Ratiometric Sensing for Ultratrace Tetracycline Using Electrochemically Active Metal–Organic Frameworks as Response Signals

A novel ratiometric sensor using an electrochemically active metal-organic framework of Mo@MOF-808 and NH2-UiO-66 as response signals was developed to detect tetracycline (TET) in ultratrace quantities. To achieve the dual-response strategy, Mo@MOF-808, with a reduction peak at -1.06 V, and NH2-UiO-66, with an oxidation peak at 0.724 V, were used as signal probes directly. Concretely, Mo@MOF-808, single-stranded DNA (ssDNA), and complex system (Apt@NH2-UiO-66) of aptamer (Apt) and NH2-UiO-66 were sequentially immobilized on the electrode. With the addition of TET, Apt was hybridized with TET and Apt@NH2-UiO-66 was detached from the electrode, resulting in an increase in the current at -1.06 V and a decrease in the current at 0.724 V. Through this strategy, the sensor achieved a wide linear range (0.1-10000 nM) and a low limit of detection (0.009792 nM) for TET. Moreover, the ratiometric sensor exhibited better sensitivity, reproducibility, and stability than a single-signal sensor. Furthermore, the constructed sensor was successfully applied to detect TET in milk samples, suggesting excellent application prospects.