https://nova.newcastle.edu.au/vital/access/ /manager/Index ${session.getAttribute("locale")} 5 https://nova.newcastle.edu.au/vital/access/ /manager/Repository/uon:34304 Thu 28 Oct 2021 12:36:45 AEDT ]]> https://nova.newcastle.edu.au/vital/access/ /manager/Repository/uon:52445 4+/Ce³⁺ compositions. Using DFT calculations combined with Bader charge analysis, it is demonstrated that stoichiometric ceria registers a higher oxidase mimetic activity than oxygen-deficient ceria with a low Ce⁴⁺/Ce³⁺ ratio due to a higher charge transfer from a substrate, 3,3',5,5' tetramethylbenzidine (TMB), to the ceria surface. We also show that the fluoride ions can significantly increase the charge transfer from the TMB surface to ceria irrespective of the surface Ce⁴⁺/Ce³⁺ ratio. Using this knowledge, we first compare the fluoride sensing properties of nanoceria with high Ce⁴⁺ and mixed Ce⁴⁺/Ce³⁺ oxidation states and further demonstrate that the linear detection range of fluoride ions can be extended to 1-10 ppm for nanoceria with mixed oxidation states. Then, we also demonstrate an assay for fluoride assisted detection of glutathione, an antioxidant with elevated levels during cancer, using nanoceria with a high surface Ce⁴⁺/Ce³⁺ ratio. The addition of fluoride ions in this assay allows the detection of glutathione in the linear range of 2.5-50 ppm with a limit of detection (LOD) of 3.8 ppm. These studies not only underpin the role of the surface Ce⁴⁺/Ce³⁺ ratio in tuning the fluoride assisted boost in the oxidase mimetic activity of nanoceria but also its strategic application in designing better colourimetric assays.]]> Thu 12 Oct 2023 15:28:04 AEDT ]]>