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Title: Perylene Diimide as a Precise Graphene-like Superoxide Dismutase Mimetic

Abstract

Here we show that the active portion of a graphitic nanoparticle can be mimicked by a perylene diimide (PDI) to explain the otherwise elusive biological and electrocatalytic activity of the nanoparticle construct. Development of molecular analogues that mimic the antioxidant properties of oxidized graphenes, in this case the poly(ethylene glycolated) hydrophilic carbon clusters (PEG–HCCs), will afford important insights into the highly efficient activity of PEG–HCCs and their graphitic analogues. PEGylated perylene diimides (PEGn–PDI) serve as well-defined molecular analogues of PEG–HCCs and oxidized graphenes in general, and their antioxidant and superoxide dismutase-like (SOD-like) properties were studied. PEGn–PDIs have two reversible reduction peaks, which are more positive than the oxidation peak of superoxide (O2•–). This is similar to the reduction peak of the HCCs. Thus, as with PEG–HCCs, PEGn–PDIs are also strong single-electron oxidants of O2•–. Furthermore, reduced PEGn–PDI, PEGn–PDI•–, in the presence of protons, was shown to reduce O2•– to H2O2 to complete the catalytic cycle in this SOD analogue. The kinetics of the conversion of O2•– to O2 and H2O2 by PEG8–PDI was measured using freeze-trap EPR experiments to provide a turnover number of 133 s–1; the similarity in kinetics further supports that PEG8–PDI is a true SOD mimetic. Finally,more » PDIs can be used as catalysts in the electrochemical oxygen reduction reaction in water, which proceeds by a two-electron process with the production of H2O2, mimicking graphene oxide nanoparticles that are otherwise difficult to study spectroscopically.« less

Authors:
; ;  [1]; ;  [2];  [1];  [3];  [1]; ORCiD logo
  1. Hematology, Internal Medicine, University of Texas Houston Medical School, Houston, Texas 77030, United States
  2. Argonne National Laboratory, X-ray Science Division, Advanced Photon Source, Argonne, Illinois 60439, United States
  3. Department of Neurology, Baylor College of Medicine, Houston, Texas 77030, United States; Center for Translational Research in Inflammatory Diseases, Michel E. DeBakey VA Medical Center, Houston, Texas 77030, United States
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Institutes of Health (NIH)
OSTI Identifier:
1413752
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: ACS Nano; Journal Volume: 11; Journal Issue: 2
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; electron paramagnetic resonance; perylene diimide; radical anion; reactive oxygen; superoxide dismutase

Citation Formats

Jalilov, Almaz S., Nilewski, Lizanne G., Berka, Vladimir, Zhang, Chenhao, Yakovenko, Andrey A., Wu, Gang, Kent, Thomas A., Tsai, Ah-Lim, and Tour, James M. Perylene Diimide as a Precise Graphene-like Superoxide Dismutase Mimetic. United States: N. p., 2017. Web. doi:10.1021/acsnano.6b08211.
Jalilov, Almaz S., Nilewski, Lizanne G., Berka, Vladimir, Zhang, Chenhao, Yakovenko, Andrey A., Wu, Gang, Kent, Thomas A., Tsai, Ah-Lim, & Tour, James M. Perylene Diimide as a Precise Graphene-like Superoxide Dismutase Mimetic. United States. doi:10.1021/acsnano.6b08211.
Jalilov, Almaz S., Nilewski, Lizanne G., Berka, Vladimir, Zhang, Chenhao, Yakovenko, Andrey A., Wu, Gang, Kent, Thomas A., Tsai, Ah-Lim, and Tour, James M. Tue . "Perylene Diimide as a Precise Graphene-like Superoxide Dismutase Mimetic". United States. doi:10.1021/acsnano.6b08211.
@article{osti_1413752,
title = {Perylene Diimide as a Precise Graphene-like Superoxide Dismutase Mimetic},
author = {Jalilov, Almaz S. and Nilewski, Lizanne G. and Berka, Vladimir and Zhang, Chenhao and Yakovenko, Andrey A. and Wu, Gang and Kent, Thomas A. and Tsai, Ah-Lim and Tour, James M.},
abstractNote = {Here we show that the active portion of a graphitic nanoparticle can be mimicked by a perylene diimide (PDI) to explain the otherwise elusive biological and electrocatalytic activity of the nanoparticle construct. Development of molecular analogues that mimic the antioxidant properties of oxidized graphenes, in this case the poly(ethylene glycolated) hydrophilic carbon clusters (PEG–HCCs), will afford important insights into the highly efficient activity of PEG–HCCs and their graphitic analogues. PEGylated perylene diimides (PEGn–PDI) serve as well-defined molecular analogues of PEG–HCCs and oxidized graphenes in general, and their antioxidant and superoxide dismutase-like (SOD-like) properties were studied. PEGn–PDIs have two reversible reduction peaks, which are more positive than the oxidation peak of superoxide (O2•–). This is similar to the reduction peak of the HCCs. Thus, as with PEG–HCCs, PEGn–PDIs are also strong single-electron oxidants of O2•–. Furthermore, reduced PEGn–PDI, PEGn–PDI•–, in the presence of protons, was shown to reduce O2•– to H2O2 to complete the catalytic cycle in this SOD analogue. The kinetics of the conversion of O2•– to O2 and H2O2 by PEG8–PDI was measured using freeze-trap EPR experiments to provide a turnover number of 133 s–1; the similarity in kinetics further supports that PEG8–PDI is a true SOD mimetic. Finally, PDIs can be used as catalysts in the electrochemical oxygen reduction reaction in water, which proceeds by a two-electron process with the production of H2O2, mimicking graphene oxide nanoparticles that are otherwise difficult to study spectroscopically.},
doi = {10.1021/acsnano.6b08211},
journal = {ACS Nano},
number = 2,
volume = 11,
place = {United States},
year = {Tue Jan 31 00:00:00 EST 2017},
month = {Tue Jan 31 00:00:00 EST 2017}
}