DFT/B3LYP Study of the Substituent Effects on the Reaction Enthalpies of the Antioxidant Mechanisms of Sesamol Derivatives in the Gas phase and water

In this paper, the study of various ortho and meta–substituted Sesamol derivatives is presented. The reaction enthalpies related to three antioxidant action mechanisms HAT, SET–PT, and SPLET for substituted Sesamols, have been calculated using the DFT/B3LYP method in gas phase and water. Calculated results show that electron-withdrawing substituents increase the bond dissociation enthalpy (BDE), ionization potential (IP), and electron transfer enthalpy (ETE), while electron-donating ones cause a rise in the proton dissociation enthalpy (PDE) and proton affinity (PA). In the ortho position, substituents show a larger effect on reaction enthalpies than in the meta position. In comparison with the gas phase, water attenuates the substituent effect on all reaction enthalpies. In the gas phase, BDEs are lower than PAs and IPs, i.e., HAT represents the thermodynamically preferred pathway. On the other hand, the SPLET mechanism represents the thermodynamically favored process in water. Results show that calculated enthalpies can be successfully correlated with Hammett constants (
m) of the substituted Sesamols. Furthermore, calculated IP and PA values for substituted Sesamols show linear dependence on the energy of the highest occupied molecular orbital (EHOMO).

antioxidant, Sesamol, solvent effect, substituent effect, DFT, EHOMO.