Irina A. Gorshkova

Sterols from six marine sponges

The free sterol fractions from marine sponges Darwinella australiensis, Haliclona sp., Agelas mauritiana, Clathria major, Didiscus aceratusand Teichaxinella labirinticafrom Western Australia were isolated and studied by HPLC, GLC, GLC-MS, and NMR methods. D. australiensis contained 7 -, 5 -, 5,7 -, 5,7,9(11) -sterols, and cholest-7-en-3β-ol was shown to be a main sterol. The free sterols from A. mauritiana proved to be stanols and 7 -series compounds, chondrillasterol was identified as a predominant constituent. Haliclona sp. contained 5 -sterols with cholesterol as a main constituent. C. major and D. aceratus contained 5 -sterols, and clionasterol was shown to be a main sterol. T. labirintica was shown to contain 3β-hydroxymethyl-A-nor-sterols. Absolute configurations at C-24 of major sterols from C. major, D. aceratusand A. mauritiana were established by NMR method. Distribution of different sterols in the studied species was discussed to provide additional viewpoint on the probable application of these natural products as chemotaxonomic markers and to understand biological roles of unusual sterols in sponges using an idea of so-called biochemical coordination.  2003 Elsevier Ltd. All rights reserved.

A New Cytotoxic Fatty Acid (5Z,9Z)-22-Methyl-5,9- tetracosadienoic Acid and the Sterols from the Far Eastern Sponge Geodinella robusta

A new fatty acid, (5Z,9Z)-22-methyl-5,9-tetracosadienoic acid (1a), and a rare fatty acid, (5Z,9Z)-23-methyl-5,9-tetracosadienoic acid (2a), the predominant constituents of the free fatty acid fraction from the lipids of the sponge Geodinella robusta, were isolated and partly separated by reversed phase high-performance liquid chromatography, followed by multifold crystallization from MeOH to give 1a and 2a in 70% and 60% purity, respectively. These fatty acids were identified as (5Z,9Z)-22-and (5Z,9Z)-23-methyl-5,9-tetracosadienoic acids by nuclear magnetic resonance techniques, including distortionless enhancement by polarization transfer, heteronuclear multiple quantum connectivity, and correlation spectroscopy experiments, as well as from mass-spectrometric data for their methyl esters, the methyl esters of their perhydro derivatives, and their pyrrolidides. Mixtures of 1a and 2a showed cytotoxic activity against mouse Ehrlich carcinoma cells and a hemolytic effect on mouse erythrocytes. The sterol fraction from the same sponge was analyzed by gas liquid chromatography mass spectrometry, and 24-methylenecholesterol was identified as a main constituent of this fraction. The implications of the co-occurrence of membranolytic long-chain fatty acids and 24-methylenecholesterol as a main membrane sterol are discussed in terms of the phenomenon of biochemical coordination.

Two different modes of inhibition of the rat brain Na+,K+-ATPase by triterpene glycosides, psolusosides A and B from the holothurian Psolus fabricii

Effects of two triterpene glycosides, isolated from the holothurian Psolus fabricii, on rat brain Na+, K(+)-ATPase (Na, K-pump; EC 3.6.1.3) were investigated. Psolusosides A and B (PsA and PsB) inhibited rat brain Na+, K(+)-ATPase with I50 values of 1 x 10(-4) M and 3 x 10(-4) M, respectively. PsA significantly stimulated [3H]ATP binding to Na+, K(+)-ATPase, weakly increased [3H]ouabain binding to the enzyme, and inhibited K(+)-phosphatase activity to a smaller degree than the total reaction of ATP hydrolysis. In contrast, PsB decreased [3H]ATP binding to Na+, K(+)-ATPase, and had no effect on [3H]ouabain binding to the enzyme. K(+)-Phosphatase activity was inhibited by PsB in parallel with Na+, K(+)-ATPase activity. The fluorescence intensity of tryptophanyl residues of Na+, K(+)-ATPase was increased by PsA and decreased by PsB in a dose-dependent manner. The excimer formation of pyrene, a hydrophobic fluorescent probe, was decreased by PsA only. The different characteristics of inhibition mode for these substances were explained by peculiarities of their chemical structures and distinctive affinity to membrane cholesterol.

INHIBITION OF MEMBRANE TRANSPORT ATPASES BY HALENAQUINOL, A NATURAL CARDIOACTIVE PENTACYCLIC HYDROQUINONE FROM THE SPONGE PETROSIA SERIATA

Halenaquinol, a natural cardioactive pentacyclic hydroquinone from the sponge Petrosia seriata, was found to be a powerful inhibitor of the rat brainstem and of the rat brain cortex Na+, K(+)-ATPases and the rabbit muscle sarcoplasmic reticulum Ca(2+)-ATPase with I50 values of 7.0 x 10(-7), 1.3 x 10(-6) and 2.5 x 10(-6) M, respectively. Halenaquinol also inhibited K(+)-phosphatase activity of the rat brain cortex Na+, K(+)-ATPase with an I50 value of 3 x 10(-6) M. Ouabain-insensitive Mg(2+)-ATPase activity of the microsomