Structures and Biogenesis of Fallaxosides D4, D5, D6 and D7, Trisulfated Non-Holostane Triterpene Glycosides from the Sea Cucumber Cucumaria fallax

Silchenko, Alexandra S.; Kalinovsky, Anatoly I.; Avilov, Sergey A.; Andryjaschenko, Pelageya V.; Dmitrenok, Pavel S.; Kalinin, Vladimir I.; Chingizova, Ekaterina A.; Minin, K. V.; Stonik, Valentin A.

doi:10.3390/molecules21070939

Cited by 14 publications

(7 citation statements)

References 13 publications

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“…Although polysulfated polysaccharides are common biopolymers of marine macrophytes and invertebrates, low molecular weight metabolites, containing several sulfate groups are extremely rare. So far, trisulfated natural compounds such as steroid glycosides were found only in sponges [15,16,17] and trisulfated triterpene glycosides, in some representatives of the class Holothuroidea [18,19].…”

Section: Resultsmentioning

confidence: 99%

Structures and Bioactivities of Psolusosides B1, B2, J, K, L, M, N, O, P, and Q from the Sea Cucumber Psolus fabricii. The First Finding of Tetrasulfated Marine Low Molecular Weight Metabolites

et al. 2019

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Ten new di-, tri- and tetrasulfated triterpene glycosides, psolusosides B1 (1), B2 (2), J (3), K (4), L (5), M (6), N (7), O (8), P (9), and Q (10), were isolated from the sea cucumber Psolus fabricii collected in the Sea of Okhotsk near the Kurile Islands. Structures of these glycosides were established by two-dimensional (2D) NMR spectroscopy and HR-ESI mass-spectrometry. It is particularly interesting that highly polar compounds 9 and 10 contain four sulfate groups in their carbohydrate moieties, including two sulfates in the same terminal glucose residue. Glycoside 2 has an unusual non-holostane aglycone with 18(16)-lactone and a unique 7,8-epoxy fragment. Cytotoxic activities of compounds 1–10 against several mouse cell lines such as Ehrlich ascites carcinoma cells, neuroblastoma Neuro 2A, normal epithelial JB-6 cells, and erythrocytes were quite different depending both on structural peculiarities of these glycosides and the type of cells subjected to their actions. Psolusoside L (5), pentaoside, with three sulfate groups at C-6 of two glucose and one 3-O-methylglucose residue and holostane aglycone, is the most active compound in the series. The presence of a sulfate group at C-2 of the terminal glucose residue attached to C-4 of the first (xylose) residue significantly decreases activities of the corresponding glycosides. Psolusosides of group B (1, 2, and known psolusoside B) are inactive in all tests due to the presence of non-holostane aglycones and tetrasaccharide-branched sugar chains sulfated by C-2 of Glc4.

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Section: Resultsmentioning

confidence: 99%

Structures and Bioactivities of Psolusosides B1, B2, J, K, L, M, N, O, P, and Q from the Sea Cucumber Psolus fabricii. The First Finding of Tetrasulfated Marine Low Molecular Weight Metabolites

et al. 2019

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“…It is interesting to note that the aglycones having both 7(8)- and 9(11)-double bonds are present in the glycosidic sum of C. quadrangularis whenever the majority of sea cucumber species usually biosynthesize the aglycones with the certain position of double bond in the triterpene nucleus. Only six species of the holothurians besides C. quadrangularis are known so far to produce simultaneously the aglycones with different positions of double bonds in the nuclei: Cucumaria frondosa [ 42 ], Australostichopus mollis [ 43 ], and Colochirus robustus [ 20 ]—the aglycones with 7(8)- and 9(11)-double bonds; Synapta maculata —the aglycones with 7(8)- and 8(9)-double bonds [ 44 ]; and Psolus fabricii and Cucumaria fallax —the aglycones with 7(8)-, 8(9)-, and 9(11)-double bonds [ 37 , 45 ].…”

