内分泌干扰物的拟靶向质谱分析新方法及其在食品包装安全研究中的应用

Endocrine disrupting chemicals (EDCs) in food packaging materials are characterized by great variety and complex migration behavior, but only little information of them is available. EDCs have become a great threat to food safety. Traditional analytical method which is targeted at a few already known compounds is no longer competent for the EDCs with great categories and amounts, and its accuracy is usually discounted by matrix effect. In this study, efficient, specific and inexpensive stable isotope labeling (SIL) probes will be designed to develop a new pseudo-targeted mass spectrometric method based on stable isotope labeling. The developed method can be well applied in the pseudotargeted analysis of all kinds of phenols, amines, acids and aldehydes. Compounds with low concentrations can be detected by the mass enhancing labeling strategy, and the analytical scope will be expanded by the pseudo-targeted manner, while the matrix effect will be overcome by the SIL technology. The new method will be applied to the early identification of unknown migrant from food packaging materials. It will also be applied to the migration tests of food packaging materials using real food samples. The exposure risks of EDCs from food packaging materials will be evaluated, and the rationality of food packaging method will be judged. The implementation of the project will accelerate the identification process of unknown EDCs, and the accuracy of the exposure risk assessment results will also be enhanced. The results will provide technical support for the production, usage and supervision of food packaging materials.

食品包装材料中的内分泌干扰物种类多、已知信息少、迁移行为复杂，严重危及食品安全。传统的靶向分析方法已无法应对种类和数量日趋增多的内分泌干扰物，分析结果也常因基质效应而偏离真实值。本项目拟在前期研究基础上，设计制备高效、特异、廉价的稳定同位素标记探针，构建基于稳定同位素标记技术的拟靶向质谱分析新方法，实现对酚类、胺类、醛类和羧酸类内分泌干扰物的拟靶向全覆盖分析。探针的质谱增敏作用可提高低含量内分泌干扰物的检出率；拟靶向分析的未知物解析功能可拓展内分泌干扰物的研究范围；同位素标记策略可克服基质效应，提高方法准确度。利用新方法对食品包装材料中的未知内分泌干扰物进行早期鉴定，并以真实食品对确认的内分泌干扰物进行迁移水平研究，评估相关化合物的暴露风险，评价常见食品包装方式的科学性。课题的实施将有效推进未知内分泌干扰物的鉴定进程，提升暴露风险评价结果的准确性，为食品包装材料的生产、使用和监管提供依据。

食品包装材料迁移物污染是影响食品安全的一大隐患。食品包装材料内分泌干扰物种类多、含量低，检测结果易受基质效应影响而偏离真实值。内分泌干扰物的拟靶向分析通常采用飞行时间质谱，但其灵敏度低，而四级杆质谱功能被固化，难以实现对未知内分泌干扰物的分析。本研究设计、制备了多种稳定同位素标记（SIL）探针，所有探针均可产生“标记探针特征离子”，具有质谱增敏作用，可用于内分泌干扰物的高灵敏、高准确分析，同时探针具有的通用型MRM参数可用于未知内分泌干扰物的拟靶向分析。具体研究结果如下： .1 设计、制备了4-(三甲氨基)苯甲酸琥珀酰亚胺脂季胺盐SIL探针，并将其用于酚类内分泌干扰物的稳定同位素标记拟靶向分析。 .2 设计、制备了4-(三甲氨基)苯甲酸季胺盐SIL探针，建立了胺类内分泌干扰物的拟靶向分析方法。 .3 设计、制备了10-甲基吖啶酮-2-磺酰肼SIL探针，建立了羧酸类内分泌干扰物的稳定同位素标记拟靶向分析方法。 .4设计、制备了重型丹磺酰肼稳定同位素标记试剂，结合商品化轻型丹磺酰肼对醛类化合物进行了质谱增敏标记，建立了醛类化合物的稳定同位素标记拟靶向分析方法..5 对食品包装材料内分泌干扰物进行了拟靶向分析和暴露风险评价。.本研究开发的SIL探针制备方法简单、质谱增敏作用显著，能有效提高分析灵敏度，并可用于未知物的MRM拟靶向分析，可在实验室间推广，有效提升食品中内分泌干扰物的监测水平。