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Analytica Chimica Acta
Volume 613, Issue 1, 14 April 2008, Pages 74-82
 
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doi:10.1016/j.aca.2008.02.052    
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Copyright © 2008 Elsevier B.V. All rights reserved.

Rapid identification of oleanane-type saponins in the roots of Stephanotis mucronata by liquid chromatography/electrospray tandem mass spectrometry

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Juanjuan Chena, Yiping Yeb, Cuirong Suna and Yuanjiang Pana, Corresponding Author Contact Information, E-mail The Corresponding Author

aDepartment of Chemistry, Zhejiang University, Hangzhou 310027, China

bInstitute of Materia Medica, Zhejiang Academy of Medical Sciences, Hangzhou 310028, China


Received 4 January 2008; 
revised 26 February 2008; 
accepted 26 February 2008. 
Available online 4 March 2008.

Abstract

The liquid chromatography/electrospray tandem mass spectrometry method was developed for analyses and characterization of oleanane-type saponins in the roots of Stephanotis mucronata. Collision-induced dissociation have been performed in order to elucidate the degradation pathways for the [M+Na]+ ions and their predominant product ions. The following characteristic fragmentation was observed from the title saponins: when the substituent (except hydroxyl group) located at C21 position, direct loss of terminal sugar residue from the [M+Na]+ ion was observed; when the substituent (except hydroxyl group) linked to C22 position, the loss of the terminal sugar cannot occur. To further confirm the structures, offline Fourier transform ion cyclotron resonance tandem mass spectrometry (FTICR-MSn) was performed. The structures of four proposed saponins have been identified by 1D and 2D NMR experiments. In this study, 12 saponins were identified. Among them, to our knowledge, four saponins were reported in this plant for the first time and four saponins were presumed to be new compounds. Hence, the described method has wide applicability to rapidly screen and provide structural information of oleanane-type saponins in crude materials.

Keywords: Stephanotis mucronata; Oleanane-type saponins; Liquid chromatography/electrospray tandem mass spectrometry; Fourier transform ion cyclotron resonance tandem mass spectrometry

Article Outline

1. Introduction
2. Experimental
2.1. Reagents and chemicals
2.2. Sample preparation
2.3. Analytical and preparative high-performance liquid chromatography
2.4. Mass spectrometry
2.5. NMR spectroscopy
3. Results and discussion
3.1. Structural characterization of S-4, 6, 7 and 12
3.2. Structural characterization of S-1–3, 5, 8–11
3.2.1. Structural characterization of S-8 and 10
3.2.2. Structural characterization of S-1
3.2.3. Structural characterization of S-3, 9 and 11
3.2.4. Structural characterization of S-2 and 5
4. Conclusions
Acknowledgements
Appendix A. Supplementary data
References





Corresponding Author Contact InformationCorresponding author. Tel.: +86 571 87951629.

Analytica Chimica Acta
Volume 613, Issue 1, 14 April 2008, Pages 74-82
 
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