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

doi:10.5246/jcps.2016.01.005

Journal of Chinese Pharmaceutical Sciences ›› 2016, Vol. 25 ›› Issue (1): 37-45.DOI: 10.5246/jcps.2016.01.005

• Original articles • Previous Articles Next Articles

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.

Abstract

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

CLC Number:

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.

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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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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