Section: Discussionmentioning

confidence: 99%

Structures and Bioactivities of Quadrangularisosides A, A1, B, B1, B2, C, C1, D, D1–D4, and E from the Sea Cucumber Colochirus quadrangularis: The First Discovery of the Glycosides, Sulfated by C-4 of the Terminal 3-O-Methylglucose Residue. Synergetic Effect on Colony Formation of Tumor HT-29 Cells of these Glycosides with Radioactive Irradiation

et al. 2020

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Thirteen new mono-, di-, and trisulfated triterpene glycosides, quadrangularisosides A–D4 (1−13) have been isolated from the sea cucumber Colochirus quadrangularis, which was collected in Vietnamese waters. The structures of these glycosides were established by 2D NMR spectroscopy and HR-ESI (High Resolution Electrospray Ionization) mass spectrometry. The novel carbohydrate moieties of quadrangularisosides D–D4 (8−12), belonging to the group D, and quadrangularisoside E (13) contain three sulfate groups, with one of them occupying an unusual position—at C(4) of terminal 3-O-methylglucose residue. Quadrangularisosides A (1) and D3 (11) as well as quadrangularisosides A1 (2) and D4 (12) are characterized by the new aglycones having 25-hydroperoxyl or 24-hydroperoxyl groups in their side chains, respectively. The cytotoxic activities of compounds 1–13 against mouse neuroblastoma Neuro 2a, normal epithelial JB-6 cells, erythrocytes, and human colorectal adenocarcinoma HT-29 cells were studied. All the compounds were rather strong hemolytics. The structural features that most affect the bioactivity of the glycosides are the presence of hydroperoxy groups in the side chains and the quantity of sulfate groups. The membranolytic activity of monosulfated quadrangularisosides of group A (1, 2) against Neuro 2a, JB-6 cells, and erythrocytes was relatively weak due to the availability of the hydroperoxyl group, whereas trisulfated quadrangularisosides D3 (11) and D4 (12) with the same aglycones as 1, 2 were the least active compounds in the series due to the combination of these two structural peculiarities. The erythrocytes were more sensitive to the action of the glycosides than Neuro 2a or JB-6 cells, but the structure–activity relationships observed for glycosides 1–13 were similar in the three cell lines investigated. The compounds 3−5, 8, and 9 effectively suppressed the cell viability of HT-29 cells. Quadrangularisosides A1 (2), C (6), C1 (7), and E (13) possessed strong inhibitory activity on colony formation in HT-29 cells. Due to the synergic effects of these glycosides (0.02 μM) and radioactive irradiation (1 Gy), a decreasing of number of colonies was detected. Glycosides 1, 3, and 9 enhanced the effect of radiation by about 30%.

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“…Quinovose has been found in the latex of Ipomoea carnea [ 13 ], and was identified as a part of the sugar moiety of hydroxy fatty acid glycosides isolated from plants of the family Convolvulaceae [ 14 ], and of triterpene glycosides found in marine organisms [ 15 ]. The presence of the reducing sugar quinovose was detected in 7 of the 16 samples of North Macedonian honey, and in 6 of the 22 Bulgarian samples.…”

Section: Resultsmentioning

confidence: 99%

NMR Profiling of North Macedonian and Bulgarian Honeys for Detection of Botanical and Geographical Origin

et al. 2020

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Bulgaria and North Macedonia have a long history of the production and use of honey; however, there is an obvious lack of systematic and in-depth research on honey from both countries. The oak honeydew honey is of particular interest, as it is highly valued by consumers because of its health benefits. The aim of this study was to characterize honeydew and floral honeys from Bulgaria and North Macedonia based on their NMR profiles. The 1D and 2D 1H and 13C-NMR spectra were measured of 16 North Macedonian and 22 Bulgarian honey samples. A total of 25 individual substances were identified, including quinovose, which was found for the first time in honey. Chemometric methods (PCA—principal component analysis, PLS-DA—partial least squares discriminant analysis, ANOVA—analysis of variance) were used to detect similarities and differences between samples, as well as to determine their botanical and geographical origin. Semiquantitative data on individual sugars and some other constituents were obtained, which allowed for the reliable classification of honey samples by botanical and geographical origin, based on chemometric approaches. The results enabled us to distinguish oak honeydew honey from other honey types, and to determine the country of origin. NMR was a rapid and convenient method, avoiding the need for other more time-consuming analytical techniques.

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Structures and Biogenesis of Fallaxosides D4, D5, D6 and D7, Trisulfated Non-Holostane Triterpene Glycosides from the Sea Cucumber Cucumaria fallax

Cited by 14 publications

References 13 publications

Structures and Bioactivities of Psolusosides B1, B2, J, K, L, M, N, O, P, and Q from the Sea Cucumber Psolus fabricii. The First Finding of Tetrasulfated Marine Low Molecular Weight Metabolites

Structures and Bioactivities of Psolusosides B1, B2, J, K, L, M, N, O, P, and Q from the Sea Cucumber Psolus fabricii. The First Finding of Tetrasulfated Marine Low Molecular Weight Metabolites

NMR Profiling of North Macedonian and Bulgarian Honeys for Detection of Botanical and Geographical Origin

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