Naslov
The DFT local reactivity descriptors of alpha-tocopherol

Autori
Fabijanić, Ivana ; Jakobušić Brala, Cvijeta ; Pilepić, Viktor

Izvornik
Journal of molecular modeling (1610-2940) 21 (2015); 99-1

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
Antioxidant reactions; Fukui function; Average local ionization energy; Proton coupled electron transfer (PCET); Hydrogen atom transfer (HAT)

Sažetak
The calculations of local reactivity descriptors, the electron donor Fukui function fˉ(r), the average local ionization energy Ī(r), the Fukui function dual descriptor f(2)(r) and the electron acceptor Fukui function f+(r) for alpha-tocopherol, the main biologically active form of vitamin E for antioxidant reactions in phospholipid membranes, is presented. The calculations are performed at B3LYP/6-311++G** level of theory in the gas-phase. The obtained results indicate that the most preferred sites for donating electron in a reaction with radical or oxidizing molecule are associated mostly with pielectrons above and below the aromatic part of the alpha-tocopherol chromanol ring. The most reactive sites for accepting electrons are associated with the leaving H(9) atom in the extension of the phenolic OH bond on the alpha-tocopherol chromanol ring plane, in place where the formation of H-bond of the precursor complex between approaching reactive oxygen radical and phenolic OH group of alpha-tocopherol could be expected. The separated reactive sites in alpha-tocopherol suggest that the proton and electron, along with the hydrogen atom transfer (HAT) process, could also be transferred to different proton and electron acceptors as in bidirectional proton coupled electron transfer (PCET) reactions. The results presented in this paper suggest that large charge redistribution and significant pi-pi interactions may be expected in antioxidant reactions of alpha-tocopherol.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

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