Multidimensional liquid chromatography for the determination of chiral coumarins and furocoumarins in Citrus essential oils

Abstract

In this work the enantiomeric distribution of chiral coumarins (meranzin and epoxyaurapten), and furocoumarins (oxypeucedanin, byakangelicol, and epoxybergamottin) in different Citrus essential oils (lemon, lime, grapefruit, and bitter orange) was determined by means of a heart-cutting multidimensional-liquid chromatography (MD-LC) system, equipped with a microsilica column in the first dimension in a combination to a cellulosic-based chiral column used in the second dimension. The normal phase-liquid chromatography-liquid chromatography (NP-LC-LC) instrumentation was equipped with a photodiode array detector and a multiport valve as interface. For method optimization and the determination of absolute configuration, natural compounds were isolated and racemic mixture was synthesized. The NP-LC-LC/PDA (where PDA is photodiode array) method provided a good baseline separation of chiral coumarins (meranzin and epoxyaurapten) and furocoumarins (epoxybergamottin and byakangelicol) present in cold-pressed Citrus essential oils without any sample pretreatment. Results obtained showed that for all the chiral compounds present in Citrus essential oils analyzed, there is always a clear prevalence of one of the two enantiomers, and do not appear influenced by the different geographical origin of the oils.