Influence of Functional Monomer Glutathione on Core-shell Double Heterostructured Nanocage NiO/NiFe2O4@Zn0.76Co0.24S Performances as Electrochemical Sensor for Bromisoval Determination
In this work, NiO/NiFe 2 O 4 @Zn 0.76 Co 0.24 S nanocages (NCs) with core-shell type double heterostructures were synthesized using a core-shell design scheme. Among them, NiO/NiFe 2 O 4 cubic cores were obtained by calcination of Ni-Fe Prussian blue analogs (PBAs), and Zn-Co-like zeolitic imidazole frameworks (ZIFs) growed in situ around these cubic cores and were sulfided to obtain NiO/NiFe 2 O 4 @Zn 0.76 Co 0.24 S NCs. The composite has a large specific surface area of 249.66 m 2 g -1 due to the inherited structure of the two bimetallic organic frameworks. And there is a core-shell double heterogeneous synergy between the Zn 0.76 Co 0.24 S NCs and p-p heterostructured NiO/NiFe 2 O 4 , which makes the modified electrode exhibit superior electrochemical performance for Bromisoval (BVU). In addition, glutathione (GSH) was explored to significantly enhance the electrochemical activity of BVU by nucleophilic substitution binding of its own -SH with -Br on BVU, which greatly improved the sensitivity. Then, GSH was developed as a new functional monomer, and beta-cyclodextrin (β-CD) was selected as a secondary functional monomer, and molecularly imprinted polymer (MIP) of BVU was prepared by CV electropolymerization to achieve a specific recognition of BVU. An electrochemical sensor based on NiO/NiFe 2 O 4 @Zn 0.76 Co 0.24 S NCs and MIP was constructed to detect BVU by DPV. Under the optimal conditions, the oxidation peak current of BVU was linear over the concentration range of 0.006-3.5 μM, with the limits of detection (LOD) and quantification (LOQ) of 0.28 nm and 0.933 nm, respectively. The sensitivity reached 11.0303 μA·μM -1 ·cm -2 . The method has a wider linear range and lower detection limits compared to other assays for BVU. And the sensor showed excellent reproducibility, repeatability and stability and had been applied to the determination of BVU in human serum and cosmetics with satisfactory results.
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