caa a22 4500 605512507 CHVBK 20210128100656.0 cr unu---uuuuu 210128e20150401xx s 000 0 eng 10.1007/s00894-015-2644-y doi (NATIONALLICENCE)springer-10.1007/s00894-015-2644-y The DFT local reactivity descriptors of α-tocopherol [Elektronische Daten] [Ivana Fabijanić, Cvijeta Jakobušić Brala, Viktor Pilepić] The calculations of local reactivity descriptors, the electron donor Fukui function f ˉ(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 α-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 π electrons above and below the aromatic part of the α-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 α-tocopherol chromanol ring plane, in the place where the formation of H-bond of the precursor complex between approaching reactive oxygen radical and phenolic OH group of α-tocopherol could be expected. The separated reactive sites in α-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 π-π interactions may be expected in antioxidant reactions of α-tocopherol. Graphical Abstract The DFT local reactivity descriptors reveal electron donor (blue) and acceptor (red) reactive sites and can be used in research of the initial stage of α-tocopherol antioxidant reactions Springer-Verlag Berlin Heidelberg, 2015 Antioxidant reactions nationallicence Average local ionization energy nationallicence Fukui function nationallicence Hydrogen atom transfer (HAT) nationallicence Proton coupled electron transfer (PCET) nationallicence Fabijanić Ivana Faculty of Pharmacy and Biochemistry, University of Zagreb, A. Kovačića 1, Zagreb, Croatia aut Jakobušić Brala Cvijeta Faculty of Pharmacy and Biochemistry, University of Zagreb, A. Kovačića 1, Zagreb, Croatia aut Pilepić Viktor Faculty of Pharmacy and Biochemistry, University of Zagreb, A. Kovačića 1, Zagreb, Croatia aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/4(2015-04-01), 1-7 1610-2940 21:4<1 2015 21 894 https://doi.org/10.1007/s00894-015-2644-y text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00894-015-2644-y text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Fabijanić Ivana Faculty of Pharmacy and Biochemistry, University of Zagreb, A. Kovačića 1, Zagreb, Croatia aut NATIONALLICENCE 700 1- Jakobušić Brala Cvijeta Faculty of Pharmacy and Biochemistry, University of Zagreb, A. Kovačića 1, Zagreb, Croatia aut NATIONALLICENCE 700 1- Pilepić Viktor Faculty of Pharmacy and Biochemistry, University of Zagreb, A. Kovačića 1, Zagreb, Croatia aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/4(2015-04-01), 1-7 1610-2940 21:4<1 2015 21 894