Antioxidant capacity of novel amine derivatives of buckminsterfullerene: Determination of inhibition rate constants in a model oxidation system

The radical scavenging efficiency of fullerenes can be significantly activated by means of a connection with hydrogen donating groups of antioxidants such as phenolic, amine and sulfhydryl. The developed system of conjugated sigma-pi bonds arranged in the fullerene molecule in a closed shape can promote a strong resonance effect on the grafted units and increase the hydrogen atom abstraction efficiency. In this case the known ability of fullerene to trap alkyl radicals might be combined with the strong chain breaking functionality to afford a new class of antioxidants with bimodal action. Explorations in the field of fullerene derivatives on their antioxidant performance provide novel information on the potential stabilization properties of this type of molecular structure. A series of amine derivatives of buckminsterfullerene (C-60) with tethered aliphatic chain, cycloaliphatic and aromatic fragments were synthesized and their antioxidant activity was determined. The antioxidant activity of the investigated derivatives was studied by measuring the inhibition rate constants for their reaction with alkyl and peroxy radicals in a model cumene initiated (2,2'-azobisisobutyronitrile, AIBN) oxidation experiments and compared to that recorded under identical experiments for buckminsterfullerene itself and commercial primary aromatic amine stabilizers. The results indicate that linking the amine moieties groups directly to the fullerene core gives rise to a new chain breaking antioxidant mode for the buckminsterfullerene while cyclic fragments containing the same but distant amine group do not reveal this ability. The inhibition rate constants for trapping of peroxy radicals by the amine derivatives were found to be higher than that of known aromatic amine antioxidants Neozone-D and Naugard 445. In addition the C-60 Part of these molecules acts synergistically by trapping alkyl radicals with inhibition rate constants which exceed that of underivatised fullerene. The amine derivative containing sterically hindered piperidine and pyrrolidine fragments also heighten the inherent rate constant of buckminsterfullerene for scavenging alkyl radicals due to the additional antioxidant contribution promoted by the radical-quenching ability of the formed nitroxyl intermediates. These novel C-60-amine conjugates may be considered as promising molecules for broad-spectrum radical scavenging antioxidants. (C) 2009 Elsevier Ltd. All rights reserved.