Electrospun polystyrene/oxidized carbon nanotubes film as both sorbent for thin film microextraction and matrix for matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

In the current study, polystyrene/oxidized carbon nanotubes (PS/OCNTs) film was prepared and applied as both an adsorbent of thin film microextraction (TFME) and matrix for matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI–TOF–MS) for the first time. The uniform size of PS/OCNTs film with OCNTs evenly and firmly immobilized in PS was obtained by electrospinning. And a novel TFME device was developed using the prepared PS/OCNTs film to enrich benzo[a]pyrene (BaP) from water, and also BaP and 1-hydroxypyrene (1-OHP) from urine sample. Then the extracted analytes on the PS/OCNTs film were directly applied to MALDI–MS analysis with PS/OCNTs film as the MALDI matrix. Our results show that PS/OCNTs film is a good TFME adsorbent toward the analytes and an excellent matrix for the sensitive determination of BaP and 1-OHP using MALDI–TOF–MS. The employment of PS/OCNTs as the matrix for MALDI can effectively avoid the large variation of signal intensity normally resulting from heterogeneous distribution of the adsorbed analyte on matrix layer, which therefore significantly improve spot-to-spot reproducibility. The introduction of PS in the film can prevent OCNTs from flying out of MALDI plate to damage the equipment. In addition, PS/OCNTs film also largely extended the duration of ion signal of target analyte compared to OCNTs matrix. The developed method was further successfully used to quantitatively determine BaP in environmental water and 1-OHP in urine samples. The results show that BaP and 1-OHP could be easily detected at concentrations of 50 pg mL−1 and 500 pg mL−1, respectively, indicating the high detection sensitivity of this method. For BaP analysis, the linear range was 0.1–20 ng mL−1 with a correlation coefficient of 0.9970 and the recoveries were in the range of 81.3 to 123.4% with the RSD ≤ 8.5% (n = 3); for urinary 1-OHP analysis, the linear range was 0.5–20 ng mL−1 with a correlation coefficient of 0.9937 and the recoveries were in the range of 79.2 to 103.4% with the RSD ≤ 7.6% (n = 3). Taken together, the developed method provides a simple, rapid, cost-effective and high-throughput approach for the analysis of BaP in environmental water and endogenous 1-OHP in urine samples.