Engineering a glycosyl-imprinted nanozyme with a dual-ligand Ce-MOF for the selective and sensitive colorimetric...

The detection of carbohydrate antigen 19 - 9 (CA19-9), a critical serum marker for gastrointestinal malignancies, is particularly challenging because of its typically low concentration and substantial matrix interference, creating a critical demand for improved detection technologies. Herein, we rationally designed and synthesized a nanozyme with dual-ligand cerium-organic framework (Ce-MOF-BN) nanozyme for glycosyl-imprinted colorimetric biosensing via a one-pot method. The crystalline porous framework is densely functionalized on its surface with spatially accessible amino and boronic acid groups, enabling the recognition and oriented immobilization of imprinting templates. A well-defined core-shell molecularly imprinted composite was successfully fabricated through the systematic optimization of the ligand ratio. The composite exhibits intrinsic oxidase-like activity without requiring H₂O₂, and the molecularly imprinted polymer (MIP) shell supplies specific cavities for the highly selective recognition of CA19-9. Under optimized assay conditions, the sensor achieves the quantitative detection of CA19-9 across a broad linear range of 0.0001-100 U/mL, with a limit of detection as low as 2.7 × 10^- 5 U/mL. This work provides valuable insights for designing next-generation high performance biomimetic sensing materials and advancing their clinical diagnostic applications.