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Molecules
2022 Jan 15;272:. doi: 10.3390/molecules27020537.
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Microwave-Assisted Desulfation of the Hemolytic Saponins Extracted from Holothuria scabra Viscera.
Savarino P
,
Colson E
,
Caulier G
,
Eeckhaut I
,
Flammang P
,
Gerbaux P
.
Abstract
Saponins are plant and marine animal specific metabolites that are commonly considered as molecular vectors for chemical defenses against unicellular and pluricellular organisms. Their toxicity is attributed to their membranolytic properties. Modifying the molecular structures of saponins by quantitative and selective chemical reactions is increasingly considered to tune the biological properties of these molecules (i) to prepare congeners with specific activities for biomedical applications and (ii) to afford experimental data related to their structure-activity relationship. In the present study, we focused on the sulfated saponins contained in the viscera of Holothuria scabra, a sea cucumber present in the Indian Ocean and abundantly consumed on the Asian food market. Using mass spectrometry, we first qualitatively and quantitatively assessed the saponin content within the viscera of H. scabra. We detected 26 sulfated saponins presenting 5 different elemental compositions. Microwave activation under alkaline conditions in aqueous solutions was developed and optimized to quantitatively and specifically induce the desulfation of the natural saponins, by a specific loss of H2SO4. By comparing the hemolytic activities of the natural and desulfated extracts, we clearly identified the sulfate function as highly responsible for the saponin toxicity.
Figure 1. General structure of the Holothuria scabra saponins [17] containing a holostanol aglycone with different side groups, including a C3-anchored glycan presenting a sulfate group on the first monosaccharidic unit.
Figure 2. Hypothetical alkaline hydrolysis of Holothurin A leading to Desholothurin A by specific removal of the sulfate group.
Figure 3. Mass spectrometry analysis of two different saponin extracts: (a) the purified saponin extract with detection of sulfated 4-sugar saponin ions, desulfated 4-sugar saponin ions, sulfated 2-sugar saponin ions and desulfated 2-sugar saponin ions; and (b) the microwave-assisted alkaline desulfation (pH 14—100 °C—5 min) reaction products with 4-sugar desulfated saponin ions and 2-sugar desulfated saponin ions.
Figure 4. Mass spectrometry qualitative and quantitative analysis of the (a) natural and (b) desulfated saponin extracts: the saponin relative proportions (%) correspond to the molar proportions in the natural and modified extracts.
Figure 5. Microwave-assisted alkaline H2SO4 loss from natural saponins: the C=C bond formation created by the desulfation process involves a vicinal hydrogen atom in the frame of an elimination reaction whose regioselectivity is still ill-defined.
Figure 6. Evaluation of the cytotoxicity of both saponin extracts: comparison between the hemolytic activity of the natural (sulfated) saponins and of the microwave-desulfated saponins. The experiment was performed in triplicates using a 2% suspension of erythrocytes from bovine blood. The HAs are expressed in % of the HE of a reference extract constituted by 500 µg·mL−1 of HC saponins (see experimental).
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