Computer-Aided Design of Nanoceria Structures as Enzyme Mimetic Agents: The Role of Bodily Electrolytes on Maximising Their Activity.

Marco Molinari, Adam Symington, Dean C. Sayle, Tamilselvan Sakthivel, Sudipta Seal, Stephen Parker

Research output: Contribution to journalArticle

Abstract

Nanoceria, typically used for ‘clean air’ catalytic converter technologies because of its ability to capture, store and release oxygen is the same material that has the potential to be used in nanomedicine. Specifically, nanoceria can also be used to control oxygen content in cellular environments; as a ‘nanozyme’, nanoceria mimics enzymes by acting as an antioxidant agent. The computational design procedures for predicting active materials for catalytic converters can therefore be used to design active ceria nanozymes. Crucially, the ceria nanomedicine is not a molecule; rather it is a crystal and exploits its unique crystal properties. Here, we use ab initio and classical computer modelling, together with experiment, to design structures for nanoceria that maximise its nanozymetic activity. We predict that the optimum shape of the nanoparticles should have (truncated) polyhedral or cuboidal morphologies to expose (active) CeO2{100} surfaces. It should also contain oxygen vacancies and surface hydroxyl species. We also show that the surface structures strongly affects the biological activity of nanoceria. Analogous to catalyst poisoning, phosphorus 'poisoning' - the interaction of nanoceria with phosphate, a common bodily electrolyte – emanates from phosphate ions binding strongly to CeO2{100} surfaces, inhibiting oxygen capture and release and hence its ability to act as an nanozyme. Conversely, phosphate interaction with {111} surfaces is weak and therefore these surfaces protect the nanozyme against poisoning. The atom-level understanding presented here also illuminates catalytic processes and poisoning in ‘clean-air’ or fuel-cell technologies because the mechanism underpinning and exploited in each technology – oxygen capture, storage and release – is identical.
LanguageEnglish
JournalACS Applied Biomaterials
Early online date23 Jan 2019
DOIs
StatusE-pub ahead of print - 23 Jan 2019

Cite this

Computer-Aided Design of Nanoceria Structures as Enzyme Mimetic Agents: The Role of Bodily Electrolytes on Maximising Their Activity. / Molinari, Marco; Symington, Adam; Sayle, Dean C.; Sakthivel, Tamilselvan; Seal, Sudipta; Parker, Stephen.

In: ACS Applied Biomaterials, 23.01.2019.

Research output: Contribution to journalArticle

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