Photodegradation mechanisms of pyrrolizidine alkaloids and risk prediction of their degradation products based on high resolution mass spectrometry and theoretical calculations

文献类型： 外文期刊

第一作者： Huang, Xuchen

作者： Huang, Xuchen;Chai, Yunfeng;Li, Shiqi;Yi, Yuexin;Wang, Chen;Ma, Guicen;Hao, Zhenxia;Zhang, Xiangchun;Chen, Hongping;Huang, Xuchen;Chai, Yunfeng;Wang, Chen;Ma, Guicen;Hao, Zhenxia;Zhang, Xiangchun;Chen, Hongping;Chai, Yunfeng;Wang, Chen;Ma, Guicen;Hao, Zhenxia;Zhang, Xiangchun;Chen, Hongping;Li, Shiqi;Yi, Yuexin;Li, Pengyang;Fu, Jianjie;Li, Pengyang;Fu, Jianjie

作者机构：

关键词： Hepatotoxic pyrrolizidine alkaloids; High-resolution mass spectrometry (HRMS); Photodegradation products; Photodegradation mechanism; Toxicity prediction

期刊名称：JOURNAL OF HAZARDOUS MATERIALS （ 影响因子：11.3； 五年影响因子：12.4 ）

ISSN： 0304-3894

年卷期： 2025 年 496 卷

页码：

收录情况： SCI

摘要： Pyrrolizidine alkaloids (PAs) and their N-oxides (PANOs) are emerging environmental pollutants, and they inevitably undergo degradation, particularly photodegradation. However, the photodegradation products of PAs/PANOs and their formation mechanisms remain poorly understood. Herein, a high-resolution mass spectrometry fragmented ions database of 34 PAs/PANOs was established, and several characteristic fragment ions, such as m/z 138.0913, 120.0808, and 94.0651, were used to screen photodegradation products retaining the necine base structure. A total of 60 photodegradation products of 11 PAs/PANOs were identified, and their fragmentation pathways under electrospray ionization were profiled in detail. The photolysis mechanism of PAs/ PANOs was analyzed by using quantum chemistry methods and radical quenching experiments. The C7 ester bond region contained multiple reactive sites that underwent oxidation reactions mediated jointly by singlet oxygen (1O2) and superoxide anion (O2 center dot- ). Initial reaction pathways of PAs/PANOs were speculated in the process, including hydroxylation, ester bond cleavage, oxidation, and C--C isomerization reactions, ultimately generating various transformation products (TPs). In silico assessments demonstrated that 13 %-33 % of TPs exhibited higher toxicity than their parent compounds, underscoring environmental and health risks. This study emphasizes the need for comprehensive risk assessments of PAs/PANOs and their photodegradation products.

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