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Oxidation and reduction products of X irradiation at 10 K in sucrose single crystals: radical identification by EPR, ENDOR, and DFT

Hendrik De Cooman UGent, Ewald Pauwels UGent, Henk Vrielinck UGent, Einar Sagstuen, Michel Waroquier UGent and Freddy Callens UGent (2010) JOURNAL OF PHYSICAL CHEMISTRY B. 114(1). p.666-674
abstract
Electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR), and ENDOR-induced EPR (EIE) measurements oil Sucrose single crystals at 10 K after in situ X irradiation at this temperature reveal the presence of at least nine different radical species. Nine proton hyperfine coupling tensors were determined from ENDOR angular variations and assigned to six of these species (R1-R6) using EIE. Spectral simulations indicate that four of those (R1-R3 and R6) dominate the EPR absorption. Assisted by periodic density functional theory (DFT) calculations, R1 and R2 are identified as H-abstracted C1- and C5-centered radicals, R3 is tentatively assigned to all H-abstracted C6-centered radical, and R6 is identified as an alkoxy radical where the abstracted hydroxy proton has migrated to a neighboring OH group via intermolecular proton transfer. The latter radical had been characterized and identified in it previous Study, but the present DFT calculations provide additional insight Into its conformation and particular properties. This Study provides the first step ill unraveling the formation mechanism of the stable Sucrose radicals detected after 1,room-temperature irradiation and contributes to the understanding of the initial stages of radiation damage to solid-state carbohydrates.
Please use this url to cite or link to this publication:
author
organization
year
type
journalArticle (original)
publication status
published
subject
keyword
DENSITY-FUNCTIONAL THEORY, GUANINE DERIVATIVES, ELECTRON MAGNETIC-RESONANCE, RADIATION-INDUCED RADICALS, NUCLEAR DOUBLE-RESONANCE, PROTON HYPERFINE COUPLINGS, SPACE GAUSSIAN PSEUDOPOTENTIALS, METHYL-D-GLUCOPYRANOSIDE, TRAPPED ELECTRONS, ESR-ENDOR
journal title
JOURNAL OF PHYSICAL CHEMISTRY B
J. Phys. Chem. B
volume
114
issue
1
pages
666 - 674
Web of Science type
Article
Web of Science id
000273404500080
JCR category
CHEMISTRY, PHYSICAL
JCR impact factor
3.603 (2010)
JCR rank
32/125 (2010)
JCR quartile
2 (2010)
ISSN
1520-6106
DOI
10.1021/jp909247z
project
HPC-UGent: the central High Performance Computing infrastructure of Ghent University
project
HPC-UGent: the central High Performance Computing infrastructure of Ghent University
language
English
UGent publication?
yes
classification
A1
additional info
This work was financially Supported by the COST (European Cooperation in the held of Scientific and Technical Research), action P15. The authors acknowledge a Postdoctoral Fellowship (E.P. and H.V.) and a Research Assistant Fellowship (H.D.C.) with the Flemish Research Foundation (FWO-Vlaanderen). Part of the computational resources and Services used in this work were provided by Ghent University.
copyright statement
I have transferred the copyright for this publication to the publisher
id
834358
handle
http://hdl.handle.net/1854/LU-834358
date created
2010-01-22 11:01:08
date last changed
2013-09-17 10:50:07
@article{834358,
  abstract     = {Electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR), and ENDOR-induced EPR (EIE) measurements oil Sucrose single crystals at 10 K after in situ X irradiation at this temperature reveal the presence of at least nine different radical species. Nine proton hyperfine coupling tensors were determined from ENDOR angular variations and assigned to six of these species (R1-R6) using EIE. Spectral simulations indicate that four of those (R1-R3 and R6) dominate the EPR absorption. Assisted by periodic density functional theory (DFT) calculations, R1 and R2 are identified as H-abstracted C1- and C5-centered radicals, R3 is tentatively assigned to all H-abstracted C6-centered radical, and R6 is identified as an alkoxy radical where the abstracted hydroxy proton has migrated to a neighboring OH group via intermolecular proton transfer. The latter radical had been characterized and identified in it previous Study, but the present DFT calculations provide additional insight Into its conformation and particular properties. This Study provides the first step ill unraveling the formation mechanism of the stable Sucrose radicals detected after 1,room-temperature irradiation and contributes to the understanding of the initial stages of radiation damage to solid-state carbohydrates.},
  author       = {De Cooman, Hendrik and Pauwels, Ewald and Vrielinck, Henk and Sagstuen, Einar and Waroquier, Michel and Callens, Freddy},
  issn         = {1520-6106},
  journal      = {JOURNAL OF PHYSICAL CHEMISTRY B},
  keyword      = {DENSITY-FUNCTIONAL THEORY,GUANINE DERIVATIVES,ELECTRON MAGNETIC-RESONANCE,RADIATION-INDUCED RADICALS,NUCLEAR DOUBLE-RESONANCE,PROTON HYPERFINE COUPLINGS,SPACE GAUSSIAN PSEUDOPOTENTIALS,METHYL-D-GLUCOPYRANOSIDE,TRAPPED ELECTRONS,ESR-ENDOR},
  language     = {eng},
  number       = {1},
  pages        = {666--674},
  title        = {Oxidation and reduction products of X irradiation at 10 K in sucrose single crystals: radical identification by EPR, ENDOR, and DFT},
  url          = {http://dx.doi.org/10.1021/jp909247z},
  volume       = {114},
  year         = {2010},
}

Chicago
De Cooman, Hendrik, Ewald Pauwels, Henk Vrielinck, Einar Sagstuen, Michel Waroquier, and Freddy Callens. 2010. “Oxidation and Reduction Products of X Irradiation at 10 K in Sucrose Single Crystals: Radical Identification by EPR, ENDOR, and DFT.” Journal of Physical Chemistry B 114 (1): 666–674.
APA
De Cooman, H., Pauwels, E., Vrielinck, H., Sagstuen, E., Waroquier, M., & Callens, F. (2010). Oxidation and reduction products of X irradiation at 10 K in sucrose single crystals: radical identification by EPR, ENDOR, and DFT. JOURNAL OF PHYSICAL CHEMISTRY B, 114(1), 666–674.
Vancouver
1.
De Cooman H, Pauwels E, Vrielinck H, Sagstuen E, Waroquier M, Callens F. Oxidation and reduction products of X irradiation at 10 K in sucrose single crystals: radical identification by EPR, ENDOR, and DFT. JOURNAL OF PHYSICAL CHEMISTRY B. 2010;114(1):666–74.
MLA
De Cooman, Hendrik, Ewald Pauwels, Henk Vrielinck, et al. “Oxidation and Reduction Products of X Irradiation at 10 K in Sucrose Single Crystals: Radical Identification by EPR, ENDOR, and DFT.” JOURNAL OF PHYSICAL CHEMISTRY B 114.1 (2010): 666–674. Print.