Understanding the influence of polymeric ionic liquid sorbent coating substituents on cannabinoid and pesticide affinity in solid-phase microextraction

To understand factors that drive pesticide-cannabinoid selectivity in solid-phase microextraction (SPME), eight new polymeric ionic liquid (PIL) sorbent coatings were designed and compared to four previously reported PIL sorbent coatings for the extraction of pesticides. The four PIL sorbent coatings consisted of either vinylimidazolium or vinylbenzylimidazolium ILs with long alkyl chain substituents (i.e.,-C8H17 or-C12H25) and bis [(trifluoromethyl)sulfonyl]imide ([NTf2 ]) anions, from which the eight new PIL sorbent coatings were adapted. Modifications to the chemical structure of IL monomers and crosslinkers included incorporation of polymerizable p-styrenesulfonate or 3-sulfopropyl acrylate anions, the addition of aromatic moieties, and/or the addition of polar functional groups (i.e.,-OH or -O-groups). A total of ten commonly regulated pesticides and six cannabinoids were examined in this study. The effect of salt on the solubility of pesticides and cannabinoids in aqueous solutions was assessed by determining their extraction efficiencies in the presence of varied methanol content. Differences in their solubilities appear to play a dominant role in enhancing pesticide-cannabinoid selectivity. The selectivity, represented as the ratio of pesticide total peak areas to cannabinoid total peak areas, also exhibited a moderate correlation to the affinity of the sorbent coatings towards both the pesticides and the cannabinoids. A positive correlation was observed for the pesticides and a negative correlation was observed for the cannabinoids, suggesting that selectivity was driven by more than the presence of salt in the samples. The sorbent coatings' affinity towards each class of analytes were examined to determine specific interactions that might influence selectivity. The two main structural modifications increasing pesticide-cannabinoid selectivity included the absence of aromatic moieties and the addition of hydrogen bond donor functional groups. Extractions of simple aromatic molecules as probes were performed under similar extraction conditions as the cannabinoids and confirmed the influence of hydrogen bonding interactions on sorbent coating affinity.