Perfluoroalkyl substances are chemical pollutants whose levels in the environment should be monitored. This work implemented nonaqueous capillary electrophoresis with conductivity detection to achieve separation of perfluoroheptanoic acid, perfluorooctanoic acid, and perfluorooctanesulfonate within 5 min. The mixture of 3‐(N‐morpholino)propanesulfonic acid and triethylamine in acetonitrile/methanol (50:50, v/v) was used as a background electrolyte. The method was linear (coefficients of determination ˃ 0.996) at analyte concentrations ranging from 2 to 20 μM with instrument detection limits varying between 0.30 and 0.75 μM depending on the analyte. The developed method was precise, the relative standard deviation of repeatability (n = 6) and reproducibility (n = 5) were less than 5.8% for the analytes used. The method was applied to the analysis of perfluoroheptanoic acid, perfluorooctanoic acid, and perfluorooctanesulfonate in wastewater samples treated by solid‐phase extraction, which further made it possible to achieve the method detection limits of perfluoroalkyl substances as low as 0.1–0.4 nM. Additionally, the applicability of the novel carbon aerogel‐based solid‐phase extraction and magnetic solid‐phase extraction were tested for the extraction of target compounds. It would be possible to transform the developed method into a portable format for on‐site analysis.

Inherently chiral, barrel-shaped, macrocyclic hosts such as cyclohexanohemicucurbit[n]urils (cycHC[n]) bind zinc porphyrins and trifluoroacetic acid externally in halogenated solvents. In the current study, we tested a set of eighteen organic guests with various functional groups and polarity, namely, thiophenols, phenols, and carboxylic and sulfonic acids, to identify a preference toward hydrogen bond–donating molecules for homologous cycHC[6] and cycHC[8]. Guests were characterized by Hirshfeld partial charges on acidic hydrogens and their binding by 1H and 19F NMR titrations. Evaluation of association constants revealed the complexity of the system and indirectly proved an external binding with stoichiometry over 2:1 for both homologs. It was found that overall binding strength is influenced by the stoichiometry of the formed complexes, the partial atomic charge on the hydrogen atom of the hydrogen bond donor, and the bulkiness of the guest. Additionally, a study on the formation of complexes with halogen anions (Cl− and Br−) in methanol and chloroform, analyzed by 1H NMR, did not confirm complexation. The current study widens the scope of potential applications for host molecules by demonstrating the formation of hydrogen-bonded complexes with multisite hydrogen bond acceptors such as cycHC[6] and cycHC[8].