Janusz Daroszewski

Discovery and Characterization of Carotenoid-Oxygen Copolymers in Fruits and Vegetables with Potential Health Benefits

We reported previously that the spontaneous oxidation of β-carotene and other carotenoids proceeds predominantly by formation of carotenoid-oxygen copolymers and that β-carotene copolymers exhibit immunological activity, including priming innate immune function and limiting inflammatory processes. Oxidative loss of carotenoids in fruits and vegetables occurs during processing. Here we report evidence for the occurrence of associated analogous copolymer compounds. Geronic acid, an indirect, low molecular weight marker of β-carotene oxidation at ∼2% of β-carotene copolymers, is found to occur in common fresh or dried foods, including carrots, tomatoes, sweet potatoes, paprika, rosehips, seaweeds, and alfalfa, at levels encompassing an approximately thousand-fold range, from low ng/g in fresh foods to μg/g in dried foods. Copolymers isolated from several dried foods reach mg/g levels: comparable to initial carotenoid levels. In vivo biological activity of supplemental β-carotene copolymers has been previously documented at μg/g levels, suggesting that some foods could have related activity.

Biologically Active Polymers from Spontaneous Carotenoid Oxidation: A New Frontier in Carotenoid Activity

In animals carotenoids show biological activity unrelated to vitamin A that has been considered to arise directly from the behavior of the parent compound, particularly as an antioxidant. However, the very property that confers antioxidant activity on some carotenoids in plants also confers susceptibility to oxidative transformation. As an alternative, it has been suggested that carotenoid oxidative breakdown or metabolic products could be the actual agents of activity in animals. However, an important and neglected aspect of the behavior of the highly unsaturated carotenoids is their potential to undergo addition of oxygen to form copolymers. Recently we reported that spontaneous oxidation of ß-carotene transforms it into a product dominated by ß-carotene-oxygen copolymers. We now report that the polymeric product is biologically active. Results suggest an overall ability to prime innate immune function to more rapidly respond to subsequent microbial challenges. An underlying structural resemblance to sporopollenin, found in the outer shell of spores and pollen, may allow the polymer to modulate innate immune responses through interactions with the pattern recognition receptor system. Oxygen copolymer formation appears common to all carotenoids, is anticipated to be widespread, and the products may contribute to the health benefits of carotenoid-rich fruits and vegetables.