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Identification of primary free radicals in trehalose dihydrate single crystals X-irradiated at 10 K

Mihaela Adeluta Tarpan UGent, Hendrik De Cooman UGent, Einar Sagstuen, Michel Waroquier UGent and Freddy Callens UGent (2011) PHYSICAL CHEMISTRY CHEMICAL PHYSICS. 13(23). p.11294-11302
abstract
Primary free radical formation in trehalose dihydrate single crystals X-irradiated at 10 K was investigated at the same temperature using X-band Electron Paramagnetic Resonance (EPR), Electron Nuclear Double Resonance (ENDOR) and ENDOR-induced EPR (EIE) techniques. The ENDOR results allowed the unambiguous determination of six proton hyperfine coupling (HFC) tensors. Using the EIE technique, these HF interactions were assigned to three different radicals, labeled R1, R2 and R3. The anisotropy of the EPR and EIE spectra indicated that R1 and R2 are alkyl radicals (i.e. carbon-centered) and R3 is an alkoxy radical (i.e. oxygen-centered). The EPR data also revealed the presence of an additional alkoxy radical species, labeled R4. Molecular modeling using periodic Density Functional Theory (DFT) calculations for simulating experimental data suggest that R1 and R2 are the hydrogen-abstracted alkyl species centered at C5’ and C5, respectively, while the alkoxy radicals R3 and R4 have the unpaired electron localized mainly at O2 and O4. Interestingly, the DFT study on R4 demonstrates that the trapping of a transferred proton can significantly influence the conformation of a deprotonated cation. Comparison of these results with those obtained from sucrose single crystals X-irradiated at 10 K indicates that the carbon situated next to the ring oxygen and connected to the CH2OH hydroxymethyl group is a better radical trapping site than other positions.
Please use this url to cite or link to this publication:
author
organization
year
type
journalArticle (original)
publication status
published
subject
keyword
DFT calculations, alkoxy, hyperfine couplings, ENDOR, EPR, ELECTRON MAGNETIC-RESONANCE, DENSITY-FUNCTIONAL THEORY, SPACE GAUSSIAN PSEUDOPOTENTIALS, RADIATION-INDUCED RADICALS, NUCLEAR DOUBLE-RESONANCE, ESR-ENDOR, SPIN-RESONANCE, RHAMNOSE CRYSTALS, TRAPPED ELECTRONS, D-GLUCOPYRANOSIDE
journal title
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Phys. Chem. Chem. Phys.
volume
13
issue
23
pages
11294 - 11302
Web of Science type
Article
Web of Science id
000291113200045
JCR category
PHYSICS, ATOMIC, MOLECULAR & CHEMICAL
JCR impact factor
3.573 (2011)
JCR rank
5/32 (2011)
JCR quartile
1 (2011)
ISSN
1463-9076
DOI
10.1039/C0CP02616F
language
English
UGent publication?
yes
classification
A1
copyright statement
I have transferred the copyright for this publication to the publisher
id
1223875
handle
http://hdl.handle.net/1854/LU-1223875
date created
2011-05-16 08:56:40
date last changed
2012-05-03 13:45:22
@article{1223875,
  abstract     = {Primary free radical formation in trehalose dihydrate single crystals X-irradiated at 10 K was investigated at the same temperature using X-band Electron Paramagnetic Resonance (EPR), Electron Nuclear Double Resonance (ENDOR) and ENDOR-induced EPR (EIE) techniques. The ENDOR results allowed the unambiguous determination of six proton hyperfine coupling (HFC) tensors. Using the EIE technique, these HF interactions were assigned to three different radicals, labeled R1, R2 and R3. The anisotropy of the EPR and EIE spectra indicated that R1 and R2 are alkyl radicals (i.e. carbon-centered) and R3 is an alkoxy radical (i.e. oxygen-centered). The EPR data also revealed the presence of an additional alkoxy radical species, labeled R4.
Molecular modeling using periodic Density Functional Theory (DFT) calculations for simulating experimental data suggest that R1 and R2 are the hydrogen-abstracted alkyl species centered at C5{\textquoteright} and C5, respectively, while the alkoxy radicals R3 and R4 have the unpaired electron localized mainly at O2 and O4. Interestingly, the DFT study on R4 demonstrates that the trapping of a transferred proton can significantly influence the conformation of a deprotonated cation.
Comparison of these results with those obtained from sucrose single crystals X-irradiated at 10 K indicates that the carbon situated next to the ring oxygen and connected to the CH2OH hydroxymethyl group is a better radical trapping site than other positions.},
  author       = {Tarpan, Mihaela Adeluta and De Cooman, Hendrik and Sagstuen, Einar and Waroquier, Michel and Callens, Freddy},
  issn         = {1463-9076},
  journal      = {PHYSICAL CHEMISTRY CHEMICAL PHYSICS},
  keyword      = {DFT calculations,alkoxy,hyperfine couplings,ENDOR,EPR,ELECTRON MAGNETIC-RESONANCE,DENSITY-FUNCTIONAL THEORY,SPACE GAUSSIAN PSEUDOPOTENTIALS,RADIATION-INDUCED RADICALS,NUCLEAR DOUBLE-RESONANCE,ESR-ENDOR,SPIN-RESONANCE,RHAMNOSE CRYSTALS,TRAPPED ELECTRONS,D-GLUCOPYRANOSIDE},
  language     = {eng},
  number       = {23},
  pages        = {11294--11302},
  title        = {Identification of primary free radicals in trehalose dihydrate single crystals X-irradiated at 10 K},
  url          = {http://dx.doi.org/10.1039/C0CP02616F},
  volume       = {13},
  year         = {2011},
}

Chicago
Tarpan, Mihaela Adeluta, Hendrik De Cooman, Einar Sagstuen, Michel Waroquier, and Freddy Callens. 2011. “Identification of Primary Free Radicals in Trehalose Dihydrate Single Crystals X-irradiated at 10 K.” Physical Chemistry Chemical Physics 13 (23): 11294–11302.
APA
Tarpan, M. A., De Cooman, H., Sagstuen, E., Waroquier, M., & Callens, F. (2011). Identification of primary free radicals in trehalose dihydrate single crystals X-irradiated at 10 K. PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 13(23), 11294–11302.
Vancouver
1.
Tarpan MA, De Cooman H, Sagstuen E, Waroquier M, Callens F. Identification of primary free radicals in trehalose dihydrate single crystals X-irradiated at 10 K. PHYSICAL CHEMISTRY CHEMICAL PHYSICS. 2011;13(23):11294–302.
MLA
Tarpan, Mihaela Adeluta, Hendrik De Cooman, Einar Sagstuen, et al. “Identification of Primary Free Radicals in Trehalose Dihydrate Single Crystals X-irradiated at 10 K.” PHYSICAL CHEMISTRY CHEMICAL PHYSICS 13.23 (2011): 11294–11302. Print.