Nanozyme based on CoFe₂O₄ modified with MoS₂ for colorimetric determination of cysteine and glutathione

A nanozyme based on CoFe₂O₄ modified with MoS₂ was constructed for colorimetric determination of cysteine (Cys) and glutathione (GSH). Firstly, ferrite CoFe₂O₄ is synthesized, and it is then modified by MoS₂ to form a flower-like polymer (MoS₂@CoFe₂O₄). In the presence of H₂O₂, a redox interaction takes place, and the resulting hydroxyl promoted a colorimetric conversion from colorless to blue in the presence of 3,3',5,5'-tetramethylbenzidine (TMB). However, once Cys or GSH is added, they are capable to compete with the interaction of the hydroxyl with TMB, resulting in an inhibition of the colorimetric conversion. The colorimetric distinction is sensitive to the amount of target. The results obtained proved that the catalytic efficiency of MoS₂@CoFe₂O₄ is 4.4-fold and 1.8-fold to that of MoS₂ and CoFe₂O₄. Meanwhile, the K_m values to TMB and H₂O₂ are 0.067 and 0.048 mM, respectively, which are 6.5-fold and 77-fold, respectively smaller than those of natural peroxidase such as HPR. This indicates that the MoS₂@CoFe₂O₄ possesses a favorable interaction affinity. Additionally, the colorimetric distinction caused by the competition between TMB and cysteine or glutathione is obvious. The signal responses to cysteine and glutathione are linear in the range 0.5~15 μM and 0.5~35 μM, and the LODs are 0.10 and 0.21 μM, respectively. In practical assay of Cys in serum, the RSD of the sample tests is 4.6%, and the recoveries for the spiked assays are 95.3% and 96.0% with the RSD of 2.1% and 4.2%, respectively.