Achieving Ultrasmall Prussian Blue Nanoparticles as High-Performance Biomedical Agents with Multifunctions

Prussian blue nanoparticles (PBNPs), which belong to the iron-based metal-organic frameworks, are important biomedical agents. Reducing the size of PBNPs can bring improved functional properties, but unfortunately, has been a long-standing challenge. Herein, sub-5 nm ultrasmall PBNPs (USPBNPs) were successfully synthesized by using ethanol/water mixture as the solvent and polyvinyl pyrrolidone (PVP) as the surface capping agent. Adjusting the ethanol/water ratio is not only able to control the nucleation time and size of PBNPs but also tune the conformation of PVP molecules so as to prevent interparticle attachment and enlargement. At an ethanol/water ratio of 3:1, highly stable USPBNPs with a size of ∼3.4 nm were synthesized. Due to their large specific surface area, they demonstrated high peroxidase-like and catalase-like activities, which outperform PBNPs synthesized by a conventional method. In addition, they also showed a high longitudinal relaxation rate (r₁) of 1.3 mM^-1 S^-1, suggesting their potential to be used as T₁ MRI agent.