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Title: Antioxidant Deactivation on Graphenic Nanocarbon Surfaces

Abstract

This article reports a direct chemical pathway for antioxidant deactivation on the surfaces of carbon nanomaterials. In the absence of cells, carbon nanotubes are shown to deplete the key physiological antioxidant glutathione (GSH) in a reaction involving dissolved dioxygen that yields the oxidized dimer, GSSG, as the primary product. In both chemical and electrochemical experiments, oxygen is only consumed at a significant steady-state rate in the presence of both nanotubes and GSH. GSH deactivation occurs for single- and multi-walled nanotubes, graphene oxide, nanohorns, and carbon black at varying rates that are characteristic of the material. The GSH depletion rates can be partially unified by surface area normalization, are accelerated by nitrogen doping, and suppressed by defect annealing or addition of proteins or surfactants. It is proposed that dioxygen reacts with active sites on graphenic carbon surfaces to produce surface-bound oxygen intermediates that react heterogeneously with glutathione to restore the carbon surface and complete a catalytic cycle. The direct catalytic reaction between nanomaterial surfaces and antioxidants may contribute to oxidative stress pathways in nanotoxicity, and the dependence on surface area and structural defects suggest strategies for safe material design.

Authors:
 [1];  [2];  [2];  [2];  [1];  [2];  [1];  [1];  [1];  [2];  [2]
  1. ORNL
  2. Brown University
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Shared Research Equipment Collaborative Research Center
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1028162
DOE Contract Number:  
DE-AC05-00OR22725
Resource Type:
Journal Article
Journal Name:
Small
Additional Journal Information:
Journal Volume: 7; Journal Issue: 19; Journal ID: ISSN 1613-6810
Country of Publication:
United States
Language:
English
Subject:
59 BASIC BIOLOGICAL SCIENCES; 77 NANOSCIENCE AND NANOTECHNOLOGY; ANNEALING; ANTIOXIDANTS; CARBON; CARBON BLACK; DEACTIVATION; DEFECTS; DESIGN; GLUTATHIONE; NANOTUBES; NITROGEN; OXYGEN; PROTEINS; SURFACE AREA; SURFACTANTS; catalysis; nanohorn; nanotube; nanomaterial toxicity; antioxidant

Citation Formats

Liu, Xinyuan, Sen, Sujat, Liu, Jingyu, Kulaots, Indrek, Geohegan, David B, Kane, Agnes, Puretzky, Alexander A, Rouleau, Christopher M, More, Karren Leslie, Palmore, G. Tayhas R., and Hurt, Robert H. Antioxidant Deactivation on Graphenic Nanocarbon Surfaces. United States: N. p., 2011. Web. doi:10.1002/smll.201100651.
Liu, Xinyuan, Sen, Sujat, Liu, Jingyu, Kulaots, Indrek, Geohegan, David B, Kane, Agnes, Puretzky, Alexander A, Rouleau, Christopher M, More, Karren Leslie, Palmore, G. Tayhas R., & Hurt, Robert H. Antioxidant Deactivation on Graphenic Nanocarbon Surfaces. United States. https://doi.org/10.1002/smll.201100651
Liu, Xinyuan, Sen, Sujat, Liu, Jingyu, Kulaots, Indrek, Geohegan, David B, Kane, Agnes, Puretzky, Alexander A, Rouleau, Christopher M, More, Karren Leslie, Palmore, G. Tayhas R., and Hurt, Robert H. 2011. "Antioxidant Deactivation on Graphenic Nanocarbon Surfaces". United States. https://doi.org/10.1002/smll.201100651.
@article{osti_1028162,
title = {Antioxidant Deactivation on Graphenic Nanocarbon Surfaces},
author = {Liu, Xinyuan and Sen, Sujat and Liu, Jingyu and Kulaots, Indrek and Geohegan, David B and Kane, Agnes and Puretzky, Alexander A and Rouleau, Christopher M and More, Karren Leslie and Palmore, G. Tayhas R. and Hurt, Robert H.},
abstractNote = {This article reports a direct chemical pathway for antioxidant deactivation on the surfaces of carbon nanomaterials. In the absence of cells, carbon nanotubes are shown to deplete the key physiological antioxidant glutathione (GSH) in a reaction involving dissolved dioxygen that yields the oxidized dimer, GSSG, as the primary product. In both chemical and electrochemical experiments, oxygen is only consumed at a significant steady-state rate in the presence of both nanotubes and GSH. GSH deactivation occurs for single- and multi-walled nanotubes, graphene oxide, nanohorns, and carbon black at varying rates that are characteristic of the material. The GSH depletion rates can be partially unified by surface area normalization, are accelerated by nitrogen doping, and suppressed by defect annealing or addition of proteins or surfactants. It is proposed that dioxygen reacts with active sites on graphenic carbon surfaces to produce surface-bound oxygen intermediates that react heterogeneously with glutathione to restore the carbon surface and complete a catalytic cycle. The direct catalytic reaction between nanomaterial surfaces and antioxidants may contribute to oxidative stress pathways in nanotoxicity, and the dependence on surface area and structural defects suggest strategies for safe material design.},
doi = {10.1002/smll.201100651},
url = {https://www.osti.gov/biblio/1028162}, journal = {Small},
issn = {1613-6810},
number = 19,
volume = 7,
place = {United States},
year = {Sat Jan 01 00:00:00 EST 2011},
month = {Sat Jan 01 00:00:00 EST 2011}
}