A novel magnetic molecular-imprinted polymer (MMIP) was used to selectively extract folic acid directly from real samples. Folic acid was used as template molecule, Fe3O4/SiO2-3-triethoxysilyl-propyl-acrylamide as functional monomer, azobisisobutyronitrile as initiation, ethylene glycol dimethacrylate as crosslinker agent, and acrylamide as the secondary monomer in a mixed ethanol-water solvent. The effect of different parameters on the extraction efficiency was studied, and the optimum conditions were established as follows: the concentrations of crosslinking and template were fixed at 0.05 and 0.06 g, absorption percentage was 96.5, pH was adjusted to 8, and extraction time was 8 h with a temperature of 25 °C. By examining the effect of pH, we tried to investigate the effect of the amide groups that present in MMIP and its intermolecular hydrogen interaction with folic acid. After optimising the effective parameters in polymer synthesis and adsorption rate, a magnetic imprinting dispersive solid-phase extraction method combined with fluorescence spectrophotometry at λem = 367 nm (MMIP-DSPE-FL) was constructed for sensitive determination of folic acid in tomato samples. The limit of quantification (LOQ) and limit of detection (LOD) values were 30.00 ± 0.01 μg L−1 and 10.00 ± 0.03 μg L−1, respectively, after the MMIP-DSPE preconcentration. Three tomato samples were analysed to give recoveries in the range of 80.2–81.6%, with relative standard deviation values below 0.6% (n = 3). The prepared MMIP-DSPE showed high selectivity toward folic acid, which could be used six times without changing adsorption capacity. The adsorption isotherm of the folic acid-imprinted polymer pursued the Langmuir model (RL = 0.029), and the kinetics model followed pseudo-first-order (R2 = 0.9974).
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