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.
KalininV.I., SilchenkoA.S., AvilovS.A., StonikV.A., SmirnovA.V. (2005) Sea cucumbers triterpene glycosides, the recent progress in structural elucidation and chemotaxonomy. Phytochemistry Reviews, 4, 221–236.
2.
KalininV.I., AmininD.L., AvilovS.A., SilchenkoA.S., StonikV.A. (2008) Triterpene glycosides from sea cucumbers (Holothurioidea, Echinodermata). Biological activities and functions. In Studies in Natural Product Chemistry (Bioactive Natural Products), Vol. 35, Atta-ur-Rahman (Ed.). Elsevier Science Publisher, Amsterdam, 135–196.
3.
ZouZ.R., YiY.H., WuH.M., WuJ.H., LiawC.C., LeeK.H. (2003) Intercedensides A–C, three new cytotoxic triterpene glycosides from the sea cucumber Mensamaria intercedens Lampert. Journal of Natural Products, 66, 1055–1060.
4.
ShashkovA.S., ChizhovO.S. (1976) 13C NMR spectroscopy in chemistry of carbohydrate and relative compounds. Bioorganicheskaya Khimiya, 2, 437–497.
5.
AfyatullovS.S., KalinovskyA.I., StonikV.A. (1987) Structures of cucumariosides C1 and C2 – two new triterpene glycosides from the sea cucumber Eupentacta fraudatrix.Khimiya Prirodnykh Soedinenii, 6, 831–837.
6.
KalininVI., AfyatullovS.S., KalinovskyA.I. (1988) Triterpene glycosides of the sea cucumber Eupentacta pseudoquinquesemita.Khimiya Prirodnykh Soedinenii, 2, 221–225.
7.
SilchenkoA.S., KalinovskyA.I., AvilovS.A., AndrijaschenkoP.V., DmitrenokP.S., MartyyasE.A., KalininV.I. (2012) Triterpene glycosides from the sea cucumber Eupentacta fraudatrix. Structure and biological activity of cucumariosides B1 and B2, two new minor non-sulfated unprecedented triosides. Natural Product Communications, 7, 1157–1162.
8.
ZouZ., YiY., WuH., YaoX., DuL., WuJ., LiawC.C., LeeK.H. (2005) Intercedensides D–I, cytotoxic triterpene glycosides from the sea cucumber Mensamaria intercedens Lampert. Journal of Natural Products, 68, 540–546.
9.
SilchenkoA.S., StonikV.A., AvilovS.A., KalininV.I., KalinovskyA.I., ZaharenkoA.M., SmirnovA.V., MolloE., CiminoG. (2005) Holothurins B2, B3 and B4, new triterpene glycosides from Mediterranean sea cucumbers of the genus Holothuria.Journal of Natural Products, 68, 564–567.
10.
AvilovSA., KalininVI., SmirnovA.V. (2004) Use of triterpene glycosides for resolving taxonomic problems in the sea cucumber genus Cucumaria (Holothorioidea, Echinodermata). Biochemical Systematics and Ecology, 32, 715–733.
11.
SilchenkoA.S., AvilovS.A., KalininV.I., StonikV.A., KalinovskyA.I., DmitrenokP.S., StepanovV.G. (2007) Monosulfated triterpene glycosides from Cucumaria okhotensis Levin et Stepanov, a new species of sea cucumbers from the Sea of Okhotsk. Russian Journal of Bioorganic Chemistry, 33, 73–82.
12.
ZhangS.Y., YiY.H., TangH.F., LiL., SunP., WuJ. (2006) Two new bioactive triterpene glycosides from the sea cucumber Pseudocolochirus violaceus, Journal of Asian Natural Products Research, 8, 1–8.
13.
AvilovS.A., KalinovskyA.I., StonikV.A. (1990) New triterpene glycoside from the sea cucumber Neothyonidium magnum.Khimiya Prirodnykh Soedinenii, 1, 53–57.
14.
CareagaV.P., MuniainC.MaierM.S. (2011) Patagonicosides B and C, two antifungal sulfated triterpene glycosides from the sea cucumber Psolus patagonicus.Chemistry and Biodiversity, 8, 467–475.
15.
ZhangS.L., LiL., YiY.H., SunP. (2006) Philinopsides E and F, two new sulfated triterpene glycosides from the sea cucumber Pentacta quadrangularis.Natural Product Research, 20, 399–407.
16.
YiY.H., XuQ.Z., LiL., ZhangS.L., WuH.M., DingJ., TongY.G., TanW.F., LiM.H., TianF., WuJ.H., LiawC.C., BastowK.F., LeeK.H. (2006) Philinopsides A and B, two new sulfated triterpene glycosides from the sea cucumber Pentacta quadrangularis.Helvetica Chimica Acta, 89, 54–63.
17.
KalininV.I., StonikV.A., KalinovskyA.I., IsakovV.V. (1989) The structure of pseudostichoposide A – main triterpene glycoside from the sea cucumber Pseudostichopus trachus.Khimiya Prirodnykh Soedinenii, 5, 678–684.
18.
