薄层色谱-碳纤维电离质谱联用技术的开发及其在中药分析中的应用

引用本文: 张强, 时秋娜, 李磊, 李利洁, 苏越, 郭寅龙. 薄层色谱-碳纤维电离质谱联用技术的开发及其在中药分析中的应用[J]. 分析化学, 2022, 50(9): 1345-1354. doi: 10.19756/j.issn.0253-3820.210868 shu

Citation: ZHANG Qiang, SHI Qiu-Na, LI Lei, LI Li-Jie, SU Yue, GUO Yin-Long. Development of Thin-layer Chromatography Carbon Fiber Ionization Mass Spectrometry and Its Application in Analysis of Traditional Chinese Medicine[J]. Chinese Journal of Analytical Chemistry, 2022, 50(9): 1345-1354. doi: 10.19756/j.issn.0253-3820.210868 shu

薄层色谱-碳纤维电离质谱联用技术的开发及其在中药分析中的应用

张强 ^1,2,3, ,
时秋娜 ^{1,
,} ,
李磊 ^1, ,
李利洁 ^1, ,
苏越 ^3, ,
郭寅龙 ^{2,
,}

1.
河南警察学院刑事科学技术系, 郑州 450046;
2.
中国科学院上海有机化学研究所, 金属有机国家重点实验室, 上海有机质谱中心, 上海 200032;
3.
上海中医药大学, 中医方证与系统生物学研究中心, 上海 201203

通讯作者: 时秋娜,E-mail:752252414@qq.com; 郭寅龙,E-mail:ylguo@sioc.ac.cn

基金项目:
教育部人文社会科学研究青年基金项目（No.20YJC820062）、河南省科技攻关项目（No.222102310354）、河南省高等学校重点科研项目（Nos.22B150003，22B150004）、河南省高校人文社会科学研究一般项目（No.2021-ZDJH-0113）、河南警察学院院级课题资助项目（No.HNJY-2021-45）和河南警察学院教学改革研究与实践项目（No.JY2021021）资助。

摘要: 开发了薄层色谱-碳纤维电离质谱(TLC-CFI-MS)联用技术用于中药分析。为了满足不同种类样品或不同分析场景的需求,分别设计了溶剂辅助TLC-CFI-MS和热辅助TLC-CFI-MS两种分析方法。考察了两种方法测定香豆素的分析性能,溶剂辅助TLC-CFI-MS的检出限(LOD)为8 μg/mL,定量限(LOQ)为30 μg/mL;热辅助TLC-CFI-MS的LOD为20 ng/mL,LOQ为50 ng/mL;热辅助TLC-CFI-MS对浓度为0.01~1 mg/mL的香豆素呈良好的线性关系。对溶剂辅助TLC-CFI-MS和热辅助TLC-CFI-MS在中药分析中的应用进行了比较,两种方法均实现了肉桂和川芎TLC分析后层析板上化合物的原位快速鉴定,成功鉴定出香豆素、桂皮醛、藁本内酯、蛇床内酯和洋川芎内酯A;通过热辅助TLC-CFI-MS方法对一批次肉桂药材中香豆素含量测定约为1.04 mg/g。TLC-CFI-MS在中药化合物的快速分析中具有良好的应用价值,有望在中药质量控制和评价等领域得到应用。

关键词:

薄层色谱
/ 碳纤维
/ 质谱
/ 中药

English

Development of Thin-layer Chromatography Carbon Fiber Ionization Mass Spectrometry and Its Application in Analysis of Traditional Chinese Medicine

ZHANG Qiang ^1,2,3, ,
SHI Qiu-Na ^{1,
,} ,
LI Lei ^1, ,
LI Li-Jie ^1, ,
SU Yue ^3, ,
GUO Yin-Long ^{2,
,}

1.
Department of Criminal Science and Technology, Henan Police College, Zhengzhou 450046, China;
2.
State Key Laboratory of Organometallic Chemistry and National Center for Organic Mass Spectrometry in Shanghai, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China;
3.
Center for Chinese Medicine Therapy and Systems Biology, Shanghai University of Traditional Chinese Medicine, Shanghai 201203, China

Corresponding author: SHI Qiu-Na, ; GUO Yin-Long,

Received Date: 29 November 2021
Revised Date: 08 March 2022
Fund Project:
Supported by the Humanity and Social Science Youth Foundation of Ministry of Education of China (No.20YJC820062), the Henan Province Science and Technology Research Project (No.222102310354), the Key Scientific Research Projects of Higher Education Institutions in Henan Province (Nos.22B150003, 22B150004), the Humanities and Social Sciences Research Project of Henan Provincial Department of Education (No.2021-ZDJH-0113), the College-level Scientific Research Project of Henan Police College (No.HNJY-2021-45) and the Teaching Reform Research and Practice Project of Henan Police College (No.JY2021021).

Abstract: To realize simple, rapid, in-situ, non-destructive analysis and identification of compounds on thin-layer chromatography, a combined technology of thin-layer chromatography with carbon fiber ionization mass spectrometry (TLC-CFI-MS) was developed, and the application of this technique in the field of Chinese medicine analysis was studied. First, to meet the needs of different types of samples or different analysis scenarios, two analysis modes of solvent-assisted TLC-CFI-MS and heat-assisted TLC-CFI-MS were designed. Then, the application of the above two analysis methods in analysis of traditional Chinese medicine was studied, and the analytical performance of the two analytical methods was examined. The limit of detection (LOD) of coumarin by solvent-assisted TLC-CFI-MS was 8 μg/mL, and the limit of quantification (LOQ) was 30 μg/mL; LOD and LOQ of heat-assisted TLC-CFI-MS were 20 ng/mL and 50 ng/mL, respectively. The heat-assisted TLC-CFI-MS demonstrated the quantitative analysis capability for coumarin in the concentration range of 0.01-1 mg/mL (R²=0.997). In addition, the application of solvent-assisted TLC-CFI-MS and heat-assisted TLC-CFI-MS in the analysis of traditional Chinese medicines was preliminarily explored. Both methods achieved rapid in-situ identification of compounds on chromatographic plates after TLC analysis of Cinnamomum cassia and Ligusticum chuanxiong. For example, coumarin and cinnamic aldehyde from Cinnamomum cassia and ligustilide, snidium lactone and ligustride A from Ligusticum chuanxiong were all identified. In addition, the coumarin content in a cinnamon sample was determined to be 1.04 mg/g by heat-assisted TLC-CFI-MS. The results suggested that TLC-CFI-MS had certain application potential in the rapid analysis of traditional Chinese medicine compounds. It would also show certain application value in the analysis of traditional Chinese medicine components, as well as quality control and evaluation.

Key words:

1. [1]
  CHENG S C, HUANG M Z, SHIEA J T. J. Chromatogr. A, 2011, 1218(19):2700-2711.CHENG S C, HUANG M Z, SHIEA J T. J. Chromatogr. A, 2011, 1218(19):2700-2711.
2. [2]
  YE Z, DAI J R, ZHANG C G, LU Y, WU L L, GONG A G W, XU H, TSIM K W K, WANG Z T. Evidence-Based Complementary Altern. Med., 2017, 2017:8647212.YE Z, DAI J R, ZHANG C G, LU Y, WU L L, GONG A G W, XU H, TSIM K W K, WANG Z T. Evidence-Based Complementary Altern. Med., 2017, 2017:8647212.
3. [3]
  WONG K H, RAZMOVSKI-NAUMOVSKI V, LI K M, LI G Q, CHAN K. J. Pharm. Biomed. Anal., 2014, 95:11-19.WONG K H, RAZMOVSKI-NAUMOVSKI V, LI K M, LI G Q, CHAN K. J. Pharm. Biomed. Anal., 2014, 95:11-19.
4. [4]
  HE F Y, HE Y, ZHENG X W, WANG R Z, LU J, DAI Z, MA S C. J. AOAC Int., 2018, 101(3):686-694.HE F Y, HE Y, ZHENG X W, WANG R Z, LU J, DAI Z, MA S C. J. AOAC Int., 2018, 101(3):686-694.
5. [5]
  BLATTER A, REICH E. J. Planar Chromatogr.-Mod. TLC, 2004, 17(5):355-359.BLATTER A, REICH E. J. Planar Chromatogr.-Mod. TLC, 2004, 17(5):355-359.
6. [6]
  MARTELANC M, VOVK I, SIMONOVSKA B. J.Chromatogr. A, 2009, 1216(38):6662-6670.MARTELANC M, VOVK I, SIMONOVSKA B. J.Chromatogr. A, 2009, 1216(38):6662-6670.
7. [7]
  COOKS R G, OUYANG Z, TAKATS Z, WISEMAN J M. Science, 2006, 311(5767):1566-1570.COOKS R G, OUYANG Z, TAKATS Z, WISEMAN J M. Science, 2006, 311(5767):1566-1570.
8. [8]
  LI Bao-Qiang, ZHANG Zhong-Yao, KONG Jing-Lin, ZHANG Lin, GUO Cheng-Hai, LI Cui-Ping. J. Chin. Mass Spectrom. Soc., 2020, 41(3):221-235. 李宝强, 张众垚, 孔景临, 张琳, 郭成海, 李翠萍. 质谱学报, 2020, 41(3):221-235.
9. [9]
  HU Qing-Yuan, MA Qiang, OUYANG Zheng, MA Xiao-Xiao. J. Chin. Mass Spectrom. Soc., 2021, 42(4):372-380. 胡清源, 马强, 欧阳证, 马潇潇. 质谱学报, 2021, 42(4):372-380.
10. [10]
  HUANG M Z, CHENG S C, CHO Y T, SHIEA J T. Anal. Chim. Acta, 2011, 702(1):1-15.HUANG M Z, CHENG S C, CHO Y T, SHIEA J T. Anal. Chim. Acta, 2011, 702(1):1-15.
11. [11]
  ALBERICI R M, SIMAS R C, SANVIDO G B, ROM O W, LALLI P M, BENASSI M, CUNHA I B S, EBERLIN M N. Anal. Bioanal. Chem., 2010, 398(1):265-294.ALBERICI R M, SIMAS R C, SANVIDO G B, ROM O W, LALLI P M, BENASSI M, CUNHA I B S, EBERLIN M N. Anal. Bioanal. Chem., 2010, 398(1):265-294.
12. [12]
  ZHANG Lin, MA Ming-Ying, LI Bao-Qiang, KONG Jing-Lin, ZHANG Si-Chun, ZHANG Xin-Rong. Chin. J. Anal. Chem., 2020, 48(10):1416-1421. 张琳, 马明英, 李宝强, 孔景临, 张四纯, 张新荣. 分析化学, 2020, 48(10):1416-1421.
13. [13]
  ZHANG Xing-Lei, ZHANG Hua, WANG Xin-Chen, HUANG Ke-Ke, WANG Dan, CHEN Huan-Wen. Chin. J. Anal. Chem., 2018, 46(11):1703-1713. 张兴磊, 张华, 王新晨, 黄科科, 王丹, 陈焕文. 分析化学, 2018, 46(11):1703-1713.
14. [14]
  WANG Zhong-Hua, HE Bing-Shu, SUN Cheng-Long, SONG Xiao-Wei, HE Jiu-Ming, ZHANG Rui-Ping, ABLIZ Zeper. Chin. J. Anal. Chem., 2018, 46(3):406-412. 王中华, 何秉淑, 孙成龙, 宋肖炜, 贺玖明, 张瑞萍, 再帕尔·阿不力孜. 分析化学, 2018, 46(3):406-412.
15. [15]
  YANG Y Y, DENG J W. TrAC, Trends Anal. Chem., 2016, 82:68-88.YANG Y Y, DENG J W. TrAC, Trends Anal. Chem., 2016, 82:68-88.
16. [16]
  HUANG Xin, LIU Wen-Long, ZHANG Yong, LIU Shu-Ying. J. Chin. Mass Spectrom. Soc., 2017, 38(1):1-10. 黄鑫, 刘文龙, 张勇, 刘淑莹. 质谱学报, 2017, 38(1):1-10.
17. [17]
  CHEN Y L, LI L N, XIONG F, XIE Y Q, XIONG A Z, WANG Z T, YANG L. Food Chem., 2021, 334:127472.CHEN Y L, LI L N, XIONG F, XIE Y Q, XIONG A Z, WANG Z T, YANG L. Food Chem., 2021, 334:127472.
18. [18]
  ZHANG Zhao-Hui, CHEN Ying-Zhuang, CHEN Bo, MA Ming. Chin. J. Anal. Chem., 2020, 48(9):1236-1243. 张朝辉, 陈应庄, 陈波, 马铭. 分析化学, 2020, 48(9):1236-1243.
19. [19]
  HARRY E L, REYNOLDS J C, BRISTOW A W T, WILSON I D, CREASER C S. Rapid Commun. Mass Spectrom., 2009, 23(17):2597-2604.HARRY E L, REYNOLDS J C, BRISTOW A W T, WILSON I D, CREASER C S. Rapid Commun. Mass Spectrom., 2009, 23(17):2597-2604.
20. [20]
  DEVENPORT N A, REYNOLDS J C, WESTON D J, WILSON I D, CREASER C S. Analyst, 2012, 137(15):3510-3513.DEVENPORT N A, REYNOLDS J C, WESTON D J, WILSON I D, CREASER C S. Analyst, 2012, 137(15):3510-3513.
21. [21]
  CEGŁOWSKI M, SMOLUCH M, RESZKE E, SILBERRING J, SCHROEDER G. Anal. Bioanal. Chem., 2016, 408(3):815-823.CEGŁOWSKI M, SMOLUCH M, RESZKE E, SILBERRING J, SCHROEDER G. Anal. Bioanal. Chem., 2016, 408(3):815-823.
22. [22]
  MORLOCK G, SCHWACK W. TrAC, Trends Anal. Chem., 2010, 29(10):1157-1171.MORLOCK G, SCHWACK W. TrAC, Trends Anal. Chem., 2010, 29(10):1157-1171.
23. [23]
  MORLOCK G, UEDA Y. J. Chromatogr. A, 2007, 1143(1):243-251.MORLOCK G, UEDA Y. J. Chromatogr. A, 2007, 1143(1):243-251.
24. [24]
  GONG X X, ZHANG D, EMBILE I B, SHE Y, SHI S Y, GAMEZ G. J. Am. Soc. Mass Spectrom., 2020, 31(9):1981-1993.GONG X X, ZHANG D, EMBILE I B, SHE Y, SHI S Y, GAMEZ G. J. Am. Soc. Mass Spectrom., 2020, 31(9):1981-1993.
25. [25]
  SAJEWICZ M, STASZEK D, NATIC M, KOWALSKA T, WAKSMUNDZKAHAJNOS M. J. Chromatogr. Sci., 2011, 49(7):560-567.SAJEWICZ M, STASZEK D, NATIC M, KOWALSKA T, WAKSMUNDZKAHAJNOS M. J. Chromatogr. Sci., 2011, 49(7):560-567.
26. [26]
  CORAN S A, MULAS S, VASCONI A. J. Chromatogr. A, 2014, 1325:221-226.CORAN S A, MULAS S, VASCONI A. J. Chromatogr. A, 2014, 1325:221-226.
27. [27]
  ZHANG L, SHI J Y, TANG J H, CHENG Z H, LU X H, KONG Y, WU T. Anal. Chim. Acta, 2017, 967:52-58.ZHANG L, SHI J Y, TANG J H, CHENG Z H, LU X H, KONG Y, WU T. Anal. Chim. Acta, 2017, 967:52-58.
28. [28]
  KIM H J, OH M S, HONG J, JANG Y P. Phytochem. Anal., 2011, 22(3):258-262.KIM H J, OH M S, HONG J, JANG Y P. Phytochem. Anal., 2011, 22(3):258-262.
29. [29]
  WU M X, WANG H Y, ZHANG J T, GUO Y L. Anal. Chem., 2016, 88(19):9547-9553.WU M X, WANG H Y, ZHANG J T, GUO Y L. Anal. Chem., 2016, 88(19):9547-9553.
30. [30]
  WU M L, CHEN T Y, CHEN Y C, CHEN Y C. Anal. Chem., 2017, 89(24):13458-13465.WU M L, CHEN T Y, CHEN Y C, CHEN Y C. Anal. Chem., 2017, 89(24):13458-13465.
31. [31]
