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-1 towards CA125 within a wide linear range from 100 μU·mL-1 to 200 U·mL-1, 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-1. Therefore, the proposed aptasensor based on Tb-MOF-on-Fe-MOF exhibits great potentials for early diagnosis of tumors.