Two-dimensional oriented growth of Zn-MOF-on-Zr-MOF architecture: A highly sensitive and selective platform for detecting cancer markers

Fabricating novel bimetallic metal organic framework (MOF) architectures and exploiting them as aptasensor scaffolds for detecting diverse analytes, especially cancer markers, have aroused widespread research attention. Herein, we report a novel strategy for obtaining ZnZr bimetallic MOFs via the MOF-on-MOF method and exploit them as an aptasensor platform for detecting the cancer marker protein tyrosine kinase-7 (PTK7). Basic characterizations reveal that the chemical structure, crystalline properties, and surface functionality of bimetallic ZnZr-MOFs can be modulated by changing the order of addition of metal precursors and organic ligands. The Zn-MOF-on-Zr-MOF hybrid exhibits a hierarchically decussated foliace, whereas Zr-MOF-on-Zn-MOF demonstrates a multilayered nanosheet structure. The electrochemical results reveal that Zr-MOF facilitates aptamer strand immobilization, whereas the Zn-MOF stabilizes the G-quadruplex formed by aptamer strands and PTK7. The Zn-MOF-on-Zr-MOF-based aptasensor outperforms the Zr-MOF-on-Zn-MOF-based one, providing ultralow detection limits of 0.84 and 0.66 pg mL-1, as obtained by electrochemical impedance spectroscopy and differential pulse voltammetry, respectively, within the PTK7 concentration range of 1.0 pg mL-1 to 1.0 ng mL-1. The proposed Zn-MOF-on-Zr-MOF-based aptasensor exhibits high selectivity in the presence of various interferences, good stability, reproducibility, and acceptability in human serum. The proposed strategy provides a new approach for fabricating ultrasensitive and selective bimetallic MOFs-based aptasensors and contributes to efforts to broaden their applications in early cancer diagnosis.