Spectroscopic study and antioxidant properties of the inclusion complexes of rosmarinic acid with natural and derivative cyclodextrins

Measurement of total antioxidant activity/capacity of polyphenols in various solvent media necessitates the use of cyclodextrins to solubilize lipophilic antioxidants of poor aqueous solubility. The inclusion complexes of the slightly water soluble antioxidant, rosmarinic acid (RA), with α-cyclodextrin (α-CD), β-cyclodextrin (β-CD), 2-hydroxypropyl-β-cyclodextrin (HP-β-CD), 2-hydroxyethyl-β-cyclodextrin (HE-β-CD), and methyl-β-cyclodextrin (M-β-CD) were investigated for the first time. The effect of cyclodextrins (CDs) on the spectral features of RA was measured in aqueous medium using UV–vis and steady-state fluorescence techniques by varying the concentrations of CDs. The molar stoichiometry of RA–CD inclusion complexes was verified as 1:1, and the formation constants of the complexes were determined from Benesi–Hildebrand equation using fluorescence spectroscopic data. Among the CDs, maximum inclusion ability was measured in the case of M-β-CD followed by HP-β-CD, HE-β-CD, β-CD and α-CD. Solid inclusion complexes were prepared by freeze drying, and their functional groups were analyzed by IR spectroscopy. Antioxidant capacity of CD-complexed rosmarinic acid was measured to be higher than that of the lone hydroxycinnamic acid by the CUPric Reducing Antioxidant Capacity (CUPRAC) method. The mechanism of the TAC increase was interpreted as the stabilization of the 1 − e oxidized o-catechol moiety of RA by enhanced intramolecular H-bonding in a hydrophobic environment provided by CDs, mostly by M-β-CD.

Fluorescence spectra of rosmarinic acid in aqueous solution with different CDs.Figure optionsDownload as PowerPoint slideResearch highlights
► Inclusion complexes of rosmarinic acid with natural and derivative cyclodextrins.
► Inclusion in derivative β-cyclodextrins is more effective than in native CDs.
► Antioxidant capacity of RA shows a slight increase when complexed with CDs.
► RA-M-β-CD has the highest antioxidant capacity of all inclusion complexes.