Novel dopamine-derived carbon modified fe-based metal–organic framework enhanced aptasensor rendering ultrasensitive electrochemical detection of oxytetracycline

Abstract

In the present work, an aptasensor with dual binding sites based on Au NPs modified with self-polymerized polydopamine (PDA) and Fe-MOF is successfully constructed. In terms of standard electron transfer, the cyclic voltammetry (CV) analysis showcases a rate constant (ks) of 96.0 s⁻¹, signifying an exceptional electron transfer rate of oxytetracycline at the sensor interface of Apt/Au@PDA@NH₂-MIL-101(Fe)/GCE. Further deepening the investigation into electrochemical kinetics using chronoamperometry (CA), we investigated the electrocatalytic parameters (K_cat) of Au@PDA@NH₂-MIL-101(Fe) in relation to oxytetracycline. The results divulged an impressive average K_cat value of 3.06 × 10⁵ M⁻¹ S^-1. This evidence robustly suggests the superior electrocatalytic activity of Au@PDA@NH₂-MIL-101(Fe) when it comes to oxytetracycline oxidation. A custom-designed portable rapid detection platform was developed, achieving detection limits of 6.88 nM under static water flow conditions and 5.56 nM under dynamic conditions. Remarkably, the self-polymerization of PDA on Au NPs not only refines their size but also boosts their interaction with biomolecules, thereby promising excellent biocompatibility. Moreover, the abundance of –COOH groups and unsaturated Fe³⁺ sites on the NH₂-MIL-101(Fe) surface furnishes a considerable number of grafting sites for the aptamer. More importantly, the redox interplay between Au@PDA and NH₂-MIL-101(Fe) accelerates electron movement, thus amplifying the electrochemical signal and the detection sensitivity for oxytetracycline.