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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

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HPC-UGent: the central High Performance Computing infrastructure of Ghent University
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.

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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.
@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},
}

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