Carotenoid radical ions: A laser flash photolysis study

Laser excitation of a single precursor, namely 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone (HHEMP), has been used for generating the radical cations and radical anions of various carotenoids in methanol. In the presence of oxygen, laser excitation of HHEMP undergoes an efficient α-cleavage reaction (Norrish type I) to form acyl radicals, which react with O₂, in a nearly diffusion-controlled reaction, to form their corresponding strong oxidizing acylperoxyl radicals (RO₂^•) (E = ~1.1 V (v SHE)), which are capable of oxidizing almost all carotenoids. Under argon-saturated conditions and in the presence of strong base (0.01 M NaOH or tetrabutylammonium hydroxide (TBAOH)), the initially formed 2-hydroxy-2-propyl radical (ACH^•), generated after LFP of HHEMP, is deprotonated to form the strong reducing acetone ketyl radical (AC^•-) (E {acetone/ AC^•-} = −2.1 V (v SHE)), which is capable of reducing all …