目的 系统研究硫磺熏蒸对金银花Lonicerae Japonicae Flos化学成分的影响，寻找代表性的金银花硫熏化学标志物。方法 采用UHPLC-Q-TOF-MS高分辨质谱法，以Waters HSS T3为色谱柱，0.1%甲酸水溶液和0.1%甲酸乙腈溶液为流动相，梯度洗脱，采用ESI负离子扫描模式对无硫金银花和硫熏金银花样品进行测定；并结合Mass Profiler Professional软件，应用主成分分析和t检验等化学计量学方法分析金银花硫熏前后差异性成分，并对主要差异成分进行鉴定。通过权重赋值法筛选硫熏化学标志物。结果 无硫金银花和硫熏金银花样品可被明显地区分开，主成分之间存在明显差异；筛选出65种差异性化学成分，对其中23种主要差异性成分进行了鉴定，为金银花酚酸类化合物的磺化产物和亚硫酸加成产物，以及环烯醚萜类化合物的亚硫酸酯和亚硫酸加成产物，其中13种含硫衍生物未见文献报道；并通过制备色谱分离和¹H-NMR确认了绿原酸磺化产物的化学结构。断马钱子酸亚硫酸酯、绿原酸磺化产物、马钱子苷A亚硫酸加成产物3个化合物权重赋值法得分较高。结论 筛选和鉴定了金银花硫熏前后主要差异性成分，断马钱子酸亚硫酸酯等3个含硫衍生物推荐为候选的硫熏化学标志物。为阐明金银花化学成分在硫熏过程中的转化机制以及硫熏金银花的筛查和金银花的质量控制提供了参考。

Objective To comprehensively investigate the effect of sulfur fumigation on the chemical composition of Jinyinhua (Lonicerae Japonicae Flos, LJF) and seek the typical chemical markers of sulfur-fumigated LJF. Methods Both non-sulfur and sulfur-fumigated LJF were analyzed by UHPLC-Q-TOF-MS. The separation was conducted using a gradient elution program with 0.1% formic acid aqueous solution and 0.1% formic acid acetonitrile as mobile phases on a Waters HSS T3 column. In addition, ESI negative ion mode was employed for the mass spectrometry analysis. Chemometrics such as principal component analysis (PCA) and t-test were used to examine the variations in the chemical components of LJF before and after sulfur fumigation combined with Mass Profiler Professional software. The main differential components were subjected for the identification. The Weight assignment method was employed to screen chemical markers of sulfur fumigation. Results The results indicated that the non-sulfur and sulfur-fumigated LJF samples could be clearly distinguished, and significant difference was observed among the principal components. Sixty-five differential components were screened out, 23 of which were identified as the sulfonated products and sulfite acid addition products of phenolic acid compounds, and sulfite esters and sulfite addition products of iridoid compounds of LJF. Thirteen sulfur-containing derivatives were not reported in the literature. The structure of the sulfonated product of chlorogenic acid was characterized by the preparative chromatography separation and ¹H NMR method. Three compounds including secologanic acid sulfite, sulfonated product of chlorogenic acid and strychnine A sulfite addition product got higher scores by the weight assignment method. Conclusion The principal differential components of LJF before and after sulfur fumigation were screened and identified. Three sulfur-containing derivatives were recommended as candidates of chemical markers of sulfur fumigation. This study provides a reference for the illustration of the transformation mechanism of chemical components in LJF during the sulfur fumigation and provided a basis for the rapid screening of sulfur-fumigated LJF and the quality control of LJF.

R284.1

苏州市科技计划项目（SYS2019116）