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The carotenogenesis in the endocarp and flavedo of Navel oranges over four consecutive maturity stages was assessed by high-performance liquid chromatography-diode array detection-atmospheric pressure chemical ionization-multistage mass spectrometry. After optimization of the extraction method, 77 carotenoids, including 26 monoesters and 33 diesters of violaxanthin, β-citraurin, and antheraxanthin, were characterized. Whereas chloroplast-specific pigments, such as (all- E )-lutein and (all- E )-β-carotene, predominated in the flavedo of green-ripe fruit, a highly complex pattern of xanthophyll esters was found in the mature oranges. Total carotenoid contents of flavedo were approximately 9-fold higher [12 605 μg/100 g of fresh weight (FW)] than those in the endocarp (1354 μg/100 g of FW) at the fully mature stage. The mature endocarp abundantly contained violaxanthin mono- and diesters, in addition to diverse antheraxanthin esters, which were exclusively detected in this fruit fraction. Likewise, β-citraurin esters were found to be unique flavedo constituents of mature fruit. Therefore, they may support the detection of fraudulent use of peel fractions during orange juice production.

Genuine Carotenoid Profiles in Sweet Orange [Citrus sinensis (L.) Osbeck cv. Navel] Peel and Pulp at Different Maturity Stages