Cucumarioside E from the Far Eastern Sea Cucumber Cucumaria japonica (Cucumariidae, Dendrochirotida), New Minor Monosulfated Holostane Triterpene Pentaoside with Glucose as the Second Monosaccharide Residue

New minor triterpene glycoside, cucumarioside E (1) has been isolated from the Far Eastern sea cucumber Cucumaria japonica. The structure of the glycoside was elucidated by 2D-NMR specroscopy and mass-spectrometry. The glycoside has glucose instead of quinovose as the second monosaccharide residue and xylose as third monosaccharide residue that is unique structural feature for triterpene glycosides carbohydrate chains from sea cucumbers belonging to the genus Cucumaria.

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Triterpene Glycosides from the Far Eastern Sea Cucumber Thyonidium (=Duasmodactyla) kurilensis (Levin): The Structures, Cytotoxicities, and Biogenesis of Kurilosides A3, D1, G, H, I, I1, J, K, and K1

Marine Drugs ◽

10.3390/md19040187 ◽

2021 ◽

Vol 19 (4) ◽

pp. 187

Author(s):

Alexandra S. Silchenko ◽

Anatoly I. Kalinovsky ◽

Sergey A. Avilov ◽

Pelageya V. Andrijaschenko ◽

Roman S. Popov ◽

...

Keyword(s):

Sea Cucumber ◽

2D Nmr ◽

Structural Features ◽

Cytotoxic Activities ◽

Hydroxyl Groups ◽

2D Nmr Spectroscopy ◽

Esi Mass Spectrometry ◽

Branched Chain ◽

Far Eastern ◽

Carbohydrate Chains

Nine new mono-, di-, and trisulfated triterpene penta- and hexaosides, kurilosides A3 (1), D1 (2), G (3), H (4), I (5), I1 (6), J (7), K (8), and K1 (9) and two desulfated derivatives, DS-kuriloside L (10), having a trisaccharide branched chain, and DS-kuriloside M (11), having hexa-nor-lanostane aglycone with a 7(8)-double bond, have been isolated from the Far-Eastern deep-water sea cucumber Thyonidium (=Duasmodactyla) kurilensis (Levin) and their structures were elucidated based on 2D NMR spectroscopy and HR-ESI mass-spectrometry. Five earlier unknown carbohydrate chains and two aglycones (having a 16β,(20S)-dihydroxy-fragment and a 16β-acetoxy,(20S)-hydroxy fragment) were found in these glycosides. All the glycosides 1–9 have a sulfate group at C-6 Glc, attached to C-4 Xyl1, while the positions of the other sulfate groups vary in different groups of kurilosides. The analysis of the structural features of the aglycones and the carbohydrate chains of all the glycosides of T. kurilensis showed their biogenetic relationships. Cytotoxic activities of the compounds 1–9 against mouse neuroblastoma Neuro 2a, normal epithelial JB-6 cells, and erythrocytes were studied. The highest cytotoxicity in the series was demonstrated by trisulfated hexaoside kuriloside H (4), having acetoxy-groups at C(16) and C(20), the latter one obviously compensated the absence of a side chain, essential for the membranolytic action of the glycosides. Kuriloside I1 (6), differing from 4 in the lacking of a terminal glucose residue in the bottom semi-chain, was slightly less active. The compounds 1–3, 5, and 8 did not demonstrate cytotoxic activity due to the presence of hydroxyl groups in their aglycones.

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Kurilosides A1, A2, C1, D, E and F—Triterpene Glycosides from the Far Eastern Sea Cucumber Thyonidium (= Duasmodactyla) kurilensis (Levin): Structures with Unusual Non-Holostane Aglycones and Cytotoxicities

Marine Drugs ◽

10.3390/md18110551 ◽

2020 ◽

Vol 18 (11) ◽

pp. 551

Author(s):

Alexandra S. Silchenko ◽

Anatoly I. Kalinovsky ◽

Sergey A. Avilov ◽

Pelageya V. Andrijaschenko ◽

Roman S. Popov ◽

...

