Halogen bonding: A new retention mechanism for the solid phase extraction of perfluorinated iodoalkanes

For the first time, halogen-bonding interaction is utilised in the solid phase extraction of perfluorinated iodoalkane (PFI). Nine PFIs, as model analytes, were tested, and analyses by UV, 19F NMR and Raman spectroscopies demonstrate that the PFIs are extracted by a strong anion exchange (SAX) sorbent from n-hexane due to the CI⋯Cl− halogen-bonding interactions. The results also show that the adsorptivities of SAX for the diiodoperfluoro-alkanes (diiodo-PFIs) were much stronger than those for the perfluoroalkyl iodides (monoiodo-PFIs). Specifically, the recoveries for 1,6-diiodoperfluorohexane and 1,8-diiodoperfluorooctane were higher than 80% when 100 mL of sample spiked with a 5 ng mL−1 analyte mixture was extracted. Interestingly, SAX had no adsorption for hexafluorobenzene at all, which is known to be unable to form a halogen bond with Cl−. The analytical performance of the halogen bond-based SPE-GC–MS method for the diiodo-PFIs was also examined in soil samples. The sorbent SAX enabled the selective extraction of four diiodo-PFIs successfully from soil samples. The recoveries of the diiodo-PFIs extracted from 5 g soil sample at the 100 ng g−1 spike level were in the range of 73.2–93.8% except 26.8% for 1,2-diiodoperfluoroethane. The limit of detection varied from 0.02 to 0.04 ng g−1 in soil samples. Overall, this work reveals the great application potential of halogen bonding in the field of solid phase extraction to selectively extract compounds with strong halogen-bonding abilities.

Figure optionsDownload as PowerPoint slideHighlights
► Halogen bonding (XB) is firstly utilised in solid phase extraction.
► The perfluorinated iodine alkanes can be extracted by CI⋯Cl− halogen bonding.
► The CI⋯Cl− halogen bond is well characterised by spectroscopy methods.
► The analytes with strong halogen-bonding abilities can be selectively extracted.