Metals/bisulfite system involved generation of 24-sulfonic-25-ene ginsenoside Rg1, a potential quality control marker for sulfur-fumigated ginseng

• Published in: Food chemistry Vol. 448; p. 139112
• Main Authors: Liu, Hui, Wu, Xiao-Qian, Qin, Xiang-Ling, Zhu, Jin-Hao, Xu, Jin-Di, Zhou, Shan-Shan, Kong, Ming, Shen, Hong, Huo, Jie-Ge, Li, Song-Lin, Zhu, He
• Format: Journal Article
• Language: English
• Published: England Elsevier Ltd 01-08-2024
• Subjects: 24-sulfo-25-ene ginsenoside Rg1; 24-sulfo-25-hydroxy ginsenoside Rg1; Fumigation; Generation mechanism; Ginseng; Ginsenosides - analysis; Ginsenosides - chemistry; Metals - analysis; Metals - chemistry; Metals/bisulfite system; Panax - chemistry; Plant Extracts - chemistry; Quality Control; Sulfites - analysis; Sulfites - chemistry; Sulfur - chemistry; Sulfur-fumigation; 25-ene SPPT; O2; HQ; Sulfur-fumigation; 25-OH SRg1; NFG; 24-sulfo-25-ene ginsenoside Rg1; Generation mechanism; 24-sulfo-25-hydroxy ginsenoside Rg1; 25-OH SPPT; PPT; SFG; SO3; SO2; SO5; SO4; CID; H2SO3; N2; UPLC-QTOF-MS/MS; HSO3; HSO5; NAC; Metals/bisulfite system; MeOH; 25-ene SRg1; ICP-MS; Ginseng
• ISSN: 0308-8146; 1873-7072
• DOI: 10.1016/j.foodchem.2024.139112

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 SO2, formed during sulfur-fumigation, reacted with water and ionized into HSO3−. On the one hand, under the metals/bisulfite system, HSO3− generates HSO5− and free radicals which converted ginsenoside Rg1 to 24,25-epoxide Rg1; on the other hand, as a nucleophilic group, HSO3− 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.
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•HSO3−, O2 and metals take part the generation of 24-sulfonic-25-ene Rg1 (25-ene SRg1).•HSO3−, O2 and metals in sulfur-fumigated ginseng composed metals/bisulfite system.•Metals/bisulfite system generates oxysulfur radicals and HSO5− in fumigated ginseng.•Oxysulfur radicals and HSO5− oxidized Rg1 to 24,25-epoxide Rg1 during fumigation.•Epoxide Rg1 reacted with HSO3−, and further dehydrated to generate 25-ene SRg1.