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Research Article

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

Tao Wen1,2,3,§, Hui Zhang1,§, Yu Chong2, Wayne G. Wamer4, Jun-Jie Yin2( ), Xiaochun Wu1( )
CAS Key Laboratory of Standardization and Measurement for NanotechnologyCAS Center for Excellence in NanoscienceNational Center for Nanoscience and TechnologyBeijing100190China
Division of Analytical ChemistryOffice of Regulatory ScienceCenter for Food Safety and Applied NutritionUS Food and Drug AdministrationCollege ParkMD20740USA
Institute of Basic Medical SciencesChinese Academy of Medical Sciences & Peking Union Medical CollegeBeijing100005China
Division of Bioanalytical ChemistryOffice of Regulatory ScienceCenter for Food Safety and Applied NutritionUS Food and Drug AdministrationCollege ParkMD20740USA

§ These authors contributed equally to this work.

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Abstract

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.

Keywords

gold nanorodoxygen activationhydroxyl radicalplasmon catalysiselectron spin resonance

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Nano Research
Volume 9 Issue 6,
June 2016
Pages 1663-1673
DOI: 10.1007/s12274-016-1060-7
Cite this article:
Wen T, Zhang H, Chong Y, et al. Probing hydroxyl radical generation from H2O2 upon plasmon excitation of gold nanorods using electron spin resonance: Molecular oxygen-mediated activation. Nano Research, 2016, 9(6): 1663-1673. https://doi.org/10.1007/s12274-016-1060-7

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Received: 25 November 2015
Revised: 23 December 2015
Accepted: 28 February 2016
Published: 29 April 2016
© Tsinghua University Press and Springer-Verlag Berlin Heidelberg 2016
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