Objective: To confirm two novel illegal additives suspected to be derivatives of diflorasone in cosmetics using by ultra-high performance liquid chromatography quadrupole/orbitrap high-resolution mass spectrometry (UHPLC-Q Orbitrap HRMS), and to establish a quantitative determination method by high performance liquid chromatography-tandem triple quadrupole mass spectrometry (HPLC-QqQ-MS). Methods: Qualitative determination was performed by UHPLC-Q Orbitrap HRMS. A Merck Purospher Star RP-18 endcapped (125 mm×2 mm,5 μm) column was used with a mobile phase of 0.1% formic acid in water (A) and acetonitrile (B), operated under gradient elution at a flow rate of 0.2 mL · min-1. Data were collected in positive ion mode. The sample extracted with methanol by ultrasonic method was screened. Two unknown chromatographic peaks were detected at 11.97 min and 12.60 min respectively, and the parent ion of m/z 467.22 was locked to obtain the secondary mass spectrum. Quantitative determination was performed by HPLC-QqQ-MS. The sample was separated on Agilent ZORBAX Eclipse Plus C18 column (150 mm×3.0 mm, 1.8 μm) by gradient elution using acetonitrile (A) and water (B). The flow rate was 0.3 mL · min-1, and the injection volume was 2 μL. The samples were ionized by positive ion mode of electrospray ionization source and determined by multiple reaction monitoring (MRM) mode. Results: The secondary mass spectrum of two unknown chromatographic peaks were very similar to the secondary mass spectrum of diflorasone diacetate. Both compounds had propionic ester similar structure (m/z 57.03), so that two compounds were presumed to be isomers of diflorasone 17-propionate and diflorasone 21-propionate and the reference substances were used for confirmation. HPLC-QqQ-MS was employed for the determination. Diflorasone 17-propionate and diflorasone 21-propionate exhibited good linear relationships within the concentration range of 1-50 ng · mL-1. The limits of detection were both 30 ng · g-1 and the limits of quantification were 100 ng · g-1. The recoveries of each concentration level in 5 representative substrates of liquid (water, oil), cream, gel and wax-based cosmetics ranged from 82.8% to 107.4%, and the recoveries were good. Nine batches of commercially available liquid products were tested, and the content of diflorasone 17-propionate in them ranged from 0.1 to 114.5 μg · g-1, while the content of diflorasone 21-propionate ranged from 3.9 to 146.8 μg · g-1. Conclusion: This study identifies two noval illegal glucocorticoid additives in cosmetics. The research approach for the screening and content determination methods in this study can provide certain technical references for the research of unknown prohibited substances in cosmetics.
GUO Jie
,
BI Si-dan
,
ZHANG Shu-dong
,
DI Zheng
,
ZHANG Zhe
,
ZHANG Hua-jun
. Establishment of a non-targeted screening and determination method for illegally added diflorasone propionate in cosmetics[J]. Chinese Journal of Pharmaceutical Analysis, 2025
, 45(7)
: 1244
-1258
.
DOI: 10.16155/j.0254-1793.2024-1075
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