Density Functional Theory Investigation of the Biocatalytic Mechanisms of pH-Driven Biomimetic Behavior in CeO2
There is considerable interest in the pH-dependent, switchable, biocatalytic properties of cerium oxide (CeO2) nanoparticles in biomedicine, where these materials exhibit beneficial antioxidant activity against reactive oxygen species (ROS) at a basic physiological pH but cytotoxic prooxidant activi...
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Published in | ACS applied materials & interfaces Vol. 14; no. 9; pp. 11937 - 11949 |
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Main Authors | , , , , |
Format | Journal Article |
Language | English |
Published |
American Chemical Society
09.03.2022
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Abstract | There is considerable interest in the pH-dependent, switchable, biocatalytic properties of cerium oxide (CeO2) nanoparticles in biomedicine, where these materials exhibit beneficial antioxidant activity against reactive oxygen species (ROS) at a basic physiological pH but cytotoxic prooxidant activity in an acidic cancer cell pH microenvironment. While the general characteristics of the role of oxygen vacancies are known, the mechanism of their action at the atomic scale under different pH conditions has yet to be elucidated. The present work applies density functional theory (DFT) calculations to interpret, at the atomic scale, the pH-induced behavior of the stable {111} surface of CeO2 containing oxygen vacancies. Analysis of the surface-adsorbed media species reveals the critical role of pH on the interaction between ROS (•O2 – and H2O2) and the defective CeO2 {111} surface. Under basic conditions, the superoxide dismutase (SOD) and catalase (CAT) biomimetic reactions can be performed cyclically, scavenging and decomposing ROS to harmless products, making CeO2 an excellent antioxidant. However, under acidic conditions, the CAT biomimetic reaction is hindered owing to the limited reversibility of Ce3+ ↔ Ce4+ and formation ↔ annihilation of oxygen vacancies. A Fenton biomimetic reaction (H2O2 + Ce3+ → Ce4+ + OH– + •OH) is predicted to occur simultaneously with the SOD and CAT biomimetic reactions, resulting in the formation of hydroxyl radicals, making CeO2 a cytotoxic prooxidant. |
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AbstractList | There is considerable interest in the pH-dependent, switchable, biocatalytic properties of cerium oxide (CeO2) nanoparticles in biomedicine, where these materials exhibit beneficial antioxidant activity against reactive oxygen species (ROS) at a basic physiological pH but cytotoxic prooxidant activity in an acidic cancer cell pH microenvironment. While the general characteristics of the role of oxygen vacancies are known, the mechanism of their action at the atomic scale under different pH conditions has yet to be elucidated. The present work applies density functional theory (DFT) calculations to interpret, at the atomic scale, the pH-induced behavior of the stable {111} surface of CeO2 containing oxygen vacancies. Analysis of the surface-adsorbed media species reveals the critical role of pH on the interaction between ROS (•O2 – and H2O2) and the defective CeO2 {111} surface. Under basic conditions, the superoxide dismutase (SOD) and catalase (CAT) biomimetic reactions can be performed cyclically, scavenging and decomposing ROS to harmless products, making CeO2 an excellent antioxidant. However, under acidic conditions, the CAT biomimetic reaction is hindered owing to the limited reversibility of Ce3+ ↔ Ce4+ and formation ↔ annihilation of oxygen vacancies. A Fenton biomimetic reaction (H2O2 + Ce3+ → Ce4+ + OH– + •OH) is predicted to occur simultaneously with the SOD and CAT biomimetic reactions, resulting in the formation of hydroxyl radicals, making CeO2 a cytotoxic prooxidant. |
Author | Liu, Zhao Koshy, Pramod Hart, Judy N Ma, Hongyang Sorrell, Charles C |
AuthorAffiliation | Sino-French Institute of Nuclear Engineering and Technology School of Materials Science and Engineering |
AuthorAffiliation_xml | – name: School of Materials Science and Engineering – name: Sino-French Institute of Nuclear Engineering and Technology |
Author_xml | – sequence: 1 givenname: Hongyang orcidid: 0000-0003-1876-3041 surname: Ma fullname: Ma, Hongyang email: hongyang.ma@unsw.edu.au organization: School of Materials Science and Engineering – sequence: 2 givenname: Zhao surname: Liu fullname: Liu, Zhao organization: Sino-French Institute of Nuclear Engineering and Technology – sequence: 3 givenname: Pramod surname: Koshy fullname: Koshy, Pramod organization: School of Materials Science and Engineering – sequence: 4 givenname: Charles C surname: Sorrell fullname: Sorrell, Charles C organization: School of Materials Science and Engineering – sequence: 5 givenname: Judy N orcidid: 0000-0001-7584-779X surname: Hart fullname: Hart, Judy N email: j.hart@unsw.edu.au organization: School of Materials Science and Engineering |
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Title | Density Functional Theory Investigation of the Biocatalytic Mechanisms of pH-Driven Biomimetic Behavior in CeO2 |
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