Simultaneous determination of α,β-unsaturated aldehydes in emulsions based on supercritical fluid chromatography-tandem mass spectrometry

Abstract

Abstract: In order to effectively improve the risk detection level of α,β-unsaturated aldehydes in edible oils, this study established a efficient and sensitive detection method using Supercritical Fluid Chromatography coupled with Triple Quadrupole Mass Spectrometry (SFC-MS/MS). By optimizing SFC-MS/MS parameters and pretreatment conditions, it was found that simultaneous detection of 8 α,β-unsaturated aldehydes could be achieved within 4 minutes though using supercritical CO2 fluid and acetonitrile as the mobile phase under negative ionization mode of electrospray ionization. The α,β-unsaturated aldehydes showed good linearity within their respective concentration ranges, with quantification limits ranging from 0.15 to 1.8 ppb and spiked recovery rates between 85.8% and 106.7%. The measurement accuracy RSD ranged from 0.22% to 7.86%. The optimized pretreatment conditions included: addition of 5 mg of 2,4-dinitrophenylhydrazine, derivatization time of 30 minutes, and extraction with acetonitrile performed four times. Furthermore, the established method was used to evaluate the mediating effect of three polyphenolic antioxidants: water-soluble gallic acid, water-oil amphipathic propyl gallate and water-oil-insoluble quercetin on the content of eight α,β-unsaturated aldehydes in linseed oil-in-water emulsion during storage. The results showed that α,β-unsaturated aldehydes accumulated rapidly during the storage process of the emulsion with malondialdehyde, 4-hydroxy-2-hexenal and 4-hydroxy-2-nonenal as the predominant α,β-unsaturated aldehydes, while the three antioxidants presented a significant mitigating effect on α,β-unsaturated aldehydes contents, with propyl gallate as the most effective one. This method is characterized by its simplicity, high efficiency in analysis, and environmental friendliness, making it suitable for sensitive and accurate detection of α,β-unsaturated aldehydes generated during processing, storage, and use of edible oils.

Key words: supercritical fluid chromatography-tandem mass spectrometry, emulsions, flaxseed oil, lipid oxidation, α,β-unsaturated aldehydes

CLC Number:

TS227

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