Modifying current thin-film microextraction (TFME) solutions for analyzing prohibited substances: Evaluating new coatings using liquid chromatography

For identifying and quantifying prohibited substances, solid-phase microextraction (SPME) continues to arouse interest as a sample preparation method. However, the practical implementation of this method in routine laboratory testing is currently hindered by the limited number of coatings compatible with the ubiquitous high-performance liquid chromatography (HPLC) systems. Only octadecyl (C(18)) and polydimethylsiloxane/divinylbenzene ligands are currently marketed for this purpose. To address this situation, the present study evaluated 12 HPLC-compatible coatings, including several chemistries not currently used in this application. The stationary phases of SPME devices in the geometry of thin film-coated blades were prepared by applying silica particles bonded with various functional ligands (C(18), octyl, phenyl-hexyl, 3-cyanopropyl, benzenesulfonic acid, and selected combinations of these), as well as unbonded silica, to a metal support. Most of these chemistries have not been previously used as microextraction coatings. The 48 most commonly misused substances were selected to assess the extraction efficacy of each coating, and eight desorption solvent compositions were used to optimize the desorption conditions. All samples were analyzed using an HPLC system coupled with triple quadrupole tandem mass spectrometry. This evaluation enables selection of the best-performing coatings for quantifying prohibited substances and investigates the relationship between extraction efficacy and the physicochemical characteristics of the analytes. Ultimately, using the most suitable coatings is essential for trace-level analysis of chemically diverse prohibited substances.