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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.

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The composition of carotenoids (carotenes and free and acylated xanthophylls) and their bioaccessibilities were determined for the first time in pulps of mandarins cultivated in Brazil. Two cultivars of mandarin, Citrus reticulata Blanco cv. 'Ponkan' and Citrus reticulata × C. sinensis cv. 'Murcott', showed higher contents of most carotenoids compared to those found in C. deliciosa Tenore cv. 'Rio'. The major carotenoids in mandarin cv. 'Ponkan' and 'Murcott' were (all-E)-β-cryptoxanthin laurate (19-21%), (all-E)-β-cryptoxanthin myristate (15-17%) and (Z)-ζ-carotene (7-12%), followed by (all-E)-β-cryptoxanthin palmitate (4-7%), free (all-E)-β-cryptoxanthin (5-6%) and (all-E)-β-carotene (4-5%), while in mandarin cv. 'Rio' (all-E)-β-cryptoxanthin myristate (22%) was the major compound, followed by (all-E)-β-cryptoxanthin laurate (16%), (all-E)-β-cryptoxanthin palmitate (11%), (all-E)-β-cryptoxanthin (9%) and (all-E)-β-carotene (6%). After in vitro digestion, the qualitative carotenoid profile of the supernatant containing the micellarized carotenoids was similar to that of fresh fruits, but the contents were significantly lower. Carotenoid and mandarin physico-chemical properties influenced the bioaccessibility of carotenoids. Free (all-E)-β-cryptoxanthin showed the highest bioaccessibility in all mandarin cultivars (33-42%), while the bioaccessibilities of β-carotene (16-36%) and the major carotenoid esters (18-33%) were lower. The overall recovery of carotenoids during in vitro digestion was around 98% after the oral phase, 79% after oral + gastric phases and 77% after oral + gastric + duodenal phases, with free (all-E)-β-cryptoxanthin and (all-E)-β-carotene being the most stable ones. Besides possible E-Z isomerization and ester hydrolysis, evident losses occurred in total carotenoid contents and also in the most individual carotenoids and they were not compensated for by the former reactions.

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