Hyperbranched polymers containing stereocontorted cores as on-line solid-phase microextraction adsorbent for polycyclic aromatic hydrocarbons

• We used click reaction to prepare a new type of polymer as the monolith column.
• The polymer was porous and could enrich PAHs well up to 100 to more than 1000 times.
• The π–π stacking interaction and the effect of small size played dominant roles to the strong adsorption affinity of the polymer monolith.
• A sensitive on-line SPME–HPLC method was set up for determination of PAHs.

A polymer monolith column was prepared using click chemistry for on-line solid phase microextraction of polycyclic aromatic hydrocarbons (PAHs), using 2,2′,7,7′-tetraethynyl-9,9′-spirobifluorene(TES) and 1,4-bis(6-azidoalkoxy)benzene (BAB) as monomers, and Cu(PPh3)3Br as the catalyst. The polymer with spirocyclic cross-links was porous and presented an appropriate interspace of PAHs. Enrichment of PAHs, in the range of 100 to more than 1000 times, was due to the π–π stacking interaction and the effect of small size. The factors affecting the on-line microextraction efficiency were optimized, and the analytical conditions were evaluated to ensure reliability.