Department of Pharmaceutical Analysis, Affiliated Hospital of Integrated Traditional Chinese and Western Medicine, Nanjing University of Chinese Medicine, Nanjing 210028, China; Department of Pharmacy, Wuhan Children's Hospital (Wuhan Maternal and Child Healthcare Hospital), Tongji Medical College, Huazhong University of Science & Technology, Wuhan 430016, China.
Department of Oncology, Affiliated Hospital of Integrated Traditional Chinese and Western Medicine, Nanjing University of Chinese Medicine, Nanjing 210028, China.
Food Chem. 2024 Aug 1;448:139112. doi: 10.1016/j.foodchem.2024.139112. Epub 2024 Mar 30.
Ginseng is a most popular health-promoting food with ginsenosides as its main bioactive ingredients. Illegal sulfur-fumigation causes ginsenosides convert to toxic sulfur-containing derivatives, and reduced the efficacy/safety of ginseng. 24-sulfo-25-ene ginsenoside Rg1 (25-ene SRg1), one of the sulfur-containing derivatives, is a potential quality control marker of fumigated ginseng, but with low accessibility owing to its unknown generation mechanism. In this study, metals/bisulfite system involved generation mechanism was investigated and verified. The generation of 25-ene SRg1 in sulfur-fumigated ginseng is that SO, formed during sulfur-fumigation, reacted with water and ionized into HSO. On the one hand, under the metals/bisulfite system, HSO generates HSO and free radicals which converted ginsenoside Rg1 to 24,25-epoxide Rg1; on the other hand, as a nucleophilic group, HSO reacted with 24,25-epoxide Rg1 and further dehydrated to 25-ene SRg1. This study provided a technical support for the promotion of 25-ene SRg1 as the characteristic quality control marker of sulfur-fumigated ginseng.
人参是一种最受欢迎的具有保健作用的食品，其主要生物活性成分为人参皂苷。非法硫磺熏蒸会导致人参皂苷转化为有毒的含硫衍生物，降低人参的功效/安全性。24-磺酸-25-烯基人参皂苷 Rg1（25-烯基 SRg1）是一种含硫衍生物，是熏蒸人参的潜在质量控制标志物，但由于其生成机制未知，其可及性较低。在这项研究中，研究并验证了涉及金属/亚硫酸氢盐系统的生成机制。硫磺熏蒸人参中 25-烯基 SRg1 的生成是在硫磺熏蒸过程中形成的 SO，与水反应并离子化为 HSO。一方面，在金属/亚硫酸氢盐系统中，HSO 生成 HSO 和自由基，将人参皂苷 Rg1 转化为 24,25-环氧 Rg1；另一方面，HSO 作为亲核基团与 24,25-环氧 Rg1 反应并进一步脱水生成 25-烯基 SRg1。本研究为人参 25-烯基 SRg1 作为硫磺熏蒸人参特征性质量控制标志物的推广提供了技术支持。
