Metal–Organic Frameworks Nanoarchitectures Boost Catalytic Activity for the Construction of Sensitive Immunosensor

Abstract Benefiting from the distinct structural features, metal‐organic frameworks (MOFs) open new significant opportunities for biomacromolecule encapsulation to design biofunctional composites, whereas their biological activity and utilization efficiency remain challenging for the construction of advanced immunosensor. Herein, biomacromolecules are spatially encapsulated integration on the cavity of peptide‐mediated MOFs with controllable nanoarchitectures, which amplifies the immunosensor signals via boosting bioactivity and utilization efficiency. Notably, the morphological evolution of MOFs composite including dodecahedrons, nanostars and flower‐shaped nanostructures is achieved by introducing peptide surface modifier to trigger the coordination defects procedure. Nanostars are evidenced with the enhanced catalytic activity of biomacromolecules, which amplifies the recognition signal via regulating the pore channel and particle size of biomacromolecules@MOFs composite, shortening the diffusion path of substrate molecules and promoting the interfacial contact. As proof‐of‐principle, imidacloprid is chosen as a model target to demonstrate the superiority of biomacromolecules@MOFs‐based immunosensor. Combining the enhanced activity of biomacromolecules with size tunability of biomacromolecules@MOFs composite, 160‐fold improvement in the sensitivity is obtained in comparison with the conventional enzyme‐based immunoassay, paving the way for the employment of controllable nanostructures for high‐sensitive biosensors.