Construction of Tb-MOF-on-Fe-MOF conjugate as a novel platform for ultrasensitive detection of carbohydrate antigen 125 and living cancer cells.

Combining different metal-organic frameworks (MOFs) into a conjugate material can integrate the properties of each MOF component and further lead to emergent properties from the synergistic heterostructured units. In this work, two kinds of bimetallic TbFe-MOFs have been designed by MOF-on-MOF strategy and utilized as a platform for anchoring carbohydrate antigen 125 (CA125) aptamer to detect CA125 and living michigan cancer foundation-7 (MCF-7) cells. Although the integrated MOF-on-MOF architectures show similar chemical and structural features to that of the top layer, the Fe-MOF-on-Tb-MOF and Tb-MOF-on-Fe-MOF have different surface nanostructures to their parent MOFs. The developed aptasensor based on Tb-MOF-on-Fe-MOF displays higher stability of the formed G-quadruplex between aptamer and CA125 than that based on Fe-MOF-on-Tb-MOF, owing to stronger immobilization behavior of the aptamer for the Tb-MOF-on-Fe-MOF composite. The developed aptasensor provides an extremely low detection limit of 58 μU·mL towards CA125 within a wide linear range from 100 μU·mL to 200 U·mL, which is significantly lower than those of all reported sensors. This aptasensor also has high selectivity, good stability, acceptable reproducibility, and excellent applicability in human serum. Moreover, the Tb-MOF-on-Fe-MOF nanoarchitecture demonstrates superior biocompatibility and good endocytosis. As a result, the developed aptasensor illustrates high sensitivity for detection of MCF-7 cells with an extremely low detection limit of 19 cell·mL. Therefore, the proposed aptasensor based on Tb-MOF-on-Fe-MOF exhibits great potentials for early diagnosis of tumors.