Photolyase-Like Catalytic Behavior of CeO₂

Abstract

Nanomaterials with intrinsic enzyme-like characteristics exhibit their great potentials as alternatives to natural enzymes. Among various enzymes, the finding of substitutes of DNA photolyases, a family of photoenzymes for repairing the ultraviolet (UV)-induced DNA damage by forming cyclobutane pyrimidine dimers (CPDs) between two adjacent thymines in a DNA strand, is still unsuccessful. CPDs raise significant health concerns in various skin diseases. Essentially, DNA photolyases selectively split dimers into monomers by photoelectrons under visible-light irradiation, and this is a photocatalytic process. However, the majority of semiconductors are unprosperous due to the accompanied photogenerated reactive oxygen species (ROS), which decompose CPDs into fragments and thereby lead to a nonselective photocatalysis. Fortunately, CeO₂ as a semiconductor might deliver the selectively photocatalytic repair of UV-induced DNA damages, where the photoelectrons are used for the CPD cleavage, and the photogenerated ROS are locally suppressed for its antioxidant nature. Herein, we reported the defective porous CeO₂ delivered the photolyase-like activity by enhancing visible-light absorption, enabling the effective interaction between CPDs and catalysts, and subsequently triggering the selective photocleavage of CPDs into monomers. Further, <i>in vitro</i> cellular and <i>in vivo</i> animal evaluations illustrated its high potentials as alternatives to DNA photolyases.