Carotenoids in Antioxidant Networks. Colorants or Radical Scavengers

Optical and electronic properties of carotenoids as also reflected in their colors have been fine-tuned through evolution, resulting in a structural diversity important for carotenoid properties as radical scavengers and as quenchers of electronically excited states. Carotenoids form antioxidant networks based on one-electron transfer with other carotenoids depending on the balance between ionization energy and electron affinity of the individual carotenoids as has been demonstrated by real-time kinetic studies and later confirmed by quantum mechanical calculations. The more hydrophilic xanthophylls serve as molecular wiring across membranes in these networks through anchoring in water/lipid interfaces resulting in synergism with more lipophilic carotenoids. Radical scavenging of such networks seems to be thermodynamically controlled according to a two-dimensional classification of potential antioxidants. Carotenoids in birds’ plumage, as reflected by their color and color intensity, seem to be indicators of good antioxidant status and health of the bird, and such antioxidant networks appear to be in “equilibrium”. Carotenoids are under other conditions involved in networks with other types of antioxidants as in egg yolk and in some fish. For the more hydrophilic (iso)­flavonoids and their glycosides, antioxidant synergism through regeneration of the lipophilic carotenoids active as radical scavengers becomes kinetically controlled at interfaces. Carotenoids appear accordingly, and also in food, as antioxidants under two types of conditions: (i) in “equilibrium” with other antioxidants in thermodynamically controlled networks serving as color indicators of good antioxidant status and (ii) as antioxidants active through radical scavenging in networks with kinetically controlled regeneration.