Peroxyl radical reactions with carotenoids in microemulsions: Influence of microemulsion composition and the nature of peroxyl radical precursor,

Abstract:The reactions of acetylperoxyl radicals with different carotenoids (7,7′-dihydro-β-carotene and ζ-carotene) in SDS and CTAC microemulsions of different compositions were investigated using laser flash photolysis (LFP) coupled with kinetic absorption spectroscopy. The primary objective of this study was to explore the influence of microemulsion composition and the type of surfactant used on the yields and kinetics of various transients formed from the reaction of acetylperoxyl radicals with carotenoids. Also, the influence of the site (hydrocarbon phases or aqueous phase) of generation of the peroxyl radical precursor was examined by using 4-acetyl-4-phenylpiperidine hydrochloride (APPHCl) and 1,1-diphenylacetone (11DPA) as water-soluble and lipid-soluble peroxyl radical precursors, respectively. LFP of peroxyl radical precursors with 7,7′-dihydro-β-carotene (77DH) in different microemulsions gives rise to the formation of three distinct transients namely addition radical (λ_max = 460 nm), near infrared transient1 (NIR, λ_max = 700 nm) and 7,7′-dihydro-β-carotene radical cation (77DH^•+, λ_max = 770 nm). In addition, for ζ-carotene (ZETA) two transients (near infrared transient1 (NIR1, λ_max = 660nm) and ζ- carotene radical cation (ZETA^•+, λ_max = 730–740 nm)) are generated following LFP of peroxyl radical precursors in the presence of ζ-carotene (ZETA) in different microemulsions. The results show that the composition of the microemulsion strongly influences the observed yield and kinetics of the transients formed from the reactions of peroxyl radicals (acetylperoxyl radicals) with carotenoids (77DH and ZETA). Also, the type of surfactant used in the microemulsions influences the yield of the transients formed. The dependence of the transient yields and kinetics on microemulsion composition (or the type of surfactant used in the microemulsion) can be attributed to the change of the polarity of the microenvironment of the carotenoid. Furthermore, the nature of the peroxyl radical precursor used (water-soluble or lipid-soluble peroxyl radical precursors) has little influence on the yields and kinetics of the transients formed from the reaction of peroxyl radicals with carotenoids. In the context of the interest in carotenoids as radical scavenging antioxidants, the fates of the addition radicals (formed from the reaction of carotenoid with peroxyl radicals) and carotenoid radical cations are discussed.