  ZHANG Qiang, SU Yue, GUO Yin-Long. J. Chin. Mass Spectrom. Soc., 2021, 42(2):118-128. 张强, 苏越, 郭寅龙. 质谱学报, 2021, 42(2):118-128.
32. [32]
  ZHANG Q, LIU X P, LI Z Q, SU Y, GUO Y L. Anal. Chim. Acta, 2019, 1048:115-122.ZHANG Q, LIU X P, LI Z Q, SU Y, GUO Y L. Anal. Chim. Acta, 2019, 1048:115-122.
33. [33]
  WANG Z Y, CAO Y Q, LU Y J, ZHANG F, SU Y, GUO Y L. Anal. Chim. Acta, 2020, 1136:62-71.WANG Z Y, CAO Y Q, LU Y J, ZHANG F, SU Y, GUO Y L. Anal. Chim. Acta, 2020, 1136:62-71.
34. [34]
  National Pharmacopoeia Committee. The Pharmacopoeia of the People's Republic of China (Part I, 2020 Ed.), Beijing:China Medical Science Press, 2020:42-43. 国家药典委员会编. 中华人民共和国药典(一部, 2020年版). 北京:中国医药科技出版社, 2020:42-43.
35. [35]
  National Pharmacopoeia Committee. The Pharmacopoeia of the People's Republic of China (Part IV, 2020 Ed.), Beijing:China Medical Science Press, 2020:59-60. 国家药典委员会编. 中华人民共和国药典(四部, 2020年版). 北京:中国医药科技出版社, 2020:59-60.
36. [36]
  HE Z D, QIAO C F, HAN Q B, SONG J Z, CHENG C L, XU H X, JIANG R W, WONG K L, BUT P P, SHAW P C. J. Chin. Pharmaceut. Sci., 2006, 15(4):195-199.HE Z D, QIAO C F, HAN Q B, SONG J Z, CHENG C L, XU H X, JIANG R W, WONG K L, BUT P P, SHAW P C. J. Chin. Pharmaceut. Sci., 2006, 15(4):195-199.
37. [37]
  ZHANG Qiang, ZHAN Shao-Xu, WANG Shan-Shan, HUANG Xiao-Bo, CHEN Jia-Jun, SHI Qiu-Na, GUO Yin-Long. J. Chin. Mass Spectrom. Soc., 2021, 42(4):470-479. 张强, 詹绍旭, 王珊珊, 黄小波, 陈佳骏, 时秋娜, 郭寅龙. 质谱学报, 2021, 42(4):470-479.
38. [38]
  KRÜGER S, WINHEIM L, MORLOCK G E. Food Chem., 2018, 239:1182-1191.KRÜGER S, WINHEIM L, MORLOCK G E. Food Chem., 2018, 239:1182-1191.
39. [39]
  MEHER A K, CHEN Y C. Anal. Chim. Acta, 2017, 966:41-46.MEHER A K, CHEN Y C. Anal. Chim. Acta, 2017, 966:41-46.
40. [40]
  YI T, FANG J Y, ZHU L, TANG Y N, JI H, ZHANG Y Z, YU J C, ZHANG X J, YU Z L, ZHAO Z Z, CHEN H B. Chin. Med., 2016, 11:26.YI T, FANG J Y, ZHU L, TANG Y N, JI H, ZHANG Y Z, YU J C, ZHANG X J, YU Z L, ZHAO Z Z, CHEN H B. Chin. Med., 2016, 11:26.
41. [41]
  HAN Wei. Modern Chin. Med., 2017, 19(9):1341-1349. 韩炜. 中国现代中药, 2017, 19(9):1341-1349.

扫一扫看文章

计量

PDF下载量: 5
文章访问数: 363
HTML全文浏览量: 6

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

薄层色谱-碳纤维电离质谱联用技术的开发及其在中药分析中的应用

通讯作者: 时秋娜,E-mail:752252414@qq.com; 郭寅龙,E-mail:ylguo@sioc.ac.cn

English

Development of Thin-layer Chromatography Carbon Fiber Ionization Mass Spectrometry and Its Application in Analysis of Traditional Chinese Medicine

Corresponding author: SHI Qiu-Na, ; GUO Yin-Long,

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

薄层色谱-碳纤维电离质谱联用技术的开发及其在中药分析中的应用

通讯作者: 时秋娜,E-mail:752252414@qq.com; 郭寅龙,E-mail:ylguo@sioc.ac.cn

English

Development of Thin-layer Chromatography Carbon Fiber Ionization Mass Spectrometry and Its Application in Analysis of Traditional Chinese Medicine

Corresponding author: SHI Qiu-Na, ; GUO Yin-Long,

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs