Keto, thione, selone, and tellone carotenoids — Changing antioxidants to antireductants

Abstract

Heterocarotenoids can be considered as xenobiotic compounds as they are foreign to living organisms. Thione carotenoids are heterocarotenoids that are particularly interesting because the presence of sulfur shifted the absorption to longer wavelengths than the corresponding keto carotenoids. This may be important for further applications such as the development of new pigments. Keto carotenoids are well-known antiradical molecules, however, nothing is known about heterocarotenoids acting as free radical scavengers. Thus, the main goal of this investigation is to study the antiradical properties of some heterocarotenoids, such as thione, selone, and tellone carotenoids. For this purpose, the energy differences between singlets and triplets are used to analyze the singlet oxygen quenching mechanism, and the electron transfer mechanism is investigated, taking into account that these may constitute antiradical molecules either donating or accepting electrons (antioxidants or antireductants). To analyze these mechanisms, vertical ionization energy (I), vertical electron affinity (A), and electrodonating (χ−) and electroaccepting (χ+) electronegativities were evaluated by applying density functional theory calculations. The investigated heterocarotenoids are as effective as keto carotenoids in terms of being either electron donors or acceptors, and therefore, they have a similar capacity for scavenging free radicals. Changing the C=O group to C=S, C=Se, or C=Te converts an antioxidant to an antireductant.