Layer-by-layer coated imidazolium – Styrene copolymers fibers for improved headspace-solid phase microextraction analysis of aromatic compounds

The design of poly(ionic liquids) (PILs) and their application as solid phase microextraction (SPME) fibers has been attracting enormous attention mainly due to the need for new SPME coating materials with improved analytical sensitivity. In this work, the tunability of PILs is explored by preparing different imidazolium monomers bearing benzyl, naphtylmethyl or pentyl pending groups that were subsequently co-polymerized, by reversible addition–fragmentation chain transfer (RAFT) polymerization with styrene. The obtained co-polymers showed excellent thermal stability up to 275 °C, with no melting point up to 250 °C. SPME fibers were prepared by an innovative approach based on layer-by-layer spray coating. The thin (<10 μm) SPME coatings were tested in GC-FID for the detection of volatile aromatic compounds such as benzene (B), toluene (T), ethylbenzene (E) and xylene (X) present in aqueous samples and the extraction parameters optimized. Superior results were obtained when comparing these LbL PILS-based SPME fibers with a commercial fiber composed of poly(dimethylsiloxane), with an increase in the detectable areas of 83%, 69%, 57% and 58% for B, T, E and X, respectively. Low relative standard deviations were obtained for the same fiber (< 5.6%) and also for different fibers (< 9.8%). Furthermore, a spiked soil sample was used to mimic a real contaminated soil sample and excellent recovery results, ranging from 67.0% to 102.2%, were obtained.