Department of Chemical Engineering and Analytical Chemistry, University of Barcelona Av. Diagonal 645, E-08028, Barcelona, Spain.
Faculty of Advanced Studies Cautitlan, National Autonomous University of Mexico, Av. 1o de Mayo S/N, Santa María Las Torres, Campo Uno, 54740, Cuautitlán Izcalli, Mexico.
Anal Chim Acta. 2021 Jun 15;1164:338519. doi: 10.1016/j.aca.2021.338519. Epub 2021 Apr 17.
This paper reports the development of an ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC‒MS/MS) method to determine eight banned dyes (Sudan I-IV, Sudan Orange, Sudan Red 7B, Para Red, Rhodamine B) in turmeric, curry, and chili products. For this purpose, the feasibility of electrospray (ESI), atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization (APPI) for the ionization of these compounds was evaluated. The tandem mass spectrometry (MS/MS) fragmentation of all targeted compounds was studied and both multistage mass spectrometry and high-resolution mass spectrometry were used to establish the fragmentation pathways and identify common fragmentation behaviors. Among the most significant ions, the most characteristic and abundant product ions observed on the triple quadrupole were selected to propose a selective and sensitive UHPLC‒MS/MS method (multiple reaction monitoring mode, MRM) of these target compounds in spices samples after a quick and easy extraction with acetonitrile. Matrix effect (ME) studies carried out in the three atmospheric pressure ionization sources have demonstrated that APCI showed the best performance with ME values ranging from 2 to 25%. Furthermore, the estimated quality parameters indicated the good performance of the proposed method, providing low method limits of detection (MLODs) (1-48 μg kg), good intra-day precision (RSD % < 15%), and accurate quantitation (relative error % < 15%). Finally, the applicability of the developed method was demonstrated by the analysis of turmeric, curry, and chili products. In total, 36 diverse samples coming from different countries were analyzed and although none of these compounds were detected above the MLODs, the analysis of spiked samples showed that the method was able to detect this family of compounds at low μg kg.
本文报道了一种超高效液相色谱-串联质谱（UHPLC-MS/MS）方法的开发，用于测定姜黄、咖喱和辣椒制品中八种禁用染料（苏丹红 I-IV、苏丹橙、苏丹红 7B、对位红、罗丹明 B）。为此，评估了电喷雾（ESI）、大气压化学电离（APCI）和大气压光电离（APPI）对这些化合物的电离的可行性。研究了所有目标化合物的串联质谱（MS/MS）碎裂，并使用多级质谱和高分辨率质谱建立了碎裂途径并识别常见的碎裂行为。在所研究的最重要离子中，选择三重四极杆上观察到的最特征和最丰富的产物离子，以提出一种在快速简便的乙腈提取后在香料样品中检测这些目标化合物的灵敏和选择性 UHPLC-MS/MS 方法（多重反应监测模式，MRM）。在三种大气压电离源中进行的基质效应（ME）研究表明，APCI 表现出最佳性能，ME 值范围为 2 至 25%。此外，所估计的质量参数表明该方法性能良好，提供了低方法检测限（MLOD）（1-48μgkg）、良好的日内精密度（RSD%<15%）和准确的定量（相对误差%<15%）。最后，通过对姜黄、咖喱和辣椒制品的分析证明了所开发方法的适用性。总共分析了来自不同国家的 36 种不同的样品，尽管没有一种化合物在 MLOD 以上被检测到，但加标样品的分析表明该方法能够在低μgkg 水平检测到该化合物家族。
