Absorption Spectra of Astaxanthin Aggregates

TL;DR

This study investigates how astaxanthin forms aggregates in hydrated solvents, affecting its absorption spectra, and uses molecular dynamics and exciton models to analyze the structural and spectral properties of these aggregates.

Contribution

It combines experimental spectral analysis with molecular dynamics and quantum chemical calculations to elucidate the structure and optical properties of astaxanthin aggregates.

Findings

H-aggregates and J-aggregates form depending on water content.

Large spectral shifts are due to excitonic interactions.

Structural models explain spectral changes with aggregation.

Abstract

Carotenoids in hydrated polar solvents form aggregates characterized by dramatic changes in their absorption spectra with respect to monomers. Here we analyze absorption spectra of aggregates of the carotenoid astaxanthin in hydrated dimethylsulfoxide. Depending on water content, two types of aggregates were produced: H-aggregates with absorption maximum around 390 nm, and J-aggregates with red-shifted absorption band peaking at wavelengths >550 nm. The large shifts with respect to absorption maximum of monomeric astaxanthin (470-495 nm depending on solvent) are caused by excitonic interaction between aggregated molecules. We applied molecular dynamics simulations to elucidate structure of astaxanthin dimer in water, and the resulting structure was used as a basis for calculations of absorption spectra. Absorption spectra of astaxanthin aggregates in hydrated dimethylsulfoxide were calculated using molecular exciton model with the resonance interaction energy between astaxanthin monomers constrained by semi-empirical quantum chemical calculation. The intramolecular vibrations of astaxanthin are modeled by a line shape function corresponding to two characteristic C-C and C=C stretching modes with frequencies of 1150 cm^-1 and 1520 cm^-1. The solvent is represented by a spectral density of harmonic vibrations. The spectral changes at increasing concentrations of water were assigned to formation of aggregates with decreasing exposure of the astaxanthin hydrophobic chain to the solvent.