Accurate Monitoring Platform for the Surface Catalysis of Nanozyme Validated by Surface-Enhanced Raman-Kinetics Model.

Surface-enhanced Raman scattering (SERS) is a supersensitive technique for monitoring catalytic reactions. However, building a SERS-kinetics model to investigate catalytic efficiency on the surface or interface of the catalyst remains a great challenge. In the present study, we successfully obtained an excellent semiconducting SERS substrate, reduced MnCo2O4 (R-MnCo2O4) nanotubes, whose favorable SERS sensitivity is mainly related to the promoted interfacial charge transfer caused by the introduction of oxygen vacancies as well as the electromagnetic enhancement effect. Furthermore, the R-MnCo2O4 nanotubes showed a favorable oxidase-like activity toward oxidation with the aid of molecular oxygen. It was also showed the oxidase-like catalytic process could be monitored using the SERS technique. A new SERS-kinetics model to monitor the catalytic efficiency of the oxidase-like reaction was developed, and the results demonstrate that the Vm values measured by the SERS-kinetics method are close to that obtained by the UV-vis approach, while the Km values measured by the SERS-kinetics method are much lower, demonstrating the better affinity between the enzyme and the substrate from SERS results and further confirming the high sensitivity of the SERS-kinetics approach and the actual enzyme-like reaction on the surface of nanozymes, which provides guidance in understanding the kinetics process and catalytic mechanism of natural enzymatic and other artificial enzymatic reactions. This work demonstrated the improved SERS sensitivity of defective semiconductors for the application of enzyme mimicking, providing a new frontier to construct highly sensitive biosensors.