Alexey V. Smirnov

Sea Cucumbers Triterpene Glycosides, the Recent Progress in Structural Elucidation and Chemotaxonomy

Triterpene glycosides are characteristic metabolites of sea cucumbers (Holothurioidea, Echinodermata). Majority of the glycosides belong to holostane type (lanostane derivatives with 18(20)-lactone). Carbohydrate chains of these glycosides contain xylose, glucose, quinovose, 3-O-methylglucose and 3-O-methyl sylose. During the last 5 years, main investigations were focused on holothurians belonging to the order Dendrochirotida collected in the North Pacific, North Atlantic, Antarctic and in subtropical waters. The glycosides of holothurians belonging to the order Aspidochirotida have also been studied. The most uncommon structural features of carbohydrate chains of new glycosides were: (1) the presence of quinovose as fifth terminal monosaccharide unit and the presence of two quinovose residues; (2) the presence of glucose instead of common xylose as fifth terminal monosaccharide unit; (3) trisaccharide carbohydrate chain; (4) the presence of two 3-O-methylxylose terminal monosaccharide units; (5) the presence of sulfate group at C-3 of quinovose residue. New glycosides without lactone or with 18(16)-lactone and having shortened side chains have also been isolated. The presence of 17α and 12α-hydroxyls, which are characteristic for glycosides from holothurians belonging to the family Holothuriidae (Aspidochirotida) in glycosides of dendrochirotids confirms parallel and relatively independent character of evolution of glycosides. All three families belonging to the order Aspidochirotida: Holothuriidae, Stichopodidae and Synallactidae have similar and parallel trends in evolution of the glycosides carbohydrate chains, namely from non-sulfated hexaosides to sulfated tetraosides. Sets of aglycones in glycosides from holothurians belonging to the genus Cucumaria (Cucumariidae, Dendrochirotida) are specific for each species. The carbohydrate chains are similar in all representatives of the genus Cucumaria.

Triterpene Glycosides from Antarctic Sea Cucumbers. 1. 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

Five new triterpene glycosides, liouvillosides A1 (1), A2 (2), A3 (3), B1 (4), and B2 (5), have been isolated from the Antarctic sea cucumber Staurocucumis liouviellei along with the known liouvilloside A(6), isolated earlier from the same species, and hemoiedemosides A (7) and B (8), isolated earlier from the Patagonian sea cucumber Hemioedema spectabilis. The isolation was carried out using a new chromatographic procedure including application of ion-pair reversed-phase chromatography followed by chiral chromatography on a cyclodextrin ChiraDex column. The structures of the new glycosides were elucidated using extensive NMR spectroscopy (1H and 13C NMR spectrometry, DEPT, 1H-(1)H COSY, HMBC, HMQC, and NOESY), ESI-FTMS, and CID MS/MS, and chemical transformations. Glycosides 1-3 are disulfated tetraosides and glycosides 4 and 5 are trisulfated tetraosides. Glycosides 2 and 3 contain 3-O-methylquinovose, found for the first time as a natural monosaccharide in sea cucumber glycosides. On the basis of analyses of glycoside structures a taxonomic revision is proposed.

Pseudostichoposide B – new triterpene glycoside with unprecedent type of sulfatation from the deep-water North-Pacific sea cucumber pseudostichopus trachus

New triterpene disulfated tetraoside, pseudostichoposide B (1) has been isolated from the sea cucumber Pseudostichopus trachus. The structure of this glycoside has been deduced by the extensive analysis of NMR and mass-spectra and chemical evidence. Except for a common sulfate group at C-4 of the first xylose residue, pseudostichoposide B contains an additional sulfate group at C-3 of quinovose residue in the carbohydrate chain, not earlier found in sea cucumber glycosides.

Two new steroid glycosides from the Far East starfish Hippasteria kurilensis

Two new steroid glycosides were isolated from the Far East starfish Hippasteria kurilensis collected in the Sea of Okhotsk. They were characterized as (22E,24R)-3-O-(2-O-methyl-β-D-xylopyranosyl)-24-O-[2-O-methyl-β-D-xylopyranosyl-(1→5)-α-L-arabinofuranosyl]-5α-cholest-22-ene-3β,4β,6α,7α,8,15β,24-heptaol (kurilensoside I) and (24S)-3-O-(2-O-methyl-β-D-xylopyranosyl)-24-O-(α-L-arabinofuranosyl)-5α-cholestane-3β,4β,6β,15α,24-pentaol (kurilensoside J). In addition, the earlier known glycosides linkosides F and L1, leviusculoside G, forbeside L, desulfated echinasteroside, and granulatoside A were isolated and identified. The structures of the new compounds were established with the help of two-dimentional NMR spectroscopy and mass- spectrometry.

Three new polyhydroxysteroids from the tropical starfish Asteropsis carinifera

Thirteen steroidal compounds including three new polyhydroxysteroids, (24R,25S)-24-methyl-5α-cholestane-3β,6α,8,15β,16β,26-hexaol, (22E,24R,25S)-24-methyl-5α-cholest-22-ene-3β,6α,8,15β,16β,26-hexaol, and (22E,24R,25S)-24-methyl-5α-cholest-22-ene-3β,4β,6α,8,15β,16β,26-heptaol, have been isolated along with ten previously known polyhydroxysteroids from the tropical starfish Asteropsis carinifera collected near the coast of Vietnam. The structures of the new compounds were elucidated by spectroscopic methods (mainly 2D NMR and ESI mass spectrometry).

Scoliorhapis stepanovi—new species of sea cucumber from the North-West Pacific (Holothuroidea: Synaptida: Chiridotidae: Taeniogyrinae) and some remarks on the genus Scoliorhapis

New species Scoliorhapis stepanovi has been collected from depths of 10-23 m on the sandy bottom of Avacha Bay (east coast of Kamchatka), Paramushir Island (North Kuril Islands), and Matua Island (Middle Kuril Islands). It is unique in having sigmoid ossicles in the body wall with points at both ends (without an open-eye, and with the two points lying in a perpendicular plane). Such sigmoids do not occur in any other taeniogyrinid species. The two-pointed sigmoids are 80-115 µm in length, and are scattered in the body wall and not clustered. Probably the two-pointed sigmoids are underdeveloped typical sigmoid with open-eye. In the tentacles there are straight and C-shaped rods, sometimes branched at the ends, 70-90 µm in length. It is assumed that atypical two-pointed sigmoid ossicles may have been originated due to deviating from the usual course of sigmoid development in the middle stages. Scoliorhapis stepanovi resembles S. lindbergi. A key for species of Scoliorhapis is provided.

BRANE UNIVERSE: GLOBAL GEOMETRY

The aim of this talk is to unvestigate the possible global geometries of some ”brane universe” scenarios in which ”our Universe” is supposed to be embedded in a space-time of larger number of dimensions, ”bulk”. In order to get the exact solutions we simplify the model as much as possible. Let us consider a (N + 1)-dimensional space-time containing a single N -dimensional thin shell (brane) and supppose that this brane is time-like and has the cosmological symmetry, i.e., it is homogeneous and isotropic. Moreover, we demand the bulk to have the slicing with the same symmetry. Then the metric of the whole space-time can be written as