芍药单萜苷在电喷雾串联质谱中丢失30 Da的裂解机制研究

doi:10.5246/jcps.2016.01.005

中国药学(英文版) ›› 2016, Vol. 25 ›› Issue (1): 37-45.DOI: 10.5246/jcps.2016.01.005

芍药单萜苷在电喷雾串联质谱中丢失30 Da的裂解机制研究

曹静, 乔雪, 季帅, 苗文娟, 果德安, 叶敏^*

北京大学医学部药学院天然药物及仿生药物国家重点实验室, 北京 100191

收稿日期:2015-09-20 修回日期:2015-10-20 出版日期:2016-01-27 发布日期:2015-11-02
通讯作者: Tel.: 86-10-82802024, E-mail: yemin@bjmu.edu.cn
基金资助:
National Natural Science Foundation of China (Grant No. 81222054), the Program for New Century Excellent Talents in University from Chinese Ministry of Education (Grant No. NCET-11-0019) and Chinese Pharmacopoeia Commission.

Insights into the neutral loss of 30 Da of Paeonia monoterpene glycosides in electrospray ionization tandem mass spectrometry and the rapid screening of monoterpene glycosides by LC/MS/MS

Jing Cao, Xue Qiao, Shuai Ji, Wenjuan Miao, De-an Guo, Min Ye^*

State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University Health Science Center, Beijing 100191, China

Received:2015-09-20 Revised:2015-10-20 Online:2016-01-27 Published:2015-11-02
Contact: Tel.: 86-10-82802024, E-mail: yemin@bjmu.edu.cn
Supported by:
National Natural Science Foundation of China (Grant No. 81222054), the Program for New Century Excellent Talents in University from Chinese Ministry of Education (Grant No. NCET-11-0019) and Chinese Pharmacopoeia Commission.

摘要/Abstract

摘要：

单萜苷是芍药的主要活性成分, 串联质谱裂解易于特征性丢失30 Da。这一现象已被很多学者报道, 然而该裂解的机制研究却报道甚少。本文利用离子阱质谱对芍药的11个单萜苷中性丢失30 Da的质谱裂解机制进行了深入研究。在离子阱质谱中, 含有半缩醛结构的化合物1–5在30%的打击能量下很容易丢失30 Da; 而对于不含有半缩醛结构的化合物6–11, 只有当打击能量增加到60%时, 才能出现较弱的丢失30 Da的碎片离子。经高分辨质谱分析, 化合物1–11丢失的30 Da均为CH₂O。通过对11个单萜苷的结构及质谱裂解特征的深入分析, 我们认为化合物1–5丢失30 Da的机制为半缩醛结构的断裂, 而其他6个不含有半缩醛结构的单萜苷丢失30 Da的机制则可能为葡萄糖基上5¢-羟甲基的断裂。此外, 在低打击能量下丢失30 Da的特征裂解可用于筛选芍药属植物中含有半缩醛的单萜苷类成分, 并用于区分来源于芍药属植物的不同中药。

关键词: 芍药, 单萜苷, 质谱裂解, 中性丢失

Abstract:

Monoterpene glycosides are the major bioactive compounds of Paeonia lactiflora Pall (P. lactiflora). Characteristic neutral loss of 30 Da has been extensively reported for monoterpene glycosides in tandem mass spectrometry. However, little is known about mechanism of this fragmentation. The neutral loss of 30 Da was studied for eleven monoterpene glycosides (1–11) from P. lactiflora by ion trap mass spectrometry in this report. Compounds 1–5 with a hemiacetal structure could readily lose 30 Da at low collision energy of 30% in MS/MS by ion trap mass spectrometry. For compounds 6–11, neutral loss of 30 Da could also be observed at low abundance, but the collision energy had to be increased to 60%. In both cases, high-accuracy mass spectrometry assigned the 30 Da as CH₂O. After careful analysis of the structures and mass spectra, we believe that the neutral loss of 30 Da in compounds 1–5 was due to cleavage of the hemiacetal structure, whereas it was ascribed to the cleavage of 5¢-hydroxymethyl group of the glucosyl residue in other monoterpene glycosides. Furthermore, the characteristic neutral loss of 30 Da at low collision energy was used to screen hemiacetals from crude extracts of P. lactiflora and related plant species. Significant differences among Paeonia species were observed by 30 Da neutral loss analysis.

Key words: Paeonia lactiflora, Monoterpene glycosides, Tandem mass spectrometry, Neutral loss

中图分类号:

R284

Supporting:

Figure S1. (-)-ESI-MS spectra of compounds 1-11 obtained on the ion trap mass spectrometer at a source fragmentation voltage of 10 V.

Figure S2. (+)-ESI-MS spectra of compounds 1-11 obtained on the ion trap mass spectrometer at a source fragmentation voltage of 10 V.

Figure S3. The optimum of capillary voltage and tube lens offset for the ion trap mass spectrometer.

Figure S4. (-)-ESI-MS spectra of compound 1 obtained on the ion trap mass spectrometer at different source fragmentation voltage.

Figure S5. (-)-ESI-MS spectra (A) and (-)-ESI-MS/MS spectra (B) of compound 1 at a collision energy of 30% when the aqueous phase is water with 0.1%(V/V) acetic acid. The precursor ion is [M+CH₃COOH–H]^–, m/z 539.

Figure S6. (-)-ESI-MS/MS spectra of compounds 6-11 obtained on the ion trap mass spectrometer at a collision energy of 30%. The precursor ion is [M–H]^– for compound 7, and [M+HCOOH–H]^– for compounds 6 and 8-11.

Figure S7. (-)-ESI mass spectra of 3 batches of PRA, 3 batches of PRR and 2 batches of MC obtained on the triple quadrupole mass spectrometer by neutral loss scan of 30 Da at a collision energy of 20.

曹静, 乔雪, 季帅, 苗文娟, 果德安, 叶敏. 芍药单萜苷在电喷雾串联质谱中丢失30 Da的裂解机制研究[J]. 中国药学(英文版), 2016, 25(1): 37-45.

Jing Cao, Xue Qiao, Shuai Ji, Wenjuan Miao, De-an Guo, Min Ye. Insights into the neutral loss of 30 Da of Paeonia monoterpene glycosides in electrospray ionization tandem mass spectrometry and the rapid screening of monoterpene glycosides by LC/MS/MS[J]. Journal of Chinese Pharmaceutical Sciences, 2016, 25(1): 37-45.

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芍药单萜苷在电喷雾串联质谱中丢失30 Da的裂解机制研究

Insights into the neutral loss of 30 Da of Paeonia monoterpene glycosides in electrospray ionization tandem mass spectrometry and the rapid screening of monoterpene glycosides by LC/MS/MS

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