Construction of Ce-MOF@COF hybrid nanostructure: Label-free aptasensor for the ultrasensitive detection of oxytetracycline residues in aqueous solution environments

Porous organic framework (COF) nanomaterials have drawn increasing attention and showed promising potential in the applications of various fields. Nevertheless, its applications in biosensing or biomedical fields are still in the early stage. In this work, we designed and synthesized a series of nanohybrids of COF and Ce-based metal organic framework (Ce-MOF) for the first time as label-free bioplatforms for a sensitive electrochemical aptasensor to detect oxytetracycline (OTC). A novel kinds of Ce-MOF@COF hybrids were prepared by adding different dosages of COF, into the preparation system of Ce-MOF, for which COF was synthesized using melamine and cyanutic acidmonomers through polycondensation (represented by MCA). Basic characterizations revealed that Ce-MOF@MCA nanohybrids not only remained their orignal crystal and chemical structure and features, such as different Ce species containing in Ce-MOF (Ce3+ and Ce4+), various functional amino-groups of MCA, and individual frameworks, but also showed a large specific surface area and interpenetrated morphologies. As a result, the Ce-MOF@MCA hybrid with high content of MCA exhibited high bioaffinity toward the OTC-targeted aptamer, further leading to the incremental detection effect for OTC detection. Among different hybrid-based aptasensors, the Ce-MOF@MCA-based one with an MCA dosage of 500 mg exhibited the lowest limit of detection at 17.4 fg mL-1 within a wider linearity of the OTC concentration within 0.1-0.5 ng mL-1. Additionally, the fabricated aptasensor displayed excellent analytical performance with great reproducibility, high selectivity and stability, and acceptable applicability for detecting OTC in various aqueous solutions, including milk, wastewater, and urine samples. This new Ce-MOF@MCA hybrid will become an excellent aptasensors platform for detecting various analytes, such as antibiotics, heavy metal ions, or cancer markers, and it have shown the promissing application potentials in the fields of biomedicine, food safety and environmental monitoring.