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基于 H-NMR 代谢组学技术比较熏硫和未熏硫白芷的化学成分
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差异及化学标志物筛选 Δ

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董 芸 ，田玫瑰 ，唐荣伟 ，唐 玲 ，赵程成 ，张 艺 ，范 刚 （1.达州中医药职业学院药学系，四川 达州
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635000；2.成都中医药大学民族医药学院，成都 611137）
中图分类号 R284 文献标志码 A 文章编号 1001-0408（2020）13-1557-05
DOI 10.6039/j.issn.1001-0408.2020.13.04
摘 要 目的：研究熏硫与未熏硫白芷药材的整体化学成分差异，并筛选可用于两者鉴别的化学标志物。方法：分别以硫熏和未
硫熏的白芷药材各16批为检测样品，以氘代甲醇-重水（1 ∶ 0.2，V/V）为提取溶剂，采用氢核磁共振（H-NMR）代谢组学技术检测两
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种方法处理的白芷药材中的初级和次级代谢产物。利用直观分析、主成分分析（PCA）和t检验比较二者的化学成分差异，并确定
化学标志物。结果：从两种白芷药材中同时检测并鉴定出了包括香豆素类、氨基酸类、糖类在内的 19 种化学成分。直观分析发
现，两种白芷药材的化学成分轮廓相似，但香豆素类和糖类成分的 H-NMR信号强度有较大的差异；PCA分析结果显示，所有样品
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按不同处理方法分成两类；t 检验结果显示，白芷熏硫后氧化前胡素、欧前胡素、葡萄糖和蔗糖含量均显著降低（P＜0.01 或 P＜
0.001），丙氨酸、亮氨酸含量均显著升高（P＜0.01或P＜0.001），而其余13种成分含量差异无统计学意义（P＞0.05）。结论：熏硫和
未熏硫白芷药材中氧化前胡素、欧前胡素、葡萄糖和蔗糖、丙氨酸、亮氨酸6种化学成分存在明显的差异，可作为化学标志物用于
市场上熏硫白芷的鉴别。
关键词 白芷；熏硫；氢核磁共振代谢组学；化学标志物；鉴别

Comparison of Chemical Constituents Differences between Angelicae dahuricae with and without Sulphur-
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fumigation and Selection of Chemical Markers Based on H-NMR Metabolomics
DONG Yun ，TIAN Meigui ，TANG Rongwei ，TANG Ling ，ZHAO Chengcheng ，ZHANG Yi ，FAN Gang 2
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（1. Dept. of Pharmacy，Dazhou Vocational College of TCM，Sichuan Dazhou 635000，China；2. College of
Ethnic Medicine，Chengdu University of TCM，Chengdu 611137，China）
ABSTRACT OBJECTIVE：To study the differences in the overall chemical constituents of Angelicae dahuricae with and without
sulphur-fumigation，and to select chemical markers that can be used for identification. METHODS：Each 16 batches of A.
dahuricae with and without sulphur-fumigation were selected as samples. Deuterated methanol-deuterium oxide（1 ∶ 0.2，V/V）was
used as extraction solvent，and H-NMR metabolomics was used to detect the primary and secondary metabolites in A. dahuricae.
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In addition，visual analysis，principal component analysis（PCA）and t-test were used to compare the component differences of A.
dahuricae by two kinds of pretreatment methods. RESULTS：A total of 19 chemical constituents such as coumarins，amino acids
and sugars were simultaneously detected and identified from two kinds of A. dahuricae. Visual analysis showed that the chemical
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profiles of the two kinds of A. dahuricae were similar，but their coumarins and carbohydrates were quite different in H-NMR
signal intensity. PCA analysis showed that all samples could be divided into two categories according to different treatment methods.
The results of t-test showed that the contents of oxypeucedanin，imperatorin，glucose and sucrose of A. dahuricae were decreased
significantly after sulphur fumigation（P＜0.01 or P＜0.001），while the contents of alanine and leucine were significantly increased
（P＜0.01 or P＜0.001）. There was no statistical significance in the contents of other 13 kinds of components （P＞0.05）.
CONCLUSIONS：There are obvious differences in the 6 chemical compounds of oxypeucedanin，imperatorin，glucose，sucrose，
alanine and leucine in A. dahuricae with and without sulphur-fumigation，which can be used as chemical markers for the
identification of sulphur-fumigated A. dahuricae in the market.
KEYWORDS Angelicae dahuricae；Sulphur-fumigation；H-NMR metabolomics；Chemical markers；Identification
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白芷为常用中药材，来源于伞形科植物白芷[Angeli- ca dahurica（Fisch. ex Hoffm.）Benth. et Hook. f.]或杭白

Δ 基 金 项 目 ：国 家 自 然 科 学 基 金 资 助 项 目（No.81874370， 芷[Angelica dahurica（Fisch. ex Hoffm.）Benth. et Hook.
No.81303310）；国家重点研发计划项目（No.2017YFC1703900） f. var. formosana（Boiss.）Shan et Yuan]的干燥根，其味
＊讲师。研究方向：中药质量控制。E-mail：524632023@qq.com
辛，性温，具有解表散寒、祛风止痛、宣通鼻窍、燥湿止
# 通信作者：副研究员，博士。研究方向：中药及民族药质量控制
与评价。电话：028-61800160。E-mail：fangang1111@163.com 带、消肿排脓等功效，可用于治疗感冒头痛、眉棱骨痛、

中国药房 2020年第31卷第13期 China Pharmacy 2020 Vol. 31 No. 13 ·1557 ·