Bahrami Y and Franco CM (2015), Structure elucidation of new acetylated saponin...

ECB-ART-43801

Mar Drugs 2015 Jan 16;131:597-617. doi: 10.3390/md13010597.

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Structure elucidation of new acetylated saponins, Lessoniosides A, B, C, D, and E, and non-acetylated saponins, Lessoniosides F and G, from the viscera of the sea cucumber Holothuria lessoni.

Bahrami Y , Franco CM .

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Sea cucumbers produce numerous compounds with a wide range of chemical structural diversity. Among these, saponins are the most diverse and include sulfated, non-sulfated, acetylated and methylated congeners with different aglycone and sugar moieties. In this study, MALDI and ESI tandem mass spectrometry, in the positive ion mode, were used to elucidate the structure of new saponins extracted from the viscera of H. lessoni. Fragmentation of the aglycone provided structural information on the presence of the acetyl group. The presence of the O-acetyl group was confirmed by observing the mass transition of 60 u corresponding to the loss of a molecule of acetic acid. Ion fingerprints from the glycosidic cleavage provided information on the mass of the aglycone (core), and the sequence and type of monosaccharides that constitute the sugar moiety. The tandem mass spectra of the saponin precursor ions [M + Na]+ provided a wealth of detailed structural information on the glycosidic bond cleavages. As a result, and in conjunction with existing literature, we characterized the structure of five new acetylated saponins, Lessoniosides A-E, along with two non-acetylated saponins Lessoniosides F and G at m/z 1477.7, which are promising candidates for future drug development. The presented strategy allows a rapid, reliable and complete analysis of native saponins.

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Genes referenced: LOC100887844

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	Figure 1. The structures of the new acetylated saponins in the viscera of H. lessoni, Lessoniosides (A–E) along with the non-acetylated Lessoniosides (F–G) compounds are described in this figure.
	Figure 2. Positive tandem MALDI (matrix-assisted laser desorption/ionization) spectrum analyses of the precursor ion (saponin) detected at m/z 1477.7. The MS2 fragmentation profile of the ion at m/z 1477.7. Figure shows the collision-induced fragmentation of parent ions at m/z 1477.7. The full and dotted arrows show the possible fragmentation pathways of this ion using CID (collision-induced dissociation). The blue arrows show the fragmentation of the isomeric congeners Lessonioside A where the red arrows indicate the decomposition patterns of Lessonioside C. These analyses revealed that this ion corresponds to isomeric compounds.
	Figure 3. The schematic diagram of the proposed isomeric structures of the ion at m/z 1477.7. This figure indicates the comprehensive feasible fragmentation pathways of the isomeric acetylated, Lessoniosides (A–E), and non-acetylated, Lessoniosides (F–G), triterpene glycosides generated from the ion at m/z 1477.7.
	Figure 4. Positive ion mode ESI-MS2 spectrum of acetylated saponins detected at m/z 1477.7 from Fraction 18. The schematic fragmentation of Lessonioside A as a representative (A), and the complete ESI-MS2 fragmentation profile of the ion at m/z 1477.7 (B). Spectrum (B) shows the presence of two different aglycones in the isomeric saponins. Full and dotted arrows illustrate the three main feasible fragmentation pathways. The blue arrows show the decomposition of the isomeric congeners Lessoniosides A, B and D where the green arrows indicate the fragmentation patterns of Lessoniosides C, E, F and G. The ion at m/z 451.1 corresponds to the hydrated three sugar units [Xyl-Xyl-MeXyl + H2O + Na].

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