Enhanced peroxidase-like activity of MOF nanozymes by co-catalysis for colorimetric detection of cholesterol

Abstract

Metal–organic frameworks (MOFs) have been widely used as nanozymes with a great development prospect due to their unique advantages. It is known that the current Fe-based or Cu-based MOF, etc., exhibits the catalytic activity of nanozymes through the Fenton catalytic reaction. And the conversion efficiency of the Fe³⁺/Fe²⁺ or Cu²⁺/Cu⁺ cycle is key to the catalytic activity. Therefore, we proposed a novel co-catalytic method to promote the reaction rate of the rate-limiting step of Cu²⁺/Cu⁺ conversion in the Fenton reaction of Cu²⁺/H₂O₂ to enhance the catalytic activity of the nanozymes. As a proof of concept, the MoCu-2MI nanozyme with high catalytic activity was successfully synthesized using Mo-doped Cu-2MI (2-methylimidazole). By using 3,3′,5,5′-tetramethylbenzidine (TMB) as the chromogenic substrate, MoCu-2MI exhibited higher peroxidase-like activity than pure Cu-2MI. Then, it was confirmed that the newly introduced Mo played a crucial co-catalytic role by characterizing the possible catalytic mechanism. Specifically, Mo acted as a co-catalyst to accelerate the electron transfer in the system, and then promote the Cu²⁺/Cu⁺ cycle in the Cu-Fenton reaction, which was conducive to accelerating the production of a large number of reactive oxygen species (ROS) from H₂O₂, and finally improve the activity. Ultimately, a biosensor platform combined with MoCu-2MI and cholesterol oxidase realized the one-step colorimetric detection of cholesterol in the range of 2–140 μM with the detection limit as low as 1.2 μM. This study provides a new strategy for regulating the activity of MOF nanozymes.