Ultrasensitive, label-free voltammetric determination of norfloxacin based on molecularly imprinted polymers and Au nanoparticle-functionalized black phosphorus nanosheet nanocomposite.

Norfloxacin (NOR) is an antibiotic commonly used to treat humans and food-producing animals. Owing to NOR abuse, its residues are frequently found in animal-derived food products and the surrounding environment. Therefore, development of an efficient analytical technique for the selective determination of trace NOR is greatly significant for food safety and environmental protection. Here, we fabricated an ultrasensitive, label-free molecularly imprinted polymer (MIP) voltammetric sensor for the selective determination of NOR, based on an Au nanoparticle-functionalized black phosphorus nanosheet nanocomposite (BPNS-AuNP) covered by a polypyrrole-imprinted film. BPNS-AuNP nanocomposites were prepared via an in-situ one-step method without the use of reducing agents. The imprinted polypyrrole film was formed on the surface of the BPNS-AuNPs in the presence of NOR. The physical properties and electrochemical behavior of the MIP/BPNS-AuNPs were investigated using various characterization techniques, and the analytical parameters were optimized. We found that BPNS-AuNPs improve the ambient stability and electrocatalytic activity, providing a large surface area for locating a higher number of specific recognition sites. Consequently, the MIP/BPNS-AuNP/GCE showed excellent sensing performance toward NOR, with a wide linear response range (0.1 nM - 10 μM), an extremely low limit of detection (0.012 nM), and extraordinary selectivity. Moreover, the MIP/BPNS-AuNP/GCE was used to determine NOR in various experimental samples with satisfactory results.