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 carbonyl-containing carotenoids. To validate this new proposed approach, retinal and β-apo-8'-carotenal (APO), with known spectroscopic data, were investigated in methanol, acetonitrile and tetrahydrofuran (THF). In addition, the radical ions of newly investigated carotenoids, namely 4-oxo-β-apo-15'-carotenoic acid (4-oxo-15'), crocetindial, 4-oxo-β-apo-10'-carotenoic acid ethyl ester (4-oxo-10') and 4-oxo-β-apo-8'-carotenoic acid ethyl ester (4-oxo-8') have been reported. Moreover, the scope of this approach has been extended to investigate the radical ions of chlorophyll b.