Probing hydroxyl radical generation from H₂O₂ upon plasmon excitation of gold nanorods using electron spin resonance: Molecular oxygen-mediated activation

Gold nanostructures are among the noble metal nanomaterials being intensely studied due to their good biocompatibility, tunable localized surface plasmon resonance (SPR), and ease of modification. These properties give gold nanostructures many potential chemical and biomedical applications. Herein, we demonstrate the critical role of oxygen activation during the decomposition of hydrogen peroxide (H₂O₂) in the presence of photoexcited gold nanorods (AuNRs) by using electron spin resonance (ESR) techniques. Upon SPR excitation, O₂ is activated first, and the resulting reactive intermediates further activate H₂O₂ to produce?OH. The reactive intermediates exhibit singlet oxygen-like (¹O₂-like) reactivity, indicated by ¹O₂-specific oxidation reaction, quenching behaviors, and the lack of the typical ¹O₂ ESR signal. In addition, by using the antioxidant sodium ascorbate (NaA) as an example, we show that hydroxyl radicals from H₂O₂ activation can induce much stronger NaA oxidation than that in the absence of H₂O₂. These results may have significant biomedical implications. For example, as oxidative stress levels are known to influence tumorigenesis and cancer progression, the ability to control redox status inside tumor microenvironments using noble metal nanostructures may provide new strategies for regulating the metabolism of reactive oxygen species and new approaches for cancer treatment.