Target-oriented molecularly imprinted polymers enable rapid ambient ionization mass spectrometric analysis of trace...

To address the urgent need for selective and rapid detection of the widespread pollutant in environment, this study developed a solid phase microextraction-constant flow desorption ionization mass spectrometry (SPME-CFDI-MS) method based on target-oriented molecularly imprinted polymer (MIP) adsorbents, using tetrachlorobisphenol A (TCBPA) as a model pollutant. Employing computational screening of interaction energies between functional monomers and TCBPA, 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) was identified as the optimal monomer with both high selectivity and sufficient capacity for TCBPA adsorption, which was subsequently validated by experimental results. The complete analysis, comprising 4 min of SPME and 1 min of CFDI-MS detection, achieved a significant enrichment factor of 36 compared to conventional electrospray ionization MS, markedly enhancing the sensitivity and efficiency of TCBPA detection. The limits of detection (LOD) of 0.0030 μg L^-1 were obtained with a linear range of 0.0050-1.0 μg L^-1 (R² = 0.9987). The precision, evaluated at 0.050 μg L^-1 TCBPA, showed relative standard deviations of 6.4% (intra-fiber, n = 5) and 7.1% (inter-fiber, n = 5). The analysis of environmental samples further confirmed the high accuracy and reliability of the developed method under complex conditions.