Facile synthesis of boronic acid-functionalized magnetic metal-organic frameworks for selective extraction and...

Precise determination of the endogenous catecholamines, dopamine (DA), epinephrine (E) and norepinephrine (NE) faces substantial challenges due to their low physiological concentrations in plasma. We synthesized, for the first time, a magnetic metal-organic framework (MIL-100) composite with boronic acid-functionalized pore-walls (denoted as MG@MIL-100-B composite) using a metal-ligand-fragment coassembly (MLFC) strategy. The composites were then applied as an effective magnetic solid-phase extraction (SPE) sorbent for determination of trace catecholamine concentrations in rat plasma through coupling with HPLC-MS/MS. The obtained nano-composites exhibited high magnetic responsivity, uniform mesopores, large specific surface area, and boronic acid-functionalized inner pore-walls. Catecholamines in rat plasma were extracted through interaction between the cis-diol structures and the boronic acid groups in the MG@MIL-100-B composites. Extraction conditions were optimized by studying SPE parameters including adsorption and desorption time, elution solvent type, pH conditions and adsorbent amount. With our approach, the detection limits (S/N = 3) were as low as 0.005 ng mL^-1 for DA and E, and 0.02 ng mL^-1 for NE. Intra- and inter-day precision ranged from 2.84-6.63% (n = 6) and 5.70-11.44% (n = 6), respectively. Recoveries from spiking experiments also showed satisfactory results of 94.40-109.51%. Finally, the MG@MIL-100-B composites were applied successfully to determine catecholamine concentrations in rat plasma.