Reaction of Chlorogenic Acid with Sulfite and Its Application in Identification of Sulfur-fumigated Herbs

Yu-ting TIAN; Yu WANG; Zhi-peng HUO; Zhao-hui SONG; Yun-gen XU; Yi HE

doi:10.13422/j.cnki.syfjx.20191613

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Reaction of Chlorogenic Acid with Sulfite and Its Application in Identification of Sulfur-fumigated Herbs

Resource and Quality Evaluation | 更新时间：2021-02-09

- Reaction of Chlorogenic Acid with Sulfite and Its Application in Identification of Sulfur-fumigated Herbs
- Chinese Journal of Experimental Traditional Medical Formulae Vol. 25, Issue 23, Pages: 122-127(2019)
- 作者机构：
  
  1.中国药科大学　药学院，南京　 210009；
  2.天士力控股集团有限公司　天士力研究院现代中药开发中心，创新中药关键技术国家重点实验室，天津　 300410；
  3.天津大学　药物科学与技术学院，天津　 300072
- 作者简介：
- 基金信息：
- DOI：10.13422/j.cnki.syfjx.20191613
  CLC： R284.1; R289; R22; R2-031
- Received：22 November 2018，
  
  Published Online：08 May 2019，
  
  Published：05 December 2019
- 稿件说明：
移动端阅览
Yu-ting TIAN, Yu WANG, Zhi-peng HUO, et al. Reaction of Chlorogenic Acid with Sulfite and Its Application in Identification of Sulfur-fumigated Herbs[J]. Chinese journal of experimental traditional medical formulae, 2019, 25(23): 122-127.
DOI：

Yu-ting TIAN, Yu WANG, Zhi-peng HUO, et al. Reaction of Chlorogenic Acid with Sulfite and Its Application in Identification of Sulfur-fumigated Herbs[J]. Chinese journal of experimental traditional medical formulae, 2019, 25(23): 122-127. DOI： 10.13422/j.cnki.syfjx.20191613.

摘要

目的：

探索绿原酸与亚硫酸钠反应产物的结构、反应位点，以及硫熏后金银花中绿原酸化学变化情况。

方法：

将绿原酸与亚硫酸钠置于温和条件下进行化学反应，利用液相色谱-离子阱-飞行时间质谱技术(LC-MS-IT-TOF)以及核磁共振波谱(

H-NMR)检测技术对反应产物进行检测，并用LC-MS-IT-TOF检测硫熏后及未硫熏的金银花水提取液。

结果：

经过对碎片离子、分子裂解规律及精确相对分子质量等质谱数据的分析，结合化学位移、峰强度以及峰裂分等核磁信号结果，初步鉴定绿原酸与亚硫酸钠的生成产物为绿原酸

，

-不饱和羰基加成产物：3-{[3-(3，4-二羟基苯基)-2-磺丙基]氧基}-1，4，5-三羟基环己烷-1-羧酸或者3-{[3-(3，4-二羟基苯基)-3-磺丙基]

氧基}-1，4，5-三羟基环己烷-1-羧酸，并在硫磺熏蒸金银花中检测到与加成产物相同的特征碎片，而在未硫熏金银花中没有发现。

结论：

该研究首次证明了绿原酸与亚硫酸反应产物结构和反应位点，并检测到硫熏金银花中的绿原酸亚硫酸加成产物。尽管目前尚未明确金银花硫熏后产生的亚硫酸加成化合物对金银花功效和毒理活性影响，仍应关注硫熏药材中活性成分的变化情况。同时该研究还可为含有

，

-不饱和羰基结构的中药硫熏后化学成分变化的研究提供参考。

Abstract

Objective:

To explore the structure and reaction sites of the reaction products of chlorogenic acid and sodium sulfite

and the chemical changes of chlorogenic acid in Lonicerae Japonicae Flos after sulfur fumigating.

Method:

Chlorogenic acid was reacted with sodium sulfite under mild conditions. Liquid chromatography-mass spectrometry-ion trap-time-of-flight (LC-MS-IT-TOF) and

H nuclear magnetic resonance spectroscopy (

H-NMR) detection techniques were used to detect the reaction products

and the sulfur-fumigated and unsulfurized Lonicerae Japonicae Flos water extract was detected by LC-MS-IT-TOF.

Result:

After analyzing the mass spectrometry data of fragment ion

molecular cleavage and accurate molecular weight

according to the results of nuclear magnetic signals of chemical shift

peak intensity and peak splitting

the products of chlorogenic acid and sodium sulfite were preliminarily identified as chlorogenic acid

-unsaturated carbonyl addition product: 3-((3-(3

4-dihydroxyphenyl)-2-sulfopropyl)oxy)-1

5-trihydroxycyclohexane-1-carboxylic acid or 3-((3-(3

4-dihy droxyphenyl)-3-sulfopropyl)oxy)-1

5-trihydroxycyclohexane-1-carboxylic acid

and the same characteristic fragments were detected as the addition product in the sulfur fumigated Lonicerae Japonicae Flos

but not found in the unsulfurized.

Conclusion:

It is the first time to demonstrate the structure and reaction sites of chlorogenic acid and sulfurous acid reaction products

and detect the chlorogenic acid sulfite addition product in sulfur-fumigated Lonicerae Japonicae Flos. Although it is still unclear how the sulfite addition compound produced by sulphur Lonicerae Japonicae Flos affects the efficacy and toxicological activity of Lonicerae Japonicae Flos

we shall still pay attention to the changes of active ingredients in sulphuric medicinal materials. Besides

this study can also provide reference for the studies of chemical composition changes after sulfuration of traditional Chinese medicine containing

-unsaturated carbonyl structure.

关键词

Keywords

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