Nanoporous array anodic titanium-supported co-polymeric ionic liquids as high performance solid-phase microextraction sorbents for hydrogen bonding compounds

• Nanoporous array anodic titanium wire was functionalized and used as fiber support.
• Two imidazolium ILs were synthesized and copolymerized in situ on metal support.
• Good extraction performance was obtained by combination of NAAT and ILs copolymer.
• Aliphatic alcohols in liquors were quantified by the GS–SPME–GC method.

A nanoporous array anodic titanium-supported co-polymeric ionic liquids (NAAT/PILs) solid-phase microextraction (SPME) fiber was prepared in situ on the titanium wire. NAAT was selected as the substrate, in view of its high surface-to-volume ratio, easy preparation, mechanical stability, and rich titanol groups on its surface which can anchor silica coupling agent containing vinyl and then introduce ionic liquid copolymers as sorbents. In this work, 1-vinyl-3-nonanol imidazolium bromide ([C9OHVIm]Br) and 1,4-di(3-vinylimidazolium) butane dibromide ([(VIM)2C4]2[Br]) were synthesized and used as monomer and crosslinker, respectively. Extraction properties of the NAAT/PILs fiber for polar alcohols and volatile fatty acids (VFAs) in aqueous matrix were examined using gaseous sampling–SPME (GS–SPME) and headspace SPME (HS–SPME) mode, respectively. Combining the superior properties of NAAT substrate and the strong hydrogen bond interaction of PILs to polar compounds, the NAAT/PILs SPME fiber showed much higher adsorption affinity to aliphatic alcohols than bare NAAT and pure PILs fibers. The detection limits (LOD) of established GS–SPME–GC–FID method are in the range of 0.35–17.30 ng L−1 with a linear range from 0.01 to 500 ng mL−1. Also, it showed high extraction performance toward volatile fatty acids (VFAs) compounds from aqueous matrix. Under the optimized SPME conditions, wide linear ranges were obtained with correlation coefficients (R2) greater than 0.99 and limits of detection were in the range of 0.85–8.74 ng L−1. Moreover, real-world samples were analyzed and good results were obtained.