Fully automated liquid chromatography-mass spectrometry determination of 17beta-estradiol in river water

Surface modified molecularly imprinted polymers (SM-MIPs) for 17beta-estradiol (E2), utilizing 6-ketoecradiol as a pseudo template were prepared. MIPs for E2 were synthesized using 4-vinyl pyridine and ethylene dimethacrylate as a functional monomer and cross-linking agent, respectively. MIPs selectively retained E2 and provided excellent chromatographic resolution from interfering compounds inherent in river water sample matrices. Therefore, freshly prepared MIPs were applied to quantitative mass spectrometric (negative electrospray ionization mode) detection of low levels of E2 in river water sample. In order to pre-concentrate the target compound for HPLC analysis, column switching was coupled with a pretreatment column packed with the MIPs. The repeatability of actual determinations of river water sample, in which background E2 was not detected, spiked with 50 ng/L of E2 was 2.2% RSD with a detection limit and qualification limit of 1.8 and 5.4 ng/L, respectively. Surface modification of MIP particlefs packed in the pretreatment column provided selective affinity and on-line concentration of low levels of E2 while simultaneously eliminating sample matrix interference, resulting in a significant increase in sensitivity and reproducibility for liquid chromatography-mass spectrometry analysis of E2 in river water sample.