Keyword(s):

Sea Cucumber ◽

2D Nmr ◽

Cytotoxic Activities ◽

Glucose Residue ◽

Monosaccharide Residue ◽

2D Nmr Spectroscopy ◽

Sugar Chain ◽

Sugar Unit ◽

Esi Mass Spectrometry ◽

Far Eastern

Six new monosulfated triterpene tetra-, penta- and hexaosides, namely, the kurilosides A1 (1), A2 (2), C1 (3), D (4), E (5) and F (6), as well as the known earlier kuriloside A (7), having unusual non-holostane aglycones without lactone, have been isolated from the sea cucumber Thyonidium (= Duasmodactyla) kurilensis (Levin) (Cucumariidae, Dendrochirotida), collected in the Sea of Okhotsk near Onekotan Island from a depth of 100 m. Structures of the glycosides were established by 2D NMR spectroscopy and HR-ESI mass spectrometry. Kurilosides of the groups A and E contain carbohydrate moieties with a rare architecture (a pentasaccharide branched by C(4) Xyl1), differing from each other in the second monosaccharide residue (quinovose or glucose, correspondingly); kurilosides of the group C are characterized by a unique tetrasaccharide branched by a C(4) Xyl1 sugar chain; and kurilosides of the groups D and F are hexaosides differing from each other in the presence of an O-methyl group in the fourth (terminal) sugar unit. All these glycosides contain a sulfate group at C-6 of the glucose residue attached to C-4 Xyl1 and the non-holostane aglycones have a 9(11) double bond and lack γ-lactone. The cytotoxic activities of compounds 1–7 against mouse neuroblastoma Neuro 2a, normal epithelial JB-6 cells and erythrocytes were studied. Kuriloside A1 (1) was the most active compound in the series, demonstrating strong cytotoxicity against the erythrocytes and JB-6 cells and a moderate effect against Neuro 2a cells.

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Structure of Cucumariosides H5, H6, H7 and H8, Triterpene Glycosides from the Sea Cucumber Eupentacta fraudatrix and Unprecedented Aglycone with 16,22-Epoxy-group

Natural Product Communications ◽

10.1177/1934578x1100600806 ◽

2011 ◽

Vol 6 (8) ◽

pp. 1934578X1100600 ◽

Cited By ~ 5

Author(s):

Alexandra S. Silchenko ◽

Anatoly I. Kalinovsky ◽

Sergey A. Avilov ◽

Pelageya V. Andryjaschenko ◽

Pavel S. Dmitrenok ◽

...

Keyword(s):

Spectral Data ◽

Sea Cucumber ◽

Epoxy Group ◽

2D Nmr ◽

Triterpene Glycosides ◽

Sulfate Group ◽

Sea Cucumbers ◽

Far Eastern ◽

Mouse Lymphocytes ◽

Eupentacta Fraudatrix

Four new triterpene glycosides cucumariosides H5 (1), H6 (2), H7 (3) and H8 (4) along with the known cucumarioside H (5) have been isolated from the Far Eastern sea cucumber Eupentacta fraudatrix. The structures of glycosides 1–4 were elucidated on the basis of spectral data (2D NMR and MS). Glycosides 1–4 belong to the group of cucumariosides H, having branched rare pentasaccharide carbohydrate moieties with one sulfate group and 3- O-methyl-D-xylose as a terminal monosaccharide unit. Glycosides 1–3 and 5 differ from each other in structures of side chains of the aglycones, while cucumarioside H8 (4) has a novel aglycone with unprecedented 16(22)-epoxy-group, never found in the sea cucumbers glycosides. Glycosides 1–3, and 5 were cytotoxic against mouse lymphocytes and hemolytic against mouse erythrocytes. Glycoside 2 was less active in comparison with others.

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Colochirosides B1, B2, B3 and C, Novel Sulfated Triterpene Glycosides from the Sea Cucumber Colochirus robustus (Cucumariidae, Dendrochirotida)

Natural Product Communications ◽

10.1177/1934578x1501001014 ◽

2015 ◽

Vol 10 (10) ◽

pp. 1934578X1501001 ◽

Cited By ~ 3

Author(s):

Alexandra S. Silchenko ◽

Anatoly I. Kalinovsky ◽

Sergey A. Avilov ◽

Pelageya V. Andryjaschenko ◽

Pavel S. Dmitrenok ◽

...

