Isolation and identification of lutein esters, including their regioisomers, in tritordeum (×Tritordeum Ascherson et Graebner) grains: Evidence for a preferential xanthophyll acyltransferase activity

Abstract

Liquid chromatography in conjunction with UV–visible spectroscopy and atmospheric pressure chemical ionisation (APCI) mass spectrometry has been used for the structural assignment of the lutein esters, including the regioisomeric forms, naturally occurring in the endosperm of tritordeum (×Tritordeum Ascherson et Graebner), a novel cereal. The distinctive mass spectrometry fragmentation pattern of lutein, characterized by a favored loss of the moieties at the position 3′ of the ε-end ring, allowed an unambiguous structural identification of four monoesters (lutein 3′-O-linoleate, lutein 3-O-linoleate, lutein 3′-O-palmitate, lutein 3-O-palmitate) and four diesters (lutein dilinoleate, lutein 3′-O-linoleate-3-O-palmitate, lutein 3′-O-palmitate-3-O-linoleate, lutein dipalmitate). This is the first time that the regioisomers of carotenoid esters have been identified in a cereal. Evidences for a preferential xanthophyll acyltransferase activity regarding the position (3 or 3′) and the acyl moiety are discussed. Further studies should be carried out in order to identify the acyltransferase enzymes and the acyl donor molecules involved in the xanthophyll esterification process.