Zwitterionic molecularly imprinted polymers for selective capillary microextraction of N1,N12-Diacetylspermine (DiAcSpm) from breast cancer

Abstract

N1,N12-diacetylspermine (DiAcSpm), a promising biomarker for cancer diagnosis, presents significant quantification challenges due to the structural homology within the polyamine family. To address this issue, we engineered a molecularly imprinted monolithic (MIM) column functionalized with biomimetic phosphorylcholine (PC) as functional monomer for the selective recognition of DiAcSpm in human urine. The zwitterionic polymer was synthesized via thermally initiated polymerization, with its morphology and pore architecture characterized through scanning electron microscopy (SEM) and brunauer-emmett-teller (BET) analysis. After optimizing capillary microextraction (CME) parameters, the MIM demonstrated a broad linear response (10–500 μM), a low detection limit (3.3 μM, S/N = 3), and high recoveries (76.8–91.2%) when coupled with HPLC-UV analysis. The biomimetic PC-based recognition significantly improved selectivity against key structural analogs, such as spermine, in complex biological matrices. This study underscores the potential of zwitterionic-based MIMs as a robust and efficient platform for the sensitive and selective monitoring of acetylated polyamines in clinical settings.