Hydroperoxyl Radicals (HOO.): Vitamin E Regeneration and H‐Bond Effects on the Hydrogen Atom Transfer. Issue 46 (6th October 2016)

• Record Type: Journal Article
• Authors: Cedrowski, Jakub; Litwinienko, Grzegorz; Baschieri, Andrea; Amorati, Riccardo
• Is Part Of: Chemistry. Volume 22:Issue 46(2016)
• Page Start: 16441
• Page End: 16445
• Publication Date: 2016-10-06
• Subjects: hydrogen atom transfer -- hydroperoxyl radicals -- reactive oxygen species -- solvent effects -- tocopherol; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201603722
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Hydroperoxyl (HOO . ) and alkylperoxyl (ROO . ) radicals show a different behavior in H‐atom‐transfer processes. Both radicals react with an analogue of α‐tocopherol (TOH), but HOO ., unlike ROO ., is able to regenerate TOH by a fast H‐atom transfer: TO . +HOO . →TOH+O2 . The kinetic solvent effect on the H‐atom transfer from TOH to HOO . is much stronger than that observed for ROO . because noncovalent interactions with polar solvents (Solv⋅⋅⋅HOO . ) destabilize the transition state. Abstract : Role reversal : Hydroperoxyl radicals (HOO . ) are able to recycle an α‐tocopherol analogue, increasing the inhibition period up to 10 times, and exhibit a strong kinetic solvent effect arising from noncovalent interactions between HOO . and H‐bond‐accepting solvents.