Isolation, characterization, identification and quantification of 6-F oxyphenisatin dipropionate, a novel illegal additive, from a fruit-flavored jelly

• Published in: Heliyon Vol. 10; no. 9; p. e29902
• Main Authors: Xia, Jintao, Wu, Wanqin, Huang, Xiuxiu, Jiang, Feng, Zhu, Songsong, Chen, Li, Fan, Xiaolong
• Format: Journal Article
• Language: English
• Published: England Elsevier Ltd 15.05.2024; Elsevier
• Subjects: de novo synthesis pathway; Illegal additive; Structural identification of diesterified oxyphenisatin analogs; Weight-loss healthcare products; Weight-loss healthcare products; Illegal additive; Structural identification of diesterified oxyphenisatin analogs; de novo synthesis pathway
• ISSN: 2405-8440; 2405-8440
• DOI: 10.1016/j.heliyon.2024.e29902

This study is aimed to screen, identify and detect illegal additives from healthcare products which claim or imply to have weight-loss effects. Ultra-high performance liquid chromatography-quadruple-time-of-flight mass spectroscopy (UPLC-Q-TOF/MS) was employed to perform non-targeted screening of illegal additives from a total of 26 batches of healthcare products with weight-loss effects. A novel oxyphenisatin dipropionate analog was discovered in a fruit-flavored jelly that was not clearly labeled as containing added drugs. After being separated and purified by silica gel column chromatography, the analog was unambiguously characterized by one-dimensional (1D) and two-dimensional (2D) nuclear magnetic resonance (NMR) spectroscopies. The molecular structure of the analog was finally identified by comparing the spectra of the analog with those of suspected candidates prepared by de novo synthesis strategy. Thereafter, a sensitive and precise reversed phase ultra performance liquid chromatography coupled with photodiode array (UPLC-PDA) detection method was developed and verified for the determination of the analog in 15 batches of real samples. In the MS/MS spectra, the signal intensity of mass/charge ratios (m/z, 242 and 214) of the novel analog fragments was highly similar to that of mass/charge ratios (m/z, 224 and 196) of oxyphenisatin dipropionate fragments. Additionally, the 1D NMR spectrum of the analog was completely consistent with that of one of the suspected candidates prepared by the de novo synthesis strategy. Based on the above analysis, the structure of the analog was determined as 3,3-bis[4'-(propionyloxy)phenyl]-6-fluoro-2-oxoindoline, which was briefly named 6-F oxyphenisatin dipropionate. A developed quantitative method showed good linearity (R2 > 0.999) in a concentration range of 1.0–100 μg/mL. The limits of detection (LOD) and quantification (LOQ) for the analog was 3 mg/kg and 10 mg/kg, respectively. The average recoveries of the analog from spiked three different matrix samples in low (1 time of LOQ), medium (2 times of LOQ), and high (10 times of LOQ) concentrations were varied from 93.9 % to 107.8 % with a precision of 0.03–1.56 %. Results of quantitative analysis in 15 batches of healthcare products revealed that the content of 6-F oxyphenisatin dipropionate in a fruit-flavored jelly and a solid beverage was 118 mg/kg and 330 mg/kg, respectively. In terms of its structure, 6-F oxyphenisatin dipropionate replaces hydrogen atom by the fluorine atom at position 6 on the indolinone fragment in oxyphenisatin dipropionate. To our best knowledge, 6-F oxyphenisatin dipropionate has never been detected as an illegal additive in foods. Such illegal addition of the analog to foods is more concealing, thus the supervision and testing departments should attach great importance to its application in food markets. •A new oxyphenisatin dipropionate analog was detected from a fruit-flavored jelly.•HRMS and NMR were utilized to characterize the structure of this analog.•All suspected candidates were prepared by de novo synthesis pathway for comparison.•Analog with an additional fluorine atom was named 6-F oxyphenisatin dipropionate.