Characterization of Limonoids in Citrus Essential Oils by Means of Supercritical Fluid Chromatography Tandem Mass Spectr

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Characterization of Limonoids in Citrus Essential Oils by Means of Supercritical Fluid Chromatography Tandem Mass Spectrometry Mariosimone Zoccali 1 & Adriana Arigò 1 & Marina Russo 2 & Fabio Salafia 1 & Paola Dugo 1,2,3 & Luigi Mondello 1,2,3 Received: 22 May 2018 / Accepted: 1 June 2018 # Springer Science+Business Media, LLC, part of Springer Nature 2018

Abstract The dual purpose of this research was to investigate the presence of limonoid aglycones in Citrus essential oils and to develop a rapid and reliable SFC-APCI-QqQ MS method for their characterization. In this study, 12 limonoid aglycones were tentatively identified in 11 different citrus essential oils. The developed method allowed a very fast separation in less then 7 min with a very low amount of organic solvent. Calibration curve of limonin was constructed by using a triple quad MS detector in order to quantify the limonin content in the analyzed samples. The content of limonin ranged from 0.5 (clementine essential oil) to 21.2 mg L−1 (bergamot essential oil) in the cold-pressed Citrus essential oils analyzed. Moreover, product ion scan (PIS) acquisition mode was also used for the structure elucidation of isobaric compounds. To the best of our knowledge, this is the first investigation on limonoid aglycones in Citrus essential oils. Keywords Limonoids . Supercritical fluid chromatography . Essential oil . MRM . APCI-MS

Introduction Cold-pressed Citrus essential oils are industrially obtained from the peels of Citrus fruits like bergamot, lemon, mandarin, sweet orange, grapefruit, lime, and bitter orange using mechanical systems (Dugo and Di Giacomo 2002). Citrus essential oils have a large food industrial profile in beverages, gelatines, candy, and pastry products. These oils are added as ingredients in food stuffs for their organoleptic properties, and also for their antimicrobial, anticancer, anti-inflammatory, antiviral, and Electronic supplementary material The online version of this article (https://doi.org/10.1007/s12161-018-1303-1) contains supplementary material, which is available to authorized users. * Luigi Mondello [email protected] 1

Dipartimento di BScienze Chimiche, Biologiche, Farmaceutiche ed Ambientali^, University of Messina, Polo Annunziata, viale Annunziata, 98168 Messina, Italy

2

Department of Medicine, University Campus Bio-Medico of Rome, via Alvaro del Portillo 21, 00128 Rome, Italy

3

Chromaleont s.r.l., c/o Dipartimento di Scienze Chimiche, Biologiche, Farmaceutiche ed Ambientali, University of Messina, Polo Annunziata, viale Annunziata, 98168 Messina, Italy

antioxidant properties (Adorjan and Buchbauer 2010; Mustafa 2015). Mono- and sesquiterpene hydrocarbons and their oxygenated derivatives, present in the volatile fraction of Citrus essential oils, give a natural flavor to beverages and sweet foods. The volatile fraction of Citrus essential oils has been extensively characterized (Tranchida et al. 2013; Zoccali et al. 2015). Most of the above mentioned properties come from the volatile fraction of Citrus essential

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