[PMIM]Br@TiO2 nanocomposite reinforced hollow fiber solid/liquid phase microextraction: An effective extraction technique for measurement of benzodiazepines in hair, urine and wastewater samples combined with high-performance liquid chromatography

• A sol–gel-derived [PMIM]Br@TiO2 nanocomposite is developed as a rapid, low-cost and eco-friendly sorbent for HF-SLPME sample preparation.
• Benzodiazepines (BZPs); alprazolam, lorazepam, diazepam and clonazepam have been selected as target compounds.
• HF-SLPME has been applied to the analysis of BZPs in hair, urine and water samples.
• The limits of detection are in the low ng mL−1 or μg g−1 levels.

A new design of hollow fiber solid–liquid phase microextraction (HF-SLPME) was developed for the determination of benzodiazepines (BZPs) in hair, urine and wastewater. The membrane extraction with 1-pentyl-3-methylimidazolium bromide coated titanium dioxide ([PMIM]Br@TiO2) sorbent used in this research is a two-phase supported membrane extraction consisting of an aqueous (donor phase), and n-octanol/nano [PMIM]Br@TiO2 (acceptor phase) system operated in direct immersion sampling mode. The 1-pentyl-3-methylimidazolium bromide (ionic liquid) coated nano TiO2 dispersed in the organic solvent (n-octanol) is held into a porous membrane supported by capillary forces and sonification. It is in contact with the feed phase, which is the aqueous sample. The experimental setup is very simple and highly affordable. The hollow fiber is disposable, so single use of the fiber reduces the risk of cross-contamination and carry-over problems. The proposed method allows the very effective and enriched recuperation of BZPs into one single extract. In order to obtain high extraction efficiency of the analytes using this novel sorbent, the main parameters were optimized. Under the optimized extraction conditions, the method showed good linearity (0.05–6000 ng mL−1), low limits of detection (0.08–0.5 ng mL−1) and good enrichment (533–1190).