Carotenoids are a large and diverse group of compounds that have been shown to have a wide range of potential health benefits. While some carotenoids have been extensively studied, many others have not received as much attention. Studying the physicochemical properties of carotenoids using electron paramagnetic resonance (EPR) and density functional theory (DFT) helped us understand their chemical structure and how they interact with other molecules in different environments. Ultimately, this can provide insights into their potential biological activity and how they might be used to promote health. In particular, some rare carotenoids, such as sioxanthin, siphonaxanthin and crocin, that are described here contain more functional groups than the conventional carotenoids, or have similar groups but with some situated outside of the rings, such as sapronaxanthin, myxol, deinoxanthin and sarcinaxanthin. By careful design or self-assembly, these rare carotenoids can form multiple H-bonds and coordination bonds in host molecules. The stability, oxidation potentials and antioxidant activity of the carotenoids can be improved in host molecules, and the photo-oxidation efficiency of the carotenoids can also be controlled. The photostability of the carotenoids can be increased if the carotenoids are embedded in a nonpolar environment when no bonds are formed. In addition, the application of nanosized supramolecular systems for carotenoid delivery can improve the stability and biological activity of rare carotenoids.

Carotenoids are well-known antioxidants. They have the ability to quench singlet oxygen and scavenge toxic free radicals preventing or reducing damage to living cells. We have found that carotenoids exhibit scavenging ability towards free radicals that increases nearly exponentially with increasing the carotenoid oxidation potential. With the oxidation potential being an important parameter in predicting antioxidant activity, we focus here on the different factors affecting it. This paper examines how the chain length and donor/acceptor substituents of carotenoids affect their oxidation potentials but, most importantly, presents the recent progress on the effect of polarity of the environment and orientation of the carotenoids on the oxidation potential in supramolecular complexes. The oxidation potential of a carotenoid in a nonpolar environment was found to be higher than in a polar environment. Moreover, in order to increase the photostability of the carotenoids in supramolecular complexes, a nonpolar environment is desired and the formation of hydrogen bonds should be avoided.

The conjugation length of an olefin and the environment of Cu²⁺ affect the Cu²⁺–olefin interaction significantly.