A computationally driven screening-construction-mechanism strategy of magnetic molecularly imprinted polymers for aliphatic aldehydes detection

Sensitive detection of aliphatic aldehydes in food is hindered by excess derivatization reagents. In this study, a computationally driven screening-construction-mechanism strategy is proposed to enrich aldehyde derivatives while mitigating the adverse effects of excess derivatization reagents. Density functional theory was employed to optimize 20 functional monomers, seven solvents, and three cross-linkers, followed by tuning template/monomer ratios and Fe 2+ dosage to synthesize magnetic molecularly imprinted polymers MMIPs-APBA under the optimal parameters. As magnetic solid-phase extraction (MSPE) adsorbents, MMIPs-APBA achieved rapid equilibrium (10 s), high selectivity for aldehyde derivatives (imprinting factor of 6.2), and minimal adsorption toward derivatization reagents (imprinting factor of 0.025), blocking over 90 % interference signals. Finally, the adsorption mechanism of aldehyde derivatives by MMIPs-APBA is elucidated by three wave function analysis methods. The developed method, combining MMIPs-APBA-based MSPE with gas chromatography–mass spectrometry, is successfully applied for the rapid and accurate determination of eight aliphatic aldehyde derivatives in food samples.