Structure investigations on assembled astaxanthin molecules

The carotenoid r,r-astaxanthin (3R,3′R-dihydroxy-4,4′-diketo-β-carotene) forms different types of aggregates in acetone-water mixtures. H-type aggregates were found in mixtures with a high part of water (e.g. 1:9 acetone-water mixture) whereas two different types of J-aggregates were identified in mixtures with a lower part of water (3:7 acetone-water mixture). These aggregates were characterized by recording UV/vis-absorption spectra, CD-spectra and fluorescence emissions. The sizes of the molecular assemblies were determined by dynamic light scattering experiments. The hydrodynamic diameter of the assemblies amounts 40 nm in 1:9 acetone-water mixtures and exceeds up to 1 μm in 3:7 acetone-water mixtures. Scanning tunneling microscopy monitored astaxanthin aggregates on graphite surfaces. The structure of the H-aggregate was obtained by molecular modeling calculations. The structure was confirmed by calculating the electronic absorption spectrum and the CD-spectrum where the molecular modeling structure was used as input.