ElyakovG.B., StonikV.A., LevinaE.V., SlankeV.P., KuznetsovaT.A., LevinV.S. (1973) Glycosides of marine invertebrates-I. A comparative study of glycoside fraction of Pacific sea cucumbers. Comparative Biochemistry and Physiology, 44B, 325–336.
19.
ElyakovG.B., KuznetsovaT.A., StonikV.A., LevinV.S., AlboresR. (1975) Glycosides of marine invertebrates-IV. A comparative study of the glycosides from Cuban sublitoral holothurians. Comparative Biochemistry and Physiology, 52B, 413–417.
20.
StonikV.A., KalininV.I., AvilovS.A. (1999) Toxins from the sea cucumbers (holothuroids): Chemical structures, properties, taxonomic distribution, biosynthesis and evolution. Journal of Natural Toxins, 8, 235–248.
21.
DangN.H., ThanhN.V., KiemP.V., HuongL.M., MinhC.V., KimY.H. (2007) Two new triterpene glycosides from the Vietnamese sea cucumber Holothuria scabra.Archives of Pharmacal Research, 30, 1387–1391.
22.
ZhangS.Y., YiY.H., TangH.F. (2006) Bioactive triterpene glycosides from the sea cucumber Holothuria fuscocinera.Journal of Natural Products, 69, 1492–1495.
23.
MoraesG., NorthcoteP.T., SilchenkoA.S., AntonovA.S., KalinovskyA.I., DmitrenokP.S., AvilovS.A., KalininV.I., StonikV.A. (2005) Mollisosides A, B1 and B2: Minor triterpene glycosides from the New Zealand and South Australian sea cucumber Australostichopus mollis.Journal of Natural Products, 68, 842–847.
24.
AntonovA.S., AvilovS.A., KalinovskyA.I., AnastyukS.D., DmitrenokP.S., EvtushenkoE.V., KalininV.I., SmirnovA.V., TaboadaS., BallesterosM., AvilaC., StonikV.A. (2008) Triterpene glycosides from Antarctic sea cucumbers I. Structure of liouvillosides A1, A2, A3, B1 and B2 from the sea cucumber Staurocucumis liouvillei, new procedure for separation of highly polar glycoside fractions and taxonomic revision. Journal of Natural Products, 71, 1677–1685.
25.
SilchenkoA.S., AvilovS.A., KalinovskyA.I., DmitrenokP.S., KalininV.I., MorreJ., DeinzerM.L., WoodwardC., CollinP.D. (2007) Glycosides from the North Atlantic sea cucumber Cucumaria frondosa V – Structures of five new minor trisulfated triterpene oligoglycosides, frondosides A7–1, A7–3, A7–4, and isofrondoside C. Canadian Journal of Chemistry, 85, 626–636.
26.
KalininV.I., StonikV.A. (1996) Application of morphological trends of evolution to phylogenetic interpretation of chemotaxonomic data. Journal of Theoretical Biology, 180, 1–10.
27.
SilchenkoA.S., KalinovskyA.I., AvilovS.A., AndrijaschenkoP.V., DmitrenokP.S., KalininV.I., StonikV.A. (2012) 3β-O-Glycosylated 16β-acetoxy-9β-H-lanosta-7,24-diene-3β,18,20β-triol, an intermediate metabolite from the sea cucumber Eupentacta fraudatrix and its biosynthetic significance. Biochemical Systematics and Ecology., 44. 53–60.
28.
SilchenkoA.S., KalinovskyA.I., AvilovS.A., AndrijaschenkoP.V., DmitrenokP.S., MartyyasE.A., KalininV.I. (2012) Triterpene glycosides from the sea cucumber Eupentacta fraudatrix. Structure and cytotoxic action of cucumariosides A2, A7, A9, A10, A11, A13 and A14, seven new minor non-sulfated tetraosides and an aglycone with uncommon 18-hydroxy group. Natural Product Communications, 7, 845–852.
29.
KalininV.I., ProkofievaN.G., LikhatskayaG.N., SchentsovaE.B., AgafonovaI.G., AvilovS.A., DrozdovaO.A. (1996) Hemolytic activities of triterpene glycosides from the holothurian order Dendrochirotida: Some trends in the evolution of this group of toxins. Toxicon, 34, 475–483.
30.
FreshneyR.I. (1994) Culture of animal cells: a manual of basic technique.Wiley-Liss, New York.
31.
AmininD.L., SilchenkoA.S., AvilovS.A., StepanovV.G., KalininV.I. (2009) Cytotoxic action of triterpene glycosides from sea cucumbers from the genus Cucumaria on mouse spleen lymphocytes. Inhibition of nonspecific esterase. Natural Product Communications, 4, 773–776.
32.
ProkofievaN.G., KalinovskayaN.I., ChaikinaE.L., KuznetsovaT.A. (1999) The hemolytic activity of the cyclic acyldepsipeptides from marine isolate of Bacillus pumilus In Biodiversity and allelopathy: from organisms to ecosystems in the Pacific.ChouC.H., WallerG.R., ReinhardtC. (Eds.). Academia Sinica, Taipei, 199–203.
