Core-Shell Heterostructured CuFe@FeFe Prussian Blue Analogue Coupling with Silver Nanoclusters via a One-Step Bioinspired Approach: Efficiently Nonlabeled Aptasensor for Detection of Bleomycin in Various Aqueous Environments.

We synthesized novel core-shell heterostructured Prussian blue analogue (PBA) nanospheres coupled with silver nanoclusters (AgNCs) via a one-step bioinspired approach and further exploited these as aptasensors for the detection of a trace antibiotic, bleomycin (BLM). Using FeFe Prussian blue (FeFe PB) as the core, a bimetallic CuFe@FeFe PBA layer was prepared by coupling with AgNCs synthesized by taking the BLM-targeted aptamer as a template (denoted by AgNCs/Apt@CuFe@FeFe). The coupling of AgNCs/Apt via a one-step bioinspired approach not only can improve the sensing performance of CuFe@FeFe-based aptasensors but also can shorten the aptasensor fabrication procedure. Due to the strong coordination interaction between abundant Fe(II) ions contained in CuFe@FeFe PBA nanospheres and BLM (represented by Fe(II)·BLM), the Fe(II)·BLM complex formed enables aptamer strands to undergo an irreversible cleavage event that can result in a significant change in electrochemical activity. Electrochemical results displayed that both CuFe@FeFe- and AgNCs/Apt@CuFe@FeFe-based aptasensors exhibited high sensitivity and selectivity, good stability and reproducibility, and acceptable applicability toward BLM. In comparison with the pristine CuFe@FeFe-based aptasensor (limit of detection (LOD) = 0.49 fg mL-1 within the BLM concentration from 1.0 to 2.0 ng mL-1), the as-prepared AgNCs/Apt@CuFe@FeFe-based aptasensor gave a extremely lower LOD value of 0.0082 fg mL-1 within a relatively narrow BLM concentration range (0.01 fg mL-1 to 0.1 pg mL-1). The proposed method can broaden the application of PBA nanomaterials in food safety and biosensing fields and provides a potential determination method for rapidly detecting BLM in various aqueous environments.