Gold nanoparticles (AuNPs) with simultaneous plasmonic and biocatalytic properties provide a promising approach to developing versatile bioassays. However, the combination of AuNPs' intrinsic enzyme-mimicking properties with their surface-enhanced Raman scattering (SERS) activities has yet to be explored. Here we designed a peroxidase-mimicking nanozyme by in situ growing AuNPs into a highly porous and thermally stable metal-organic framework called MIL-101. The obtained AuNPs@MIL-101 nanozymes acted as peroxidase mimics to oxidize Raman-inactive reporter leucomalachite green into the active malachite green (MG) with hydrogen peroxide and simultaneously as the SERS substrates to enhance the Raman signals of the as-produced MG. We then assembled glucose oxidase (GOx) and lactate oxidase (LOx) onto AuNPs@MIL-101 to form AuNPs@MIL-101@GOx and AuNPs@MIL-101@LOx integrative nanozymes for in vitro detection of glucose and lactate via SERS. Moreover, the integrative nanozymes were further explored for monitoring the change of glucose and lactate in living brains, which are associated with ischemic stroke. The integrative nanozymes were then used to evaluate the therapeutic efficacy of potential drugs (such as astaxanthin for alleviating cerebral ischemic injuries) in living rats. They were also employed to determine glucose and lactate metabolism in tumors. This study not only demonstrated the great promise of combining AuNPs' multiple functionalities for versatile bioassays but also provided an interesting approach to designing nanozymes for biomedical and catalytic applications.

Reactive oxygen species (ROS) scavenging Mn3O4 nanozymes effectively protected live mice from ROS-induced ear-inflammation in vivo.

A peroxidase catalyzes the oxidation of a substrate with a peroxide. The search for peroxidase-like and other enzyme-like nanomaterials (called nanozymes) mainly relies on trial-and-error strategies, due to the lack of predictive descriptors. To fill this gap, here we investigate the occupancy of eg orbitals as a possible descriptor for the peroxidase-like activity of transition metal oxide (including perovskite oxide) nanozymes. Both experimental measurements and density functional theory calculations reveal a volcano relationship between the eg occupancy and nanozymes’ activity, with the highest peroxidase-like activities corresponding to eg occupancies of ~1.2. LaNiO3-δ, optimized based on the eg occupancy, exhibits an activity one to two orders of magnitude higher than that of other representative peroxidase-like nanozymes. This study shows that the eg occupancy is a predictive descriptor to guide the design of peroxidase-like nanozymes; in addition, it provides detailed insight into the catalytic mechanism of peroxidase-like nanozymes.