Tuning the selectivity of polymeric ionic liquid sorbent coatings for the extraction of polycyclic aromatic hydrocarbons using solid-phase microextraction

A new generation polymeric ionic liquid (PIL), poly(1-4-vinylbenzyl)-3-hexadecylimidazolium bis[(trifluoromethyl)sulfonyl]imide (poly(VBHDIm + NTf 2 −)), was synthesized and is shown to exhibit impressive selectivity towards the extraction of 12 polycyclic aromatic hydrocarbons (PAHs) from aqueous samples when used as a sorbent coating in direct-immersion solid-phase microextraction (SPME) coupled to gas chromatography (GC). The PIL was imparted with aromatic character to enhance π–π interactions between the analytes and the sorbent coating. For comparison purposes, a PIL with similar structure but lacking the π–π interaction capability, poly(1-vinyl-3-hexadecylimidazolium bis[(trifluoromethyl)sulfonyl]imide) (poly(HDIm + NTf 2 −)), as well as a commercial polydimethylsiloxane (PDMS) sorbent coating were evaluated and exhibited much lower extraction efficiencies. Extraction parameters, including stir rate and extraction time, were studied and optimized. The detection limits of poly(VBHDIm + NTf 2 −), poly(HDIm + NTf 2 −), and PDMS coatings varied between 0.003–0.07 μg L −1, 0.02–0.6 μg L −1, and 0.1–6 μg L −1, respectively. The partition coefficients (log K fs ) of eight PAHs to the three studied fiber coatings were estimated using a static SPME approach. This study represents the first report of analyte partition coefficients to any PIL-based material.