Bimetallic cerium/copper organic framework-derived cerium and copper oxides embedded by mesoporous carbon: Label-free aptasensor for ultrasensitive tobramycin detection

We reported a novel bimetallic cerium/copper-based metal organic framework (Ce/Cu-MOF) and its derivatives pyrolyzed at different temperatures, followed by exploiting them as the scaffold of electrochemical aptamer sensors for extremely sensitive detection of trace tobramycin (TOB) in human serum and milk. After the calcination at high temperature, the meal coordination centers (Ce and Cu) were transferred to metal oxides containing various chemical valences, such as Ce(III), Ce(IV), Cu(II) and Cu(0), which were embedded within the mesoporous carbon network originated from the organic ligands (represented by CeO2/CuOx@mC). Owning to the strong synergistic effect among the metal oxides, mesoporous carbon, and small cavities and open channels of MOF, the as-prepared CeO2/CuOx@mC nanocomposites not only possess good electrochemical activity but also exhibit strong bioaffinity toward the aptamer strands. By comparing the electrochemical biosensing peroformances using on the Ce/Cu-MOF- and the series of CeO2/CuOx@mC-based aptasensors, the constructed CeO2/CuOx@mC900-based (calcinated at 900 °C) aptasensor exhibits an extremely low detection limit of 2.0 fg mL−1 within a broad linear TOB concentration range from 0.01 pg mL−1 to 10 ng mg L−1. It demonstrates that the proposed aptasensor is substantially superior to those previously reported in the literature, along with high selectivity, good stability and reproducibility, and acceptable applicability in human serum and milk. Thereby, the newly fabricated aptasensing approach based on bimetallic CeO2/CuOx@mC has a considerable potential for the quantitative detection of antibiotics in the food safety and biomedical field.