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动力学方法结合热辅助纸喷雾电离质谱法直接测定功能食品中多种d/l-氨基酸的对映体过量

Kinetic Method Coupled with Thermal-Assisted Paper Spray Ionization Mass Spectrometry for Direct Determination of Enantiomeric Excess of Multiple d/l-Amino Acids in Functional Foods.

作者信息

Gao Wen-Bo, Xu Shu-Ting, Yan Yong-Jie, Yang Cheng, Yan Xiu-Ping

机构信息

State Key Laboratory of Food Science and Resources, Jiangnan University, Wuxi 214122, China.

International Joint Laboratory on Food Safety, Jiangnan University, Wuxi 214122, China.

出版信息

J Am Soc Mass Spectrom. 2025 Apr 2;36(4):906-913. doi: 10.1021/jasms.5c00050. Epub 2025 Mar 13.

Abstract

Amino acids are commonly used as nutritional fortification substances in functional foods, and their chiral configuration is an important determinant of food function. Rapid chiral screening methods are urgently needed in food analysis but are limited by the long-time chiral separation and matrix interference. In this study, we show a kinetic method coupled to thermal-assisted paper spray ionization mass spectrometry for direct determination of enantiomeric excess () of multiple d/l-amino acids in complex food matrixes without sample pretreatment. 3-(2-Naphthyl)-l-alanine was selected as a new chiral reference ligand for the kinetic method to achieve efficient chiral differentiation (discrimination degree is 8.7 for d/l-phenylalanine and 10.2 for d/l-tyrosine). An additional thermal-auxiliary device was developed for paper spray ionization mass spectrometry to facilitate the enantiomeric purity determination. The developed method allowed a rapid simultaneous enantiomeric purity determination of multiple chiral amino acids (d/l-phenylalanine and d/l-tyrosine) within 30 s. Good linearities were achieved for the quantitation of ( = 0.9996 for phenylalanine and 0.9995 for tyrosine) with unknown amino acid concentrations ranging from 10 μM to 600 μM. The developed method was successfully applied for the enantiomeric purity determination of multiple chiral amino acids in functional capsules and beverages and showed great potential for efficient enantiomer-related food safety screening and nutrition analysis.

摘要

氨基酸通常用作功能性食品中的营养强化物质,其手性构型是食品功能的重要决定因素。食品分析中迫切需要快速的手性筛选方法,但受限于长时间的手性分离和基质干扰。在本研究中,我们展示了一种结合热辅助纸喷雾电离质谱的动力学方法,用于直接测定复杂食品基质中多种d/l-氨基酸的对映体过量(ee),无需样品预处理。选择3-(2-萘基)-l-丙氨酸作为动力学方法的新型手性参考配体,以实现高效的手性区分(d/l-苯丙氨酸的区分度为8.7,d/l-酪氨酸的区分度为10.2)。为纸喷雾电离质谱开发了一种额外的热辅助装置,以促进对映体纯度的测定。所开发的方法能够在30秒内快速同时测定多种手性氨基酸(d/l-苯丙氨酸和d/l-酪氨酸)的对映体纯度。对于未知氨基酸浓度范围为10 μM至600 μM的ee定量,实现了良好的线性关系(苯丙氨酸的R² = 0.9996,酪氨酸的R² = 0.9995)。所开发的方法成功应用于功能性胶囊和饮料中多种手性氨基酸的对映体纯度测定,在高效对映体相关食品安全筛选和营养分析方面显示出巨大潜力。

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