Composition by LC-MS/MS of New Carotenoid Esters in Mango and Citrus

Abstract

Interest in the composition of carotenoid esters of fruits is growing because esterification may affect their bioavailability. Thus, the aim was to provide a detailed identification of carotenoid esters in citrus and mango. Orange cv. 'Valencia' and cv. 'Pera' presented 9 free carotenoids, 38 monoesters, and 60 diesters. Violaxanthin and luteoxanthin derivatives were the major ones, followed by antheraxanthin, lutein, zeaxanthin, β-cryptoxanthin, and zeinoxanthin esters, many of them reported for the first time in orange pulp. The carotenoid ester composition of tangor cv. 'Murcott', reported for the first time, showed 8 free carotenoids, 34 monoesters, and 33 diesters, with β-cryptoxanthin esters as major compounds, followed by violaxanthin and zeaxanthin esters. In citrus, carotenoids were acylated mainly with capric, lauric, myristic, myristoleic, palmitic, palmitoleic, and oleic acids. In mango, 5 free carotenoids, 2 monoesters, and 19 diesters were identified, from which many violaxanthin and neoxanthin esters were reported for the first time.

Italian Lycium barbarum L. Berry: Chemical Characterization and Nutraceutical Value

“…The main advantage of the extraction procedure followed in this work [30], is represented by the possibility to study the native forms of carotenoids in fact, avoiding the saponification step, all the esterified xanthophylls can be detected by HPLC. The evaluation of carotenoid ester profile represents a very studied topic in the last years [5,31], while the determination of carotenoids after saponification gives only information about the free xanthophyll's and carotenoids, losing all the information about the individual carotenoid compound. This last approach was used by some researchers that studied the carotenoid composition in L. barbarum berry [32].…”

New Method for Carotenoid Extraction and Analysis by HPLC-DAD-MS/MS in Freeze-Dried Citrus and Mango Pulps

“…Therefore, a reliable quantification of carotenoids present in the non-saponified extract of orange was impaired. 5 Precision of analysis (extraction, saponification and chromatographic quantitation) was evaluated by means of intra-day repeatability, and results are expressed as RSD (%) in Table 5. Values of RSD ranged from 3.4% for (all-E)-lutein and (all-E)-β-carotene (level 3) to 7.8% for (all-E)-β-cryptoxanthin, confirming the repeatability of the developed method.…”

“…These carotenoids are very difficult to separate, even in a C30 column with gradient elution since both compounds also coeluted under different chromatographic conditions. 5,33 One of the major carotenoids in pulp of mango cv. 'Tommy Atkins' is also (9Z)-violaxanthin, but in this fruit the MS spectrum of (all-E)-antheraxanthin was not detected.…”

“…'Murcott', but since the non-saponified extract was characterized in that work, a different mobile phase and gradient elution was applied to achieve separation of carotenoid esters and these compounds were not quantified. 5 …”

“…4,5 Orange pulp is rich in xanthophylls (carotenoids containing oxygen molecule(s) in the structure), more specifically in hydroxylated epoxy-carotenoids such as violaxanthin and antheraxanthin. 6 Carotenoid analysis usually comprises several steps, including sampling, extraction, partition, saponification (depending on the purpose), chromatographic analysis, identification and quantification.…”