Enabling cost-effective safety monitoring of shellfish is an important measure for the healthy development of the coastal marine economy. Herein, a new aptamer@metal-organic framework (MOF)-functionalized affinity monolithic column was proposed and applied in selective in-tube solid-phase microextraction (IT-SPME) coupled with HPLC for the accurate recognition of domoic acid (DA) in shellfish. Using a surface engineering strategy, ZIF-8 MOF was grown in situ inside the poly(epoxy-MA-co-POSS-MA) hybrid monolith. A high BET surface area and abundant metal reactive sites of the MOF framework were obtained for anchoring massive aptamers with terminal-modified phosphate groups. Various characterizations, such as SEM, elemental mapping, XRD, and BET, were performed, and the affinity performance was also studied. The presence of a massive amount of aptamers with a super coverage density of 3140 μmol L-1 bound on ZIF-8 MOF activated a high-performance bionic-affinity interface, and perfect specificity was exhibited with little interference of tissue matrixes, thus assuring the highly selective capture of DA from the complex matrixes. Under the optimal conditions, DA toxins in shellfish were detected with the limit of detection (LOD) of 7.0 ng mL-1 (equivalent to 14.0 μg kg-1), representing a 5-28 fold enhancement in detection sensitivity over traditional SPE or MIP adsorbents reported previously. The recoveries of fortified mussel and clam samples were achieved as 91.8 ± 1.2%-94.1 ± 1.9% (n = 3) and 91.2 ± 1.1%-94.5 ± 3.6% (n = 3), respectively. This work sheds light on a cost-effective method for online selective IT-SPME and the accurate monitoring of DA toxins using an aptamer@MOF-mediated affinity monolith system coupled with the inexpensive HPLC-UV technique.
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