title: A determination of antioxidant efficiencies using ESR and computational methods.
abstract: Using Transition-State Theory, experimental rate constants, determined over a range of temperatures, for reactions of Vitamin E type antioxidants are analysed in terms of their enthalpies and entropies of activation. It is further shown that computational methods may be employed to calculate enthalpies and entropies, and hence Gibbs free energies, for the overall reactions. Within the linear free energy relationship (LFER) assumption, that the Gibbs free energy of activation is proportional to the overall Gibbs free energy change for the reaction, it is possible to rationalise, and even to predict, the relative contributions of enthalpy and entropy for reactions of interest, involving potential antioxidants. A method is devised, involving a competitive reaction between *CH3 radicals and both the spin-trap PBN and the antioxidant, which enables the relatively rapid determination of a relative ordering of activities for a series of potential antioxidant compounds, and also of their rate constants for scavenging *CH3 radicals (relative to the rate constant for addition of *CH3 to PBN).
authors.affiliation: School of Pharmacy and Chemistry, Liverpool John Moores University, Byrom St., Liverpool L3 3AF, UK. c.j.rhodes@livjm.ac.uk
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Rhodes
authors.forename: Thuy T
authors.initials: TT
authors.lastname: Tran
authors.forename: Harry
authors.initials: H
authors.lastname: Morris
mesh_terms: D000975:Antioxidants / Q000032:analysis*; D019295:Computational Biology; D004578:Electron Spin Resonance Spectroscopy; D019277:Entropy; D016166:Free Radical Scavengers / Q000737:chemistry; D007700:Kinetics; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D021281:Quantitative Structure-Activity Relationship; D019097:Spin Trapping; D013696:Temperature; D013816:Thermodynamics; D014810:Vitamin E / Q000737:chemistry
chemical_list: D000975:Antioxidants; D016166:Free Radical Scavengers; D014810:Vitamin E; C051224:methyl radical; D008697:Methane