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ENDOR and HYSCORE Analysis and DFT-Assisted Identification of the Third Major Stable Radical in Sucrose Single Crystals X-Irradiated at Room Temperature

Hendrik De Cooman, Ewald Pauwels UGent, Henk Vrielinck UGent, Einar Sagstuen, Sabine Van Doorslaer, Freddy Callens UGent and Michel Waroquier UGent (2009) PHYSICAL CHEMISTRY CHEMICAL PHYSICS. 11(7). p.1105-1114
abstract
Recently, the chemical structure of two of the three major stable radicals (T2 and T3) produced in sucrose single crystals by X-irradiation at room temperature was identified by comparing Density Functional Theory (DFT) calculations of Electron Magnetic Resonance parameters with experimental results [H. De Cooman, E. Pauwels, H. Vrielinck, E. Sagstuen, F. Callens and M. Waroquier, J. Phys. Chem. B, 2008, 112, 7298-7307]. Ambiguities concerning an unusual proton hyperfine coupling (HFC) tensor prevented the identification of the third major stable radical (T1). In the present work, experimental results of continuous wave Electron Nuclear Double Resonance experiments on sucrose single crystals and Hyperfine Sublevel Correlation Spectroscopy experiments on sucrose powder are presented that lift these remaining ambiguities. Using the final set of experimental HFC tensors and employing advanced DFT calculations, the chemical structure of the T1 radical is established: an allylic-type radical with approximately half of the spin density localised on the C2' carbon of the fructose unit, involving glycosidic bond cleavage at the fructose side and a concerted formation of a carbonyl group at the C1' carbon. The electronic structure of the T1 radical is discussed in more detail by means of additional DFT calculations, yielding a better understanding of the peculiar properties of the unusual proton HFC tensor mentioned above.
Please use this url to cite or link to this publication:
author
organization
year
type
journalArticle (original)
publication status
published
journal title
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Phys. Chem. Chem. Phys.
volume
11
issue
7
pages
1105 - 1114
publisher
ROYAL SOC CHEMISTRY
place of publication
Cambridge, England
Web of Science type
Article
Web of Science id
000263113300013
JCR category
PHYSICS, ATOMIC, MOLECULAR & CHEMICAL
JCR impact factor
4.116 (2009)
JCR rank
3/33 (2009)
JCR quartile
1 (2009)
ISSN
1463-9084
1463-9076
DOI
10.1039/b816641b
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 Flemish Research Foundation (FWO-Vlaanderen). The authors acknowledge a Postdoctoral Fellowship (E. Pauwels and H. Vrielinck) and a Research Assistant Fellowship (H. De Cooman) with the same institution.
id
484180
handle
http://hdl.handle.net/1854/LU-484180
date created
2009-02-12 12:05:01
date last changed
2017-01-02 09:56:06
@article{484180,
  abstract     = {Recently, the chemical structure of two of the three major stable radicals (T2 and T3) produced in sucrose single crystals by X-irradiation at room temperature was identified by comparing Density Functional Theory (DFT) calculations of Electron Magnetic Resonance parameters with experimental results [H. De Cooman, E. Pauwels, H. Vrielinck, E. Sagstuen, F. Callens and M. Waroquier, J. Phys. Chem. B, 2008, 112, 7298-7307]. Ambiguities concerning an unusual proton hyperfine coupling (HFC) tensor prevented the identification of the third major stable radical (T1). In the present work, experimental results of continuous wave Electron Nuclear Double Resonance experiments on sucrose single crystals and Hyperfine Sublevel Correlation Spectroscopy experiments on sucrose powder are presented that lift these remaining ambiguities. Using the final set of experimental HFC tensors and employing advanced DFT calculations, the chemical structure of the T1 radical is established: an allylic-type radical with approximately half of the spin density localised on the C2' carbon of the fructose unit, involving glycosidic bond cleavage at the fructose side and a concerted formation of a carbonyl group at the C1' carbon. The electronic structure of the T1 radical is discussed in more detail by means of additional DFT calculations, yielding a better understanding of the peculiar properties of the unusual proton HFC tensor mentioned above.},
  author       = {De Cooman, Hendrik and Pauwels, Ewald and Vrielinck, Henk and Sagstuen, Einar and Van Doorslaer, Sabine and Callens, Freddy and Waroquier, Michel},
  issn         = {1463-9084},
  journal      = {PHYSICAL CHEMISTRY CHEMICAL PHYSICS},
  language     = {eng},
  number       = {7},
  pages        = {1105--1114},
  publisher    = {ROYAL SOC CHEMISTRY},
  title        = {ENDOR and HYSCORE Analysis and DFT-Assisted Identification of the Third Major Stable Radical in Sucrose Single Crystals X-Irradiated at Room Temperature},
  url          = {http://dx.doi.org/10.1039/b816641b},
  volume       = {11},
  year         = {2009},
}

Chicago
De Cooman, Hendrik, Ewald Pauwels, Henk Vrielinck, Einar Sagstuen, Sabine Van Doorslaer, Freddy Callens, and Michel Waroquier. 2009. “ENDOR and HYSCORE Analysis and DFT-Assisted Identification of the Third Major Stable Radical in Sucrose Single Crystals X-Irradiated at Room Temperature.” Physical Chemistry Chemical Physics 11 (7): 1105–1114.
APA
De Cooman, H., Pauwels, E., Vrielinck, H., Sagstuen, E., Van Doorslaer, S., Callens, F., & Waroquier, M. (2009). ENDOR and HYSCORE Analysis and DFT-Assisted Identification of the Third Major Stable Radical in Sucrose Single Crystals X-Irradiated at Room Temperature. PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 11(7), 1105–1114.
Vancouver
1.
De Cooman H, Pauwels E, Vrielinck H, Sagstuen E, Van Doorslaer S, Callens F, et al. ENDOR and HYSCORE Analysis and DFT-Assisted Identification of the Third Major Stable Radical in Sucrose Single Crystals X-Irradiated at Room Temperature. PHYSICAL CHEMISTRY CHEMICAL PHYSICS. Cambridge, England: ROYAL SOC CHEMISTRY; 2009;11(7):1105–14.
MLA
De Cooman, Hendrik, Ewald Pauwels, Henk Vrielinck, et al. “ENDOR and HYSCORE Analysis and DFT-Assisted Identification of the Third Major Stable Radical in Sucrose Single Crystals X-Irradiated at Room Temperature.” PHYSICAL CHEMISTRY CHEMICAL PHYSICS 11.7 (2009): 1105–1114. Print.