Fullerenols
possess excellent antioxidant activity, in which they
can scavenge all of the major physiologically relevant reactive oxygen
species (ROS). However, the underlying ROS-scavenging mechanisms of
C60 fullerenols are not completely understood. Using density
functional theory calculations, we investigated •OH-, O2
•–-, and H2O2-scavenging mechanisms of C60 fullerenols
and the correlations between hydroxyl distributions and radical-scavenging
ability. For scavenging •OH and O2
•–, H• donation and electron
transfer via hydrogen bonds, respectively, are the dominant mechanisms
for C60 fullerenols. Although the obtained fullerenols
simultaneously contain radicals and anions, there is an isolated OH
anion which possesses the activity of eliminating H2O2. The •OH-scavenging activity depends on
the distribution of hydroxyls according to the calculations for ten
C60(OH)24 isomers. Fullerenols, in which the
distribution of hydroxyls leads to low redox potential (ε) values,
possess high scavenging activity. For the nonmagnetic fullerenols,
activity relies on the number of sp2 substructures, in
which the greater their number is, the lower the activity of the fullerenols.
The results will be of fundamental importance in understanding the
antioxidant activities of fullerenols.