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@ARTICLE{Allen:7756,
author = {Allen, B.. and Kotchey, G. and Chen, Y. and Yanamala, N.
and Klein-Seetharaman, J. and Kagan, V. and Star, A.},
title = {{M}echanistic {I}nvestigations of {H}orseradish
{P}eroxidase-{C}atalyzed {D}egradation of {S}ingle-{W}alled
{C}arbon {N}anotubes},
journal = {Journal of the American Chemical Society},
volume = {131},
issn = {0002-7863},
address = {Washington, DC},
publisher = {American Chemical Society},
reportid = {PreJuSER-7756},
pages = {17194 - 17205},
year = {2009},
note = {This work was supported by AFOSR, Grant no. FA
9550-09-1-0478; NIOSH OH008282 and the 7th Framework
Programme of the European Commission (NANOMMUNE).},
abstract = {Single-walled carbon nanotubes (SWNTs) have been
investigated for a variety of applications including
composite materials, electronics, and drug delivery.
However, these applications may be compromised depending on
the negative effects of SWNTs to living systems. While
reports of toxicity induced by SWNTs vary, means to
alleviate or quell these effects are in small abundance. We
have reported recently the degradation of carboxylated SWNTs
through enzymatic catalysis with horseradish peroxidase
(HRP). In this full Article, we investigated the degradation
of both carboxylated and pristine SWNTs with HRP and
compared these results with chemical degradation by hemin
and FeCl(3). The interaction between pristine and
carboxylated SWNTs with HRP was further studied by computer
modeling, and the products of the enzymatic degradation were
identified. By examining these factors with both pristine
and carboxylated SWNTs through a variety of techniques
including atomic force microscopy (AFM), transmission
electron microscopy (TEM), Raman spectroscopy,
ultraviolet-visible-near-infrared (UV-vis-NIR) spectroscopy,
gas chromatography-mass spectrometry (GC-MS),
high-performance liquid chromatography (HPLC), and liquid
chromatography-mass spectrometry (LC-MS), degradation
pathways were elucidated. It was observed that pristine
SWNTs demonstrate no degradation with HRP incubation but
display significant degradation when incubated with either
hemin or FeCl(3). Such data signify a heterolytic cleavage
of H(2)O(2) with HRP as pristine nanotubes do not degrade,
whereas Fenton catalysis results in the homolytic cleavage
of H(2)O(2) producing free radicals that oxidize pristine
SWNTs. Product analysis shows complete degradation produces
CO(2) gas. Conversely, incomplete degradation results in the
formation of different oxidized aromatic hydrocarbons.},
keywords = {Biocatalysis / Horseradish Peroxidase: metabolism /
Microscopy, Atomic Force / Microscopy, Electron,
Transmission / Nanotubes, Carbon / Spectrum Analysis:
methods / Nanotubes, Carbon (NLM Chemicals) / Horseradish
Peroxidase (NLM Chemicals) / J (WoSType)},
cin = {ISB-2},
ddc = {540},
cid = {I:(DE-Juel1)ISB-2-20090406},
pnm = {Programm Biosoft},
pid = {G:(DE-Juel1)FUEK443},
shelfmark = {Chemistry, Multidisciplinary},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:19891488},
UT = {WOS:000272207300042},
doi = {10.1021/ja9083623},
url = {https://juser.fz-juelich.de/record/7756},
}