Abstract
Orange peel is a by-product produced in large amounts that acts as a source of natural pigments such as carotenoids. Xanthophylls, the main carotenoid class found in citrus fruit, can be present in its free form or esterified with fatty acids, forming esters. This esterification modifies the compound’s chemical properties, affecting their bioavailability in the human body, and making it important to characterize the native carotenoid composition of food matrices. We aimed to evaluate the non-saponified carotenoid extracts of orange peel (cv. Pera) obtained using alternative green approaches: extraction with ionic liquid (IL), analyzed by high performance liquid chromatography coupled to a diode array detector with atmospheric pressure chemical ionization and mass spectrometry HPLC-DAD-APCI-MS, and supercritical fluid extraction (SFE), followed by supercritical fluid chromatography with atmospheric pressure chemical ionization and triple quadrupole mass spectrometry detection (SFC-APCI/QqQ/MS) in an online system. Both alternative green methods were successfully applied, allowing the total identification of five free carotenoids, one apocarotenoid, seven monoesters, and 11 diesters in the extract obtained with IL and analyzed by HPLC-DAD-APCI-MS, and nine free carotenoids, six carotenoids esters, 19 apocarotenoids, and eight apo-esters with the SFE-SFC-APCI/QqQ/MS approach, including several free apocarotenoids and apocarotenoid esters identified for the first time in oranges, and particularly in the Pera variety, which could be used as a fruit authenticity parameter.
Highlights
Citrus fruits are among the most produced and consumed fruits worldwide, either fresh or as juice, and especially oranges
Reagents and solvents of analytical grade used during carotenoid extraction were purchased from Synth (Diadema, Brazil). 1-Methylimidazole and 1-chlorobutane, used for the
Despite the scarcity of literature regarding the native carotenoid composition of foods, this type of characterization is crucial for improving our understanding about the bioaccessibility and bioavailability of these compounds and to quantify the natural occurrence of carotenoids and the relationships among them
Summary
Citrus fruits are among the most produced and consumed fruits worldwide, either fresh or as juice, and especially oranges Osbeck), which are known for their large consumption and economic importance. Brazil is one of the largest exporters of orange juice around the world; among the most important cultivars in Brazil, the sweet orange cv. Pera has good juice quality and accounts for approximately 30% of the orange crop expected for 2019–2020 [1]. This high volume of juice production generates a large amount of waste. The orange peel in turn, can represent an interesting source of carotenoids, which are natural pigments responsible for adding the color to fruits and vegetables, and for providing health-related benefits when ingested by humans [2]. Carotenoid intake is related to improvements in the immune system and reduced risk of developing degenerative diseases, such as cardiovascular diseases, cancer, macular degeneration, and Alzheimer’s disease [3,4,5]
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