and the Environment, Marie Curie Building (Annex), Campus of Rabanales, University of Córdoba, 14071, Córdoba, Spain.
² Department of Analytical Chemistry, Institute of Chemistry for Energy and the Environment, Marie Curie Building (Annex), Campus of Rabanales, University of Córdoba, 14071, Córdoba, Spain. Electronic address: qa1sicrm@uco.es.

PMID: 38772668
DOI: 10.1016/j.aca.2024.342688

Abstract

Background: Chlorophenols are routinely determined in aquatic systems to check compliance with the restrictive international legislations set for protection of human and aquatic life. Their control requires affordable analytical methods, particularly in labs at low- and medium-income countries. Liquid chromatography-UV detection is a convenient technique for this purpose, but the availability of suitable sample processing remains pending. Organic solvents are inefficient for extracting the whole range of chlorophenols whereas solid-phase extractions are expensive and labour-intensive. So, an efficient, fast and cheap extraction of chlorophenols, amenable to any lab, would help to cope with their worldwide analytical control in natural waters.

Results: A supramolecular solvent (SUPRAS) was tailored for providing mixed interaction mechanisms aimed at the efficient extraction of chlorophenols prior to LC-UV. The SUPRAS was synthesized from the self-assembly of hexylphosphonic acid under acidic conditions and consisted of sponge-like nanostructures made up of amphiphile and water. The phosphoryl (PO) group was selected as the major driver of the extraction because of its ability to act as halogen and hydrogen bond acceptor for chlorophenols. Additional interactions were hydrogen bonds from O-H amphiphilic groups and the surrounding water, and dispersion and CH-π interactions in the hydrocarbon chains. The number of binding sites in the SUPRAS could be modulated by addition of salt. The SUPRAS formed in situ in the sample, the extraction took 5 min, the concentration factor was around 220, quantification limits (0.1-0.3 μg L^-1) were below the EU standards, and the method worked for natural waters.

Significance: A fast, low-cost, and organic solvent-free sample processing only requiring conventional lab equipment (stirrers and centrifuges) provided SUPRAS extracts that could be directly analyzed by LC-UV. SUPRAS synthesis occurred spontaneously in the water sample under addition of hexylphosphonic acid and the whole process required low skills. The method meets the analytical and operational performances for the analytical control of chlorophenols in natural waters and it is within the reach of any lab.

Keywords: Chlorophenols; Environmental waters; Halogen bonding; Hexylphosphonic acid; Hydrogen bonding; Supramolecular solvent.