Bahrami Y et al. (2014), Structure elucidation of five novel isomeric sa...

ECB-ART-43559

Mar Drugs 2014 Aug 08;128:4439-73. doi: 10.3390/md12084439.

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Structure elucidation of five novel isomeric saponins from the viscera of the sea cucumber Holothuria lessoni.

Bahrami Y , Zhang W , Chataway T , Franco C .

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Sea cucumbers are prolific producers of a wide range of bioactive compounds. This study aimed to purify and characterize one class of compound, the saponins, from the viscera of the Australian sea cucumber Holothuria lessoni. The saponins were obtained by ethanolic extraction of the viscera and enriched by a liquid-liquid partition process and adsorption column chromatography. A high performance centrifugal partition chromatography (HPCPC) was applied to the saponin-enriched mixture to obtain saponins with high purity. The resultant purified saponins were profiled using MALDI-MS/MS and ESI-MS/MS which revealed the structure of isomeric saponins to contain multiple aglycones and/or sugar residues. We have elucidated the structure of five novel saponins, Holothurins D/E and Holothurinosides X/Y/Z, along with seven reported triterpene glycosides, including sulfated and non-sulfated saponins containing a range of aglycones and sugar moieties, from the viscera of H. lessoni. The abundance of novel compounds from this species holds promise for biotechnological applications.

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Genes referenced: agl LOC100887844

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	Figure 1. (+) Electrospray ionization- mass spectrometry (ESI-MS) spectrum of saponins purified by HPCPC from Fraction # 18 of the extract from the viscera of H. lessoni.
	Figure 2. Positive tandem ESI spectrum analysis of saponins detected at m/z 1127.6, Fraction 17; (A) and Fraction 18; (B) Full and dotted arrows show the two main feasible fragmentation pathways. The figures indicate the collision-induced fragmentation of parent ions at m/z 1127.6. The consecutive losses of the aglycone (Agl), xylose (Xyl), quinovose (Qui) and 3-O-methylglucose (MeGlc) residues affords product ions detected at m/z 657.2, 507.2, 361.1 and 185.0, respectively, which indicate the structure of a novel saponin. The predominant peak (A and B) at m/z 493.2 corresponds to either the diagnostic sugar residue or the aglycone moiety. The major abundant peak (A and B) at m/z 507 also corresponds to either the key sugar residue or the aglycone moiety.
	Figure 3. Schematic fragmentation patterns of the ion detected at m/z 1127.6.
	Figure 4. The schematic diagram of the proposed isomeric structures of ion at m/z 1127.6.
	Figure 5. (+) ion mode ESI-MS/MS spectrum of sulfated saponins detected at 1227.4. Full and dotted arrows show the three main feasible fragmentation pathways. The consecutive losses of NaHSO4, Agl, Xyl, MeGlc and Qui residues affords product ions detected at m/z 1107.5, 639.0, 507.0, 331.1 and 185.0, respectively.
	Figure 6. Schematic fragmentation patterns of the ion detected at m/z 1227.4.
	Figure 7. (+) ion mode ESI-MS/MS spectrum of saponins detected at m/z 1259.5 from Fraction 22. This spectrum shows the presence of two different aglycones indicating the presence of isomeric saponins. The consecutive losses of NaHSO4, Agl, Xyl, Qui and MeGlc followed by Glc residue affords product ions detected at m/z 1139.5, 639.2, 507.2, 361.1 and 185.0, respectively, which indicate the structure of Holothurin A3. Full and dotted arrows illustrate the three main possible fragmentation pathways.
	Figure 8. Schematic fragmentation patterns of the ion detected at m/z 1259.5.
	Figure 9. A schematic diagram of the proposed isomeric structures of ion at m/z 1259.5.
	Figure 10. The MALDI mass spectrum of HPCPC Fraction 18 from the viscera of the H. lessoni in the (+) ion mode. A mass range of 1000 to 1500 Da is shown here.
	Figure 11. Schematic fragmentation patterns of the ion detected at m/z 1243.5, Holothurin A.
	Figure 12. The structure of identified saponins in the viscera of H. lessoni. Holothurins D/E and Holothurinosides X/Y/Z are the novel compounds described in this paper.