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EMR Study and DFT-assisted identification of transient radicals in X‑irradiated crystalline sucrose

Jevgenij Kusakovskij (UGent) , Freddy Callens (UGent) and Henk Vrielinck (UGent)
(2015) JOURNAL OF PHYSICAL CHEMISTRY B. 119(22). p.6562-6570
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HPC-UGent: the central High Performance Computing infrastructure of Ghent University
Abstract
Solid-state sucrose is a well-known dosimetric system, which is capable of reliable dose estimates only at a considerable time after exposure. Immediately after irradiation at room temperature, its electron paramagnetic resonance (EPR) spectrum is dominated by contributions from unstable radicals, which are studied here using continuous-wave EPR and electron−nuclear double resonance (ENDOR) spectroscopy. Four hyperfine tensors of proton couplings were determined, associated with two radical species, and subsequently compared to density functional theory calculation results, which led to the identification of the species with lower abundance (U2) as a radical formed by a H abstraction from C4. The more abundant center (U1) has not been definitively identified yet, but we present compelling evidence that it should be a C6 centered radical. Comparison of the simulated EPR spectra with all available data to the experimental ones suggests that the EPR spectrum of X-irradiated sucrose immediately after irradiation can now be almost entirely understood.
Keywords
sucrose, radiation-induced radicals, EPR, single crystals, X-rays, ENDOR, ELECTRON MAGNETIC-RESONANCE, DENSITY-FUNCTIONAL THEORY, SPACE GAUSSIAN PSEUDOPOTENTIALS, RADIATION-INDUCED DEFECTS, SINGLE-CRYSTALS, SPIN-RESONANCE, PARAMAGNETIC-RESONANCE, EPR-SPECTRUM, PARAMETERS, SUGAR

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Citation

Please use this url to cite or link to this publication:

Chicago
Kusakovskij, Jevgenij, Freddy Callens, and Henk Vrielinck. 2015. “EMR Study and DFT-assisted Identification of Transient Radicals in X‑irradiated Crystalline Sucrose.” Journal of Physical Chemistry B 119 (22): 6562–6570.
APA
Kusakovskij, J., Callens, F., & Vrielinck, H. (2015). EMR Study and DFT-assisted identification of transient radicals in X‑irradiated crystalline sucrose. JOURNAL OF PHYSICAL CHEMISTRY B, 119(22), 6562–6570.
Vancouver
1.
Kusakovskij J, Callens F, Vrielinck H. EMR Study and DFT-assisted identification of transient radicals in X‑irradiated crystalline sucrose. JOURNAL OF PHYSICAL CHEMISTRY B. 2015;119(22):6562–70.
MLA
Kusakovskij, Jevgenij, Freddy Callens, and Henk Vrielinck. “EMR Study and DFT-assisted Identification of Transient Radicals in X‑irradiated Crystalline Sucrose.” JOURNAL OF PHYSICAL CHEMISTRY B 119.22 (2015): 6562–6570. Print.
@article{5964611,
  abstract     = {Solid-state sucrose is a well-known dosimetric system, which is capable of reliable dose estimates only at a considerable time after exposure. Immediately after irradiation at room temperature, its electron paramagnetic resonance (EPR) spectrum is dominated by contributions from unstable radicals, which are studied here using continuous-wave EPR and electron\ensuremath{-}nuclear double resonance (ENDOR) spectroscopy. Four hyperfine tensors of proton couplings were determined, associated with two radical species, and subsequently compared to density functional theory calculation results, which led to the identification of the species with lower abundance (U2) as a radical formed by a H abstraction from C4. The more abundant center (U1) has not been definitively identified yet, but we present compelling evidence that it should be a C6 centered radical. Comparison of the simulated EPR spectra with all available data to the experimental ones suggests that the EPR spectrum of X-irradiated
sucrose immediately after irradiation can now be almost entirely understood.},
  author       = {Kusakovskij, Jevgenij and Callens, Freddy and Vrielinck, Henk},
  issn         = {1520-6106},
  journal      = {JOURNAL OF PHYSICAL CHEMISTRY B},
  keyword      = {sucrose,radiation-induced radicals,EPR,single crystals,X-rays,ENDOR,ELECTRON MAGNETIC-RESONANCE,DENSITY-FUNCTIONAL THEORY,SPACE GAUSSIAN PSEUDOPOTENTIALS,RADIATION-INDUCED DEFECTS,SINGLE-CRYSTALS,SPIN-RESONANCE,PARAMAGNETIC-RESONANCE,EPR-SPECTRUM,PARAMETERS,SUGAR},
  language     = {eng},
  number       = {22},
  pages        = {6562--6570},
  title        = {EMR Study and DFT-assisted identification of transient radicals in X\unmatched{2011}irradiated crystalline sucrose},
  url          = {http://dx.doi.org/10.1021/acs.jpcb.5b02468},
  volume       = {119},
  year         = {2015},
}

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