Modulating the selectivity of solid-phase microextraction fibers based on morphological, compositional, and size-depended control of bimetallic oxide nanostructures grown on nickel-titanium alloy substrates.

Nickel-titanium oxide nanotubes (NiTiONTs), nanoparticles, and nanopores were in situ grown on NiTi fiber substrates by controlling anodization parameters. The adsorption performance of different bimetallic oxide nanostructures was evaluated using typical aromatic compounds including chlorophenols, phthalic acid esters, ultraviolet filters (UVFs), and polycyclic aromatic hydrocarbons (PAHs) coupled to HPLC-UV. The results clearly indicate that these NiTiO nanostructures show good extraction capability for UVFs and PAHs. The extraction performance of UVFs and PAHs greatly depends on the surface morphologies and sizes of the grown NiTiO nanostructures along with their elemental compositions. Compared with NiTiO nanoparticle and nanopore coatings, the longer well-aligned NiTiONT coating exhibits better extraction capability and selectivity for PAHs than for UVFs. Therefore, the extraction parameters of the NiTi@NiTiONT fiber for PAHs were investigated and optimized. Under optimized conditions, the proposed method was linear in the range 0.05-200 μg L with correlation coefficients above 0.999. Limits of detection were between 0.008 and 0.124 μg L. Relative standard deviations (RSDs) of the intra-day and the inter-day analyses with the single fiber varied from 4.09 to 6.33%. RSDs for fiber-to-fiber reproducibility of the proposed method with five fibers prepared in different batches were between 5.75 and 7.43%. The applicability of the proposed method was investigated by the enrichment and determination of target PAHs in environmental water samples and relative recoveries of 84.5 ± 6.5 - 116 ± 7.8% were achieved. Notably, the prepared fiber was stable up to 250 times. Graphical abstract.