Enhanced Antioxidant Activity under Biomimetic Settings of Ascorbic Acid Included in Halloysite Nanotubes

Antioxidant activity of native vitamin C (ascorbic acid, AH2) is hampered by instability in solution. Selective loading of AH2 into the inner lumen of natural halloysite nanotubes (HNT) yields a composite nanoantioxidant (HNT/AH2), which was characterized and investigated for its reactivity with the persistent 1,1-diphenyl-2-picrylhydrazyl (DPPH&bull
) radical and with transient peroxyl radicals in the inhibited autoxidation of organic substrates, both in organic solution (acetonitrile) and in buffered (pH 7.4) water in comparison with native AH2. HNT/AH2 showed excellent antioxidant performance being more effective than native ascorbic acid by 131% in acetonitrile and 290% (three-fold) in aqueous solution, under identical settings. Reaction with peroxyl radicals has a rate constant of 1.4 &times
106 M&minus
1 s&minus
1 and 5.1 &times
104 M&minus
1, respectively, in buffered water (pH 7.4) and acetonitrile, at 30 &deg
C. Results offer physical understanding of the factors governing HNT/AH2 reactivity. Improved performance of HNT/AH2 is unprecedented among forms of stabilized ascorbic acid and its relevance is discussed on kinetic grounds.