Selective Separation and Analysis of Catecholamines in Urine Based on Magnetic Solid Phase Extraction by Mercaptophenylboronic Acid Functionalized Fe₃O₄-NH₂@Au Magnetic Nanoparticles Coupled with HPLC

A novel magnetic solid phase extraction based on mercaptophenylboronic acid (MPBA)-functionalized Fe3O4-NH2@Au nanomaterial (Fe3O4-NH2@Au-MPBA) was developed for selective separation and enrichment of catecholamines (including dopamine, norepinephrine and adrenaline). Fe3O4-NH2@Au-MPBA nanoparticles were achieved by self-assembly-anchoring MPBA molecules on the surface of Fe3O4-NH2@Au nanocomposites, which were synthesized via a facial ultrasonic auxiliary in situ reduction process. The interaction between cis-diol from catecholamines and boronic acid was reversible and could be flexibly controlled by adjusting pH value. The catecholamines could be quickly adsorbed by Fe3O4-NH2@Au-MPBA in weak alkaline solution (pH 8.0–9.0) and subsequently released in acid solution (pH 1.0–2.0). The process of adsorption and dissociation was very fast. Furthermore, the three catecholamines could be detected in urine from children by high performance liquid chromatography (HPLC) with electrochemical detector. Under optimal conditions, norepinephrine (NE), epinephrine (EP) and dopamine (DA) were separated very well from internal standard and exhibited a good linearity in the range of 2.5–500.0 ng mL−1, with correlation coefficients of r2 > 0.9907. Limits of detection (LOD) (signal to noise = 3) were 0.39, 0.27 and 0.60 ng mL−1 for NE, EP and DA, respectively. Recoveries for the spiked catecholamines were in the range of 85.4–105.2% with the relative standard deviation (RSD) < 11.5%