Synthesis of Stable Cerium Oxide Nanoparticles Coated with Phosphonic Acid-Based Functional Polymers

Functional polymers, such as poly(ethylene glycol) (PEG), terminated with a single phosphonic acid, hereafter PEG-Ph are often applied to coat metal oxide surfaces during post-synthesis steps but are not sufficient to stabilize sub-10 nm particles in protein-rich biofluids. The instability is attributed to the weak binding affinity of post-grafted phosphonic acid groups, resulting in a gradual detachment of the polymers from the surface. Here, we assess these polymers as coating agents using an alternative route, namely, the one-step wet-chemical synthesis, where PEG-Ph is introduced with cerium precursors during the synthesis. Characterization of the coated cerium oxide nanoparticles (CNPs) indicates a core-shell structure, where the cores are 3 nm cerium oxide and the shell consists of functionalized PEG polymers in a brush configuration. Results show that CNPs coated with PEG_1k-Ph and PEG_2k-Ph are of potential interest for applications as nanomedicines due to their high Ce(III) content and increased colloidal stability in cell culture media. We further demonstrate that the CNPs in the presence of hydrogen peroxide show an additional absorbance band in the UV-vis spectrum, which is attributed to Ce-O₂^2- peroxo-complexes and could be used in the evaluation of their catalytic activity for scavenging reactive oxygen species.