Preparation of solid-phase microextraction fibers by in-mold coating strategy for derivatization analysis of 24-epibrassinolide in pollen samples

A novel and simple in-mold coating strategy was proposed for the preparation of uniform solid-phase microextraction (SPME) coatings. Such a strategy is based on the direct synthesis of the polymer coating on the surface of a solid fiber using a glass capillary as the mold. The capillary was removed and the polymer with well-controlled thickness could be coated on the silica fiber reproductively. Following the strategy, a new poly(acrylamide-co-ethylene glycol dimethacrylate) (poly(AM-co-EGDMA)) coating was prepared for the preconcentration of 24-epibrassinolide (24-epiBL) from plant matrix. The coating had the enrichment factor of 32 folds, and the extraction efficiency per unit thickness was 5 times higher than that of the commercial polydimethylsiloxane/divinylbenzene (PDMS/DVB) coating. A novel method based on SPME coupled with derivatization and large volume injection-high performance liquid chromatography (LVI-HPLC) was developed for the analysis of 24-epiBL. The linear range was 0.500–20.0 μg/L with the detection limit of 0.13 μg/L. The amounts of endogenous 24-epiBL in rape and sunflower breaking-wall pollens samples were determined with satisfactory recovery (77.8–104%) and reproducibility (3.9–7.9%). The SPME-DE/LVI-HPLC method is rapid, reliable, convenient and applicable for complicated plant samples.

► In-mold coating strategy for preparation of uniform SPME coating was proposed.
► A method based on the combination of SPME, derivatization and LVI-HPLC was developed.
► SPME-DE/LVI-HPLC method was applied to analyze endogenous 24-epibrassinolide.