N. V. Ivanchina

Biological activities of steroid glycosides from starfish

Glycosides of polyhydroxysteroids from starfish were compared with regard to hemolytic activities on mouse red blood cells and cytotoxicity on developing eggs of sea urchin Strongylocentrotus intermedius. Mediasteroside M(1) from Mediaster murrayi with a 2-O-methyl group at a xylose residue exerted lower activity than mediasteroside M(2) without this group. Ceramasteroside C(2) from Ceramaster patagonicus having a 2,4-di-O-Me-Xylp residue had more activity in comparison with ceramasteroside C(3) with 2-O-Me-Xylp. Activities of rathbuniosides R(1) (four OH-groups) and R(2) (five OH-groups) from Asterias rathbuni, and culcitosides C(2) (six OH-groups) and C(3) (five OH-groups) from Culcita novaeguineae were inversely proportional to the number of hydroxyl groups of the aglycon. There was a correlation between cytotoxic and hemolytic activities. The results indicated that salt concentration, temperature and pH values are important for the hemolytic activity of steroid glycosides.

Sulfated steroid compounds from the starfish Aphelasterias japonica of the Kuril population

Four sulfated steroid compounds were isolated from the Kuril population of the starfish Aphelasterias japonica. The structure of a new glycoside, aphelasteroside D, was elucidated as (24R)-29-O-[2-O-sulfo-β-D-glucopyranosyl]-24-ethyl-5α-cholestane-3β,5,6β,8β,15α,29-hexol sodium salt. Other three substances were identified as the known pycnopodioside C, 3-O-sulfo-24,25-dihydromarthasterone, and 3-O-sulfothornasterol A, the latter compound being isolated as a tyrammonium salt for the first time.

Asterosaponin P2 from the Far-Eastern starfishpatiria (asterina) pectinifera

A new polyhydroxylated steroidal glycoside, asterosaponin P2, was isolated from the Far-Eastern starfishPatiria (Asterina) pectinifera. The glycoside was identified as the 24R)-29-O-[2-O-sulfo-α-L-arabinofuranosyl]-24-ethyl-5α-cholestane-3β, 6α,8β,15α,16β,29-hexol Na salt.

Sulfated steroid glycosides from the Viet Namese starfish Linckia laevigata

Five sulfated steriodal compounds including one new glycoside called linckoside L7 (1) and four previously known glycosides 2–5 were isolated from the starfish Linckia laevigata. The structure sodium (22E, 24R)-3-O-(2-O-methyl-β-D-xylopyranosyl)-29-O-(β-D-xylopyranosyl)-24-ethylcholest-4,22-dien-3β,6β,8,15α,16β,29-hexaol 15-O-sulfate was proposed for L7. Linckoside L7 inhibited fertilization and egg-cell development in the sea urchin Strongylocentrotus intermedius.

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.

Absolute configuration of side chains of polyhydroxylated steroidal compounds from the starfish Henricia derjugini

The absolute configurations of the side chains of polyhydroxylated steroids from the starfish Henricia derjugini were determined by Mosher’s method using 1H NMR spectra of R-(+)- and S-(−)-α-methoxy-α-(trifluoromethyl)phenylacetates of these compounds. The chiral centers have the (24S) configuration in a steroidal hexaol and henricioside H1, the (24R,25S) configuration in henricioside H2, and the (24R, 25R) configuration in henricioside H3.

Polar steroidal compounds from the Far-Eastern starfish Lethasterias nanimensis chelifera

In addition to the salts described previously (with a sulfated steroid as the anion and the alkaloid salsolinol as the cation), nine other steroidal compounds including three new compounds were isolated from the Far-Eastern starfish Lethasterias nanimensis chelifera collected near the coast of the Onekotan island (Kuril isles). A nonsteroidal compound found in this starfish is (1S,3S)-1-methyl-1,2,3,4-tetrahydro-β-carboline-3-carboxylic acid. The structures of the isolated compounds were determined by NMR spectroscopy and mass spectrometry.

Structures of new polar steroids from the Far-Eastern starfish Ctenodiscus crispatus

A fraction of sulfated polyhydroxylated steroids from the Far-Eastern starfish Ctenodiscus crispatus was investigated. The main component of this fraction was identified as (22E,24R,25R)-24-methyl-5α -cholest-22-en-3β,5,6β,15α,25,26-hexol 26-O-sulfate. For the compound stereoisomeric with respect to the side chain, the (24R,25S) or (24S,25R) relative configurations were assigned to the C(24) and C(25) chiral centers. The structures of two other compounds isolated from the fraction were identified as (22E, 24ξ)-26,27-bisnor-24-methyl-5α-cholest-22-en-3β,5,6β,15α,25-pentol 25-O-sulfate and (22E, 24ξ,25ξ)-24-methyl-5α-cholest-22-en-3β,5,6β,8,15α,25,26-heptol 26-O-sulfate.

Asteropsiside A and other asterosaponins from the starfish Asteropsis carinifera

Three asterosaponins were isolated from the tropical starfish Asteropsis carinifera: a new one, asteropsiside A, and two known ones, regularoside A and thornasteroside A. The structure of the new compound was established using 2D NMR spectroscopy and ESI mass spectrometry as the sodium salt of 3-O-sulfonato-(20E)-6-O-{β-d-fucopyranosyl-(1→2)-β-d-galactopyranosyl-(1→4)-[β-d-quinovopyranosyl-(1→2)]-β-d-xylopyranosyl-(1→3)-β-d-quinovopyranosyl}-3β,6α-dihydroxy-5α-cholesta-9(11),20(22)-dien-23-one. Regularoside A and thornasteroside A were shown to display the ability to inhibit the growth of the T-47D and RPMI-7951 tumor cell colonies in vitro.

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).