目的 系統(tǒng)研究硫磺熏蒸對金銀花Lonicerae Japonicae Flos化學(xué)成分的影響，尋找代表性的金銀花硫熏化學(xué)標(biāo)志物。方法 采用UHPLC-Q-TOF-MS高分辨質(zhì)譜法，以Waters HSS T3為色譜柱，0.1%甲酸水溶液和0.1%甲酸乙腈溶液為流動相，梯度洗脫，采用ESI負(fù)離子掃描模式對無硫金銀花和硫熏金銀花樣品進(jìn)行測定；并結(jié)合Mass Profiler Professional軟件，應(yīng)用主成分分析和t檢驗(yàn)等化學(xué)計(jì)量學(xué)方法分析金銀花硫熏前后差異性成分，并對主要差異成分進(jìn)行鑒定。通過權(quán)重賦值法篩選硫熏化學(xué)標(biāo)志物。結(jié)果 無硫金銀花和硫熏金銀花樣品可被明顯地區(qū)分開，主成分之間存在明顯差異；篩選出65種差異性化學(xué)成分，對其中23種主要差異性成分進(jìn)行了鑒定，為金銀花酚酸類化合物的磺化產(chǎn)物和亞硫酸加成產(chǎn)物，以及環(huán)烯醚萜類化合物的亞硫酸酯和亞硫酸加成產(chǎn)物，其中13種含硫衍生物未見文獻(xiàn)報(bào)道；并通過制備色譜分離和¹H-NMR確認(rèn)了綠原酸磺化產(chǎn)物的化學(xué)結(jié)構(gòu)。斷馬錢子酸亞硫酸酯、綠原酸磺化產(chǎn)物、馬錢子苷A亞硫酸加成產(chǎn)物3個(gè)化合物權(quán)重賦值法得分較高。結(jié)論 篩選和鑒定了金銀花硫熏前后主要差異性成分，斷馬錢子酸亞硫酸酯等3個(gè)含硫衍生物推薦為候選的硫熏化學(xué)標(biāo)志物。為闡明金銀花化學(xué)成分在硫熏過程中的轉(zhuǎn)化機(jī)制以及硫熏金銀花的篩查和金銀花的質(zhì)量控制提供了參考。

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

蘇州市科技計(jì)劃項(xiàng)目（SYS2019116）