A new and highly efficient CuMOF-based nanoenzyme and its application to the aptamer SERS/FL/RRS/Abs quadruple-mode analysis of ultratrace malachite green

Malachite green (MG) is highly toxic, persistent, and carcinogenic, and its widespread use is a danger to the ecosystem and a threat to public health and food safety, making it necessary to develop new sensitive multimode molecular spectroscopy methods. In this work, a new copper-based nanomaterial (CuNM) was prepared by a high-temperature roasting using a copper metal–organic framework (CuMOF) as precursor. The as-prepared CuNM was characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy, transmission electron microscopy (TEM), and BET surface area analysis. CuNM was found to catalyze the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) by H₂O₂ to produce the oxidation product TMBOX; however, subsequently, the MG aptamer (Apt) could be adsorbed on the CuNM surface by intermolecular interaction, which would inhibit the catalytic performance. After the addition of MG to be tested, the CuNM previously adsorbed by the Apt was transformed into its free state, thus restoring its catalytic activity. This new nanocatalytic indicator reaction could be monitored by surface-enhanced Raman scattering (SERS)/resonance Rayleigh scattering (RRS)/fluorescence (FL)/absorption (Abs) quadruple-mode methods. The SERS determination range was 0.004–0.4 nmol L⁻¹ MG, with a limit of detection of 0.0032 nM. In this way, a rapid, stable, and sensitive method for the determination of MG residues in the environment was established.