Herein, a hierarchically porous Zr-MOF-labeled electrochemical aptasensor based on the composite of PtPd@Ni-Co hollow nanoboxes (PtPd@Ni-Co HNBs) and poly (diallyldimethylammonium chloride)-functionalized graphene (PDDA-Gr) was developed for ultrasensitive detection of chloramphenicol (CAP). PtPd@Ni-Co HNBs have excellent conductivity and provide binding sites for aptamers; the functionalized PDDA-Gr improves its dispersibility and conductivity as a substrate material, which can be successfully used to increase the electrode surface area and support more PtPd@Ni-CoHNBs. Besides, hierarchically porous Zr-MOFs (HP-UiO-66) were utilized as signal probes and showed a stronger load capacity for signal molecules than conventional UiO-66. In the presence of CAP, two ingeniously designed Exo III-assisted cyclic amplification strategies further improved the sensitivity of the aptasensor: CAP causes cycle I to release a large amount of trigger DNA (Tr DNA), and then, Tr DNA initiated cycle II, which causes the exposed capture DNA to further bind the signal probes. With these advantages, the constructed aptasensors performed with satisfactory sensitivity in a wide linear range (10 fM-10 nM) and a detection limit of 0.985 fM. Several signal amplification strategies adopted in this study have effectively improved the performance of the sensor, providing a new avenue for the development of ultrasensitive sensors in the food analysis field.
Keywords: PDDA-Gr; PtPd@Ni-Co hollow nanoboxes; Zr-MOFs; chloramphenicol; electrochemical aptasensor; recycling amplification.