Carotenoids and β-Cyclodextrin Inclusion Complexes: Raman Spectroscopy and Theoretical Investigation

In the present study, the inclusion processes of beta-carotene, astaxanthin, lycopene, and norbixin (NOR) into the beta-cyclodextrin (beta-CD) cavity were investigated by means of Raman spectroscopy and quantum mechanics calculations. The Raman nu(1) band assigned to C=C stretching was sensitive to the host-guest interaction and in general undergoes a blue shift (3-13 cm(-1)) after inclusion takes place, which is the consequence of the localization of single and double bonds. This is supported by the molecular modeling prediction, which inclusion complexes show the nu(1) band blue shifted by 1-8 cm(-1). The calculated complexation energies was small for most of derivatives and was found to be -11.1 kcal mol(-1) for inclusion of AST and +0.27 kcal mol(-1) for NOR. The stability order was qualitatively correlated to topological parameters accounting for the opening angle of the chain. This means that after inclusion the guest molecules assume a slightly more extended conformation, which enhances the host-guest contact, improving the interaction energy. The results discussed here clearly demonstrate the matrix effect on the carotenes' spectroscopic profile and should contribute to fully characterize the raw samples.