Tandem Mass Spectrometric Analysis of a Complex Triterpene Saponin Mixture of Chenopodium Quinoa

Overview

Journal J Am Soc Mass Spectrom

Specialty Chemistry

Date 2006 Apr 11

PMID 16603377

Citations 29

Authors

Tobias Madl

Heinz Sterk

Martin Mittelbach

Gerald N Rechberger

Affiliations

Soon will be listed here.

Abstract

A nano-HPLC electrospray ionization multi-stage tandem mass spectrometry (nLC-ESI-MS/MS) approach was applied to a complex crude triterpene saponin extract of Chenopodium quinoa seed coats. In ESI-MS/MS spectra of triterpene saponins, characteristic fragmentation reactions are observed and allow the determination of aglycones, saccharide sequences, compositions, and branching. Fragmentation of aglycones provided further structural information. The chemical complexity of the mixture was resolved by a complete profiling. Eighty-seven triterpene saponins comprising 19 reported and 68 novel components were identified and studied by MS. In addition to four reported, five novel triterpene aglycones were detected and characterized according to their fragmentation reactions in ESI-MS/MS and electron ionization mass spectrometry (EI-MS). As a novelty fragmentation pathways were proposed and analyzed based upon quantum chemical calculations using a hybrid Hartree-Fock density functional method. Accuracy of the assignment procedure was proven by isolation and structure determination of a novel compound. As the relative distribution and composition of saponins varies between different cultivars and soils, the presented strategy allows a rapid and complete analysis of Chenopodium quinoa saponin distribution and composition, and is particularly suitable for quality control and screening of extracts designated for pharmaceutical, agricultural, and industrial applications.

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References

Estrada A, Li B, Laarveld B . Adjuvant action of Chenopodium quinoa saponins on the induction of antibody responses to intragastric and intranasal administered antigens in mice. Comp Immunol Microbiol Infect Dis. 1998; 21(3):225-36. DOI: 10.1016/s0147-9571(97)00030-1. View

Kite G, Howes M, Simmonds M . Metabolomic analysis of saponins in crude extracts of Quillaja saponaria by liquid chromatography/mass spectrometry for product authentication. Rapid Commun Mass Spectrom. 2004; 18(23):2859-70. DOI: 10.1002/rcm.1698. View

Braca A, Bader A, Siciliano T, Morelli I, De Tommasi N . New Pyrrolizidine Alkaloids and Glycosides from Anchusa strigosa. Planta Med. 2003; 69(9):835-41. DOI: 10.1055/s-2003-43202. View

Oleszek W . Chromatographic determination of plant saponins. J Chromatogr A. 2002; 967(1):147-62. DOI: 10.1016/s0021-9673(01)01556-4. View

Dini I, Tenore G, Schettino O, Dini A . New oleanane saponins in Chenopodium quinoa. J Agric Food Chem. 2001; 49(8):3976-81. DOI: 10.1021/jf010361d. View

Cui M, Song F, Zhou Y, Liu Z, Liu S . Rapid identification of saponins in plant extracts by electrospray ionization multi-stage tandem mass spectrometry and liquid chromatography/tandem mass spectrometry. Rapid Commun Mass Spectrom. 2000; 14(14):1280-6. DOI: 10.1002/1097-0231(20000730)14:14<1280::AID-RCM26>3.0.CO;2-C. View

Guo M, Song F, Bai Y, Liu Z, Liu S . Rapid analysis of a triterpenoid saponin mixture from plant extracts by electrospray ionization multi-stage tandem mass spectrometry (ESI-MSI). Anal Sci. 2002; 18(4):481-4. DOI: 10.2116/analsci.18.481. View

Woldemichael G, Wink M . Identification and biological activities of triterpenoid saponins from Chenopodium quinoa. J Agric Food Chem. 2001; 49(5):2327-32. DOI: 10.1021/jf0013499. View

Takahashi H, NAMIKAWA Y, Tanaka M, Fukuyama Y . Triterpene glycosides from the cultures of Phytolacca americana. Chem Pharm Bull (Tokyo). 2001; 49(2):246-8. DOI: 10.1248/cpb.49.246. View

10.

Liu Y, Liang F, Cui L, Xia M, Zhao L, Yang Y . Multi-stage mass spectrometry of furostanol saponins combined with electrospray ionization in positive and negative ion modes. Rapid Commun Mass Spectrom. 2004; 18(2):235-8. DOI: 10.1002/rcm.1310. View

11.

Broberg S, Nord L, Kenne L . Oligosaccharide sequences in Quillaja saponins by electrospray ionization ion trap multiple-stage mass spectrometry. J Mass Spectrom. 2004; 39(6):691-701. DOI: 10.1002/jms.642. View

12.

Huhman D, Sumner L . Metabolic profiling of saponins in Medicago sativa and Medicago truncatula using HPLC coupled to an electrospray ion-trap mass spectrometer. Phytochemistry. 2002; 59(3):347-60. DOI: 10.1016/s0031-9422(01)00432-0. View

13.

Wang X, Sakuma T, Asafu-Adjaye E, Shiu G . Determination of ginsenosides in plant extracts from Panax ginseng and Panax quinquefolius L. by LC/MS/MS. Anal Chem. 1999; 71(8):1579-84. DOI: 10.1021/ac980890p. View

14.

Dini I, Tenore G, Dini A . Oleanane saponins in "kancolla", a sweet variety of Chenopodium quinoa. J Nat Prod. 2002; 65(7):1023-6. DOI: 10.1021/np010625q. View

15.

Mahoney A, Lopez J, G Hendricks D . An evaluation of the protein quality of quinoa. J Agric Food Chem. 1975; 23(2):190-3. DOI: 10.1021/jf60198a035. View

16.

Fang S, Hao C, Liu Z, Song F, Liu S . Application of Electrospray Ionization Mass Spectrometry Combined with Sequential Tandem Mass Spectrometry Techniques for the Profiling of Steroidal Saponin Mixture Extracted from Tribulus terrestris. Planta Med. 2007; 65(1):68-73. DOI: 10.1055/s-1999-13966. View

17.

Dal Piaz F, De Leo M, Braca A, De Simone F, Morelli I, De Tommasi N . Electrospray ionization mass spectrometry for identification and structural characterization of pregnane glycosides. Rapid Commun Mass Spectrom. 2005; 19(8):1041-52. DOI: 10.1002/rcm.1885. View

18.

van Setten D, ten Hove G, Wiertz E, Kamerling J, Van de Werken G . Multiple-stage tandem mass spectrometry for structural characterization of saponins. Anal Chem. 1998; 70(20):4401-9. DOI: 10.1021/ac980365q. View

19.

Lee , Yang , PARR . Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B Condens Matter. 1988; 37(2):785-789. DOI: 10.1103/physrevb.37.785. View

20.

Li B, Abliz Z, Tang M, Fu G, Yu S . Rapid structural characterization of triterpenoid saponins in crude extract from Symplocos chinensis using liquid chromatography combined with electrospray ionization tandem mass spectrometry. J Chromatogr A. 2005; 1101(1-2):53-62. DOI: 10.1016/j.chroma.2005.09.058. View