Keyword(s):

Mass Spectrometry ◽

Hemolytic Activity ◽

Sea Cucumber ◽

2D Nmr ◽

Carcinoma Cells ◽

Triterpene Glycosides ◽

Ehrlich Carcinoma ◽

Cytotoxic Activities ◽

2D Nmr Spectroscopy ◽

Carbohydrate Chains

Four new triterpene glycosides, colochirosides B1 (1), B2 (2), B3 (3) and C (4) have been isolated from the sea cucumber Colochirus robustus (Cucumariidae, Dendrochirotida). Six known earlier glycosides from representatives of two families of the order Dendrochirotida have also been found in C. robustus. Structures of the glycosides have been elucidated by 2D NMR spectroscopy and mass spectrometry. All the glycosides belong to the holostane series and contain tetrasaccharide linear carbohydrate chains with one or two sulfate groups. Cytotoxic activities of glycosides 1-4 against the ascite form of mouse Ehrlich carcinoma cells and hemolytic activities against mouse erythrocytes have been studied. Hemolytic activity of the glycosides was higher than cytotoxic. Glycosides 3 and 4 demonstrated strong effects, whereas compounds 1 and 2 containing the hydroxy-group in the side chains showed moderate hemolytic activity and were not cytotoxic.

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Psolusosides C1, C2, and D1, Novel Triterpene Hexaosides from the Sea CucumberPsolus fabricii (Psolidae, Dendrochirotida)

Natural Product Communications ◽

10.1177/1934578x1801301213 ◽

2018 ◽

Vol 13 (12) ◽

pp. 1934578X1801301 ◽

Cited By ~ 1

Author(s):

Alexandra S. Silchenko ◽

Sergey A. Avilov ◽

Anatoly I. Kalinovsky ◽

Vladimir I. Kalinin ◽

Pelageya V. Andrijaschenko ◽

...

Keyword(s):

Sea Of Okhotsk ◽

Sea Cucumber ◽

Apostichopus Japonicus ◽

2D Nmr ◽

Shallow Waters ◽

Monosaccharide Residue ◽

2D Nmr Spectroscopy ◽

The Third ◽

Kurile Islands ◽

Carbohydrate Chains

Three new triterpene glycosides, psolusosides C1 (1), C2 (2) and D1 (3) have been isolated from the sea cucumber Psolus fabricii collected in the Sea of Okhotsk in the shallow waters of Onekotan Island (Kurile Islands). Five known glycosides: cladolosides B, M1, P2, isolated earlier from the sea cucumbers of genus Cladolabes and holotoxin A1 with 27- nor-25-oxo-holotoxin A1, isolated earlier from Apostichopus japonicus have also been found. The glycoside structures were elucidated by 2D NMR spectroscopy and HR mass-spectrometry. Compounds 1–3 possess hexasaccharide carbohydrate chains, identical for 1 and 2 and different in the third monosaccharide residue for 3. All the glycosides comprise holostane type aglycones with a 9(11)-double bond and a 16-keto-group and differ from each other in the side chains structures.

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Structures and Biological Activities of Typicosides A1, A2, B1, C1 and C2, Triterpene Glycosides from the Sea Cucumber Actinocucumis typica

Natural Product Communications ◽

10.1177/1934578x1300800307 ◽

2013 ◽

Vol 8 (3) ◽

pp. 1934578X1300800

Author(s):

Alexandra S. Silchenko ◽

Anatoly I. Kalinovsky ◽

Sergey A. Avilov ◽

Pelageya V. Andryjaschenko ◽

Pavel S. Dmitrenok ◽

...

Keyword(s):

Sea Cucumber ◽

Biological Activities ◽

Monosaccharide Composition ◽

Triterpene Glycosides ◽

Ehrlich Carcinoma ◽

Cytotoxic Activities ◽

Monosaccharide Residue ◽

2D Nmr Spectroscopy ◽

The Third ◽

Carbohydrate Chains

Five new minor triterpene glycosides, typicosides A1 (1), A2 (2), B1 (3), C1 (4) and C2 (5), along with two known glycosides, intercedenside A and holothurin B3, have been isolated from the sea cucumber Actinocucumis typica. Structures of the glycosides were elucidated by 2D NMR spectroscopy and MS. Glycosides 1–5 are linear mono- and disulfated tetraosides differing from each other in both aglycone structures and monosaccharide composition of the carbohydrate chains. Typicosides A1 (1) and A2 (2) have identical monosulfated carbohydrate moieties with a xylose residue as the third monosaccharide unit and differ from each other in aglycon structures. Typicoside B1 (3) has glucose as the third monosaccharide residue. Typicosides C1 (4) and C2 (5) contain the same disulfated carbohydrate chains and differ from each other in structures of aglycone side chains. Antifungal activity of glycosides 1–5 against three species of fungi along with cytotoxic activity against mouse spleen lymphocytes and mouse Ehrlich carcinoma cells (ascite form), as well as hemolytic activities against mouse erythrocytes have been studied. All new glycosides, except for typicoside C1 (4), containing a hydroxy-group in the aglycone side chain, demonstrate rather strong hemolytic and cytotoxic activities.

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Glycosides from the sea cucumber Cucumaria frondosa. IV. Structure of frondosides A2-4, A2-7, and A2-8, three new minor monosulfated triterpene glycosides

Canadian Journal of Chemistry ◽

10.1139/v05-243 ◽

2005 ◽

Vol 83 (12) ◽

pp. 2120-2126 ◽

Cited By ~ 10

Author(s):

Alexandra S Silchenko ◽

Sergey A Avilov ◽

Alexandr S Antonov ◽

Anatoly I Kalinovsky ◽

Pavel S Dmitrenok ◽

...

Keyword(s):

Double Bond ◽

Spectral Data ◽

Sea Cucumber ◽

2D Nmr ◽

Triterpene Glycosides ◽

Sea Cucumbers ◽

Cucumaria Frondosa

Frondosides A2-4 (1), A2-7 (2), and A2-8 (3) are new monosulfated triterpene glycosides isolated from the sea cucumber Cucumaria frondosa. Their structures have been elucidated on the basis of spectral data (2D NMR and MS). Frondosides A2-7 (2) and A2-8 (3) are isomers and differ from each other only by the position of a double bond in their non-holostane-type aglycones.Key words: Cucumaria frondosa, sea cucumbers, frondosides, triterpene glycosides.

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Glycosides from the sea cucumber Cucumaria frondosa. III. Structure of frondosides A2-1, A2-2, A2-3, and A2-6, four new minor monosulfated triterpene glycosides

Canadian Journal of Chemistry ◽

10.1139/v04-163 ◽

2005 ◽

Vol 83 (1) ◽

pp. 21-27 ◽

Cited By ~ 16

Author(s):

Alexandra S Silchenko ◽

Sergey A Avilov ◽

Alexandr S Antonov ◽

Anatoly I Kalinovsky ◽

Pavel S Dmitrenok ◽

...

Keyword(s):

Spectral Data ◽

Sea Cucumber ◽

2D Nmr ◽

Triterpene Glycosides ◽

Side Chain ◽

Unsaturated Ketone ◽

Sea Cucumbers ◽

Cucumaria Frondosa

Frondosides A2-1 (1), A2-2 (2), A2-3 (3), and A2-6 (4) are new monosulfated holostane pentaosides isolated from the sea cucumber Cucumaria frondosa. Their structures have been elucidated on the basis of spectral data (2D NMR and MS). Frondoside A2-2 (2) contains an α,β-unsaturated ketone fragment in the side chain of the aglycon, unique for triterpene glycosides of sea cucumbers.Key words: Cucumaria frondosa, sea cucumbers, frondosides, triterpene glycosides.

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Structures of Violaceusosides C, D, E and G, Sulfated Triterpene Glycosides from the Sea Cucumber Pseudocolochirus violaceus (Cucumariidae, Dendrochirotida)

Natural Product Communications ◽

10.1177/1934578x1400900329 ◽

2014 ◽

Vol 9 (3) ◽

pp. 1934578X1400900 ◽

Cited By ~ 3

Author(s):

Alexandra S. Silchenko ◽

Anatoly I. Kalinovsky ◽

Sergey A. Avilov ◽

Pelageya V. Andryjaschenko ◽

Pavel S. Dmitrenok ◽

...

Keyword(s):

Sea Cucumber ◽

2D Nmr ◽

Triterpene Glycosides ◽

Ehrlich Carcinoma ◽

Cytotoxic Activities ◽

Sugar Composition ◽

2D Nmr Spectroscopy ◽

Chemical Structures ◽

The Family ◽

Carbohydrate Chains

Four new triterpene glycosides, violaceusosides C (1), D (2), E (3) and G (4) have been isolated from the sea cucumber Pseudocolochirus violaceus (Cucumariidae, Dendrochirotida). Eight known glycosides, DS-holothurin A and holothurinoside A, isolated earlier from Holothuria forskalii (order Aspidochirotida); and violaceuside A, lefevreoside C, philinopside E, intercedenside B, violaceuside II and liovilloside A isolated earlier from representatives of the family Cucumariidae, order Dendrochirotida have also been found in P. violaceus. The chemical structures of the glycosides were elucidated by 2D NMR spectroscopy and mass spectrometry. Violaceusosides C (1), D (2), E (3) and G (4) have holostane-type aglycones and tetrasaccharide linear carbohydrate chains differing in the sugar composition and the number and position of sulfate groups. Violaceusosides E (3) and G (4) are characterized by the presence of a sulfate group at C-3 of the quinovose residue that is very rare among sea cucumber glycosides. Cytotoxic activities of the glycosides 1–4 against cells of the ascite form of mouse Ehrlich carcinoma and hemolytic activities against mouse erythrocytes have been studied. Violaceusosides C (1) and D (2) demonstrated moderate cytotoxic and hemolytic effects, while violaceusosides E (3) and G (4) have more powerful activities.

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Fallaxosides C1, C2, D1 and D2, Unusual Oligosulfated Triterpene Glycosides from the Sea Cucumber Cucumaria fallax (Cucumariidae, Dendrochirotida, Holothurioidea) and Taxonomic Status of this Animal

Natural Product Communications ◽

10.1177/1934578x1601100718 ◽

2016 ◽

Vol 11 (7) ◽

pp. 1934578X1601100 ◽

Cited By ~ 1

Author(s):

Alexandra S. Silchenko ◽

Anatoly I. Kalinovsky ◽

Sergey A. Avilov ◽

Pelageya V. Andryjaschenko ◽

Pavel S. Dmitrenok ◽

...

Keyword(s):

Mass Spectrometry ◽

Hemolytic Activity ◽

Sea Cucumber ◽

Taxonomic Status ◽

2D Nmr ◽

Carcinoma Cells ◽

Triterpene Glycosides ◽

Ehrlich Carcinoma ◽

2D Nmr Spectroscopy ◽

Spleen Lymphocytes

Four new triterpene glycosides, fallaxosides C1 (1), C2 (2), D1 (3) and D2 (4) along with the known cucumarioside A3-2 (5) and koreoside A (6) have been isolated from the sea cucumber Cucumaria fallax (Cucumariidae, Dendrochirotida). Structures of the glycosides have been elucidated by 2D NMR spectroscopy and mass spectrometry. All of the glycosides are rare non-holostane derivatives having shortened side chains and contain pentasaccharide carbohydrate moieties with two or three sulfate groups. Structures of these triterpene glycosides and their comparison with those earlier isolated from Cucumaria spp. and Pseudocnus dubiosus leoninus allow us to suggest that the present assignment of C. fallax to the genus Pseudocnus is not correct, and this species should be assigned to the genus Cucumaria. Cytotoxic activity of glycosides 1–5 against the ascite form of mouse Ehrlich carcinoma cells and mouse spleen lymphocytes and hemolytic activity against mouse erythrocytes have been studied. The glycosides were expectedly not active in all the tests due to the absence of an 18(20)-lactone in their aglycones and the presence of several sulfate groups. There was one exception, cucumarioside A3-2 (5), which demonstrated a weak cytotoxicity against lymphocytes and moderate hemolytic activity.

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