MOF-818(Cu)-derived bi-nanozymes of laccase and catecholase mimics and colorimetric sensing to epinephrine

Abstract

Cu-based nanozyme shows good oxidase-like activities due to the changeable states of Cu(II) and Cu(I), which are proven to be effective in the electron transfer in the redox process. Herein, the self-made MOF-818 with more Cu(II) loading was synthesized through a modified two-steps hydrothermal routes, which was then used as a sacrificial precursor to construct copper/zirconium composite oxides nanozymes (CN-MOF-818). The pyrolysis temperature was varied to obtain the best enzyme-like activities of the resulting CN-MOF-818. The laccase-like and catecholase-like activities were evaluated by using the oxidation of the mixture of 4-aminoantipyrine (4-AAP) and 2,4-dichlorophenol (2,4-DP), and 3,5-Di-tert-butylcatechol (3,5-DTBC) respectively. The enzyme-like activities were optimized through altering the catalytic conditions, and the corresponding enzyme catalytic kinetics including Km and Vmax were also determined. The enzyme-like mechanism of the CN-MOF-818 were also discussed based on EPR technique and the in-situ FT-IR analyses. In comparison with the pristine MOF-818 and the other reported Cu-based mimics, the as-prepared CN-MOF-818 exhibits the higher oxidase mimetic activities. These CN-MOF-818 can also be employed to detect the epinephrine with a low detection limit of 1.63 μM.