Polyaniline/titanium dioxide nanorods functionalized carbon fibers for in-tube solid-phase microextraction of phthalate esters prior to high performance liquid chromatography-diode array detection.

To improve extraction performance of carbon fibers (CFs) towards phthalate esters (PAEs), titanium dioxide (TiO2) nanorods array was in-situ grown on the surface of CFs, then polyaniline (PANI) was used to modify it. PANI/TiO2 nanorods-CFs were placed into a polyetheretherketone tube for solid-phase microextraction (SPME). Combining the tube to high performance liquid chromatography (HPLC), it was evaluated and displayed good extraction performance for several PAEs. Compared with bare CFs, TiO2 nanorods and PANI, PANI/TiO2 nanorods presented best performance, attributed to the unique advantages between high surface area of TiO2 nanorods and multiple adsorption interactions (like π-π stacking, hydrogen bond) of PANI. After the optimization of the important factors (sampling volume, sampling rate, sample pH, concentrations of organic solvent and salt in sample, and desorption time), the online in-tube SPME-HPLC method was established. It provided low limits of detection (0.01-0.05 μg L-1) and wide linear ranges (0.03-30, 0.10-30, 0.17-30 μg L-1) with correlation coefficients larger than 0.9991. The relative standard deviations (n=6) between intra-day and inter-day tests were in the ranges of 3.5-10.3% and 4.7-13.9%, respectively. The method was successfully used to determine seven PAEs in real water samples. Besides of satisfactory durability, the material also exhibited superior extraction performance than some materials.