1,2,3-propanetriol radicals formed during oxidative stress

The presented results attempt to approximate the proper structure of the radical formed as a result of the oxidation of 1,2,3-propanetriol. To fulfil the aim unstable radical originated in 1,2,3-propanetriol was trapped by PBN. Resulted spin adduct was measured using EPR spectroscopy and the isotropic hyperfine coupling constants a_iso (¹⁴ N) and a_iso (¹ H) were obtained by simulation of the EPR spectrum. The next step consisted of conducting a comparative analysis of EPR parameters, based on the calculations conducted at the DFT and MP2 methods level in open-shell formalism including solvent effects. For comparison, calculations were also carried out at the level of combined methods (UB3LYP/QCISD and UMP2/QCISD) in terms of the ONIOM formalism. Comparison of the experimental EPR data of the isotropic hyperfine coupling constants a_iso (¹⁴ N) and a_iso (¹ H) with the calculated parameters indicate that oxidation of 1,2,3-propanetriol leads to a carbon centred radical where unpaired electron is situated on the second (middle) carbon of 1,2,3-propanetriol. What is important, this conclusion could be made regardless of the chosen calculation method. However, it could be stated that for calculation of the isotropic hyperfine coupling constants a_iso (¹⁴ N) and a_iso (¹ H) of PBN/gly• adducts, UMP2 polarisable conductor calculation model with two ethanol molecules is explicitly defined.