Structural Study on Hypochlorous Acid-Mediated Chlorination of Betanin and Its Decarboxylated Derivatives from an Anti-Inflammatory Beta vulgaris L. Extract

Hypochlorous acid (HOCl) produced by neutrophils is a part of the natural innate immune response system in the human body, but excessive levels of HOCl can ultimately be detrimental to health. Recent reports suggest that betacyanin plant pigments can act as potent scavengers of inflammatory factors and are notably effective against HOCl. In this contribution, chlorination mechanism and position of the electrophilic substitution in betacyanins was studied by high-resolution mass spectrometry and further structural analyses by NMR techniques, which completed the identification of the chlorinated betacyanins. For the study on the influence of the position of decarboxylation on the chlorination mechanism, a comparison of the chlorination position between betanin as well as 17-, and 2,17-decarboxylated betanins was performed. The structural study confirmed that the chlorination position in betanin occurs within the dihydropyridinic moiety at carbon C-18. Therefore, out of the aqueous free chlorine equilibrium species: HOCl, OCl(−), Cl(2), and Cl(2)O, the most potent chlorinating agents are HOCl and Cl(2)O postulated previously and the attack of the Cl(⁺) ion on the carbon C-18 with a cyclic intermediate version is considered.