Supramolecular assemblies of carotenoids.

Carotenoid self-assemblies were formed by aqueous dilution of ethanolic solutions. The four 3',6'-epimers of capsanthol ((all-E,3R,5'R)-3,3',6'-trihydroxy-beta,kappa-carotene) give rise to right- and left-handed card-pack and head-to-tail types of self-assemblies detected by exciton couplets appearing in the CD spectra. Slow kinetics of formation followed for some of the aggregates indicate the complexity of the process. The exciton signals do not appear from equimolar mixtures of related compounds that produce identical type of aggregates of opposite sense on their own. Transformation of self-assembly may reflect the population of kappa-ring rotamers.

Chiral detection of carotenoid assemblies.

Carotenoid assemblies were produced by aqueous dilution of ethanolic solutions. UV/VIS and CD spectroscopy revealed the formation of J- and H-types of aggregates of both right- and left-handed kinds. Simulation of UV/VIS spectra of the aggregates showed characteristic differences between the two types. 6'-Epimers of capsanthol ((all-E,3R,3'S,5'R)-beta,kappa-carotene-3,3',6'-triols) formed assemblies with increased chirality in dilute solution. While the absorption of 6'R-capsanthol giving H-type aggregate does not depend on the concentration, 6'S-capsanthol yielding J-type assembly showed concentration-dependent absorption intensity. Dilute aggregate of 6'R-capsanthol is characterized by an extremely large A value of -6,600. The transformation of J- to H-type assembly was observed in the mixtures of the epimers producing an intermediate kind of aggregate. A hypothetical structure for H-type assemblies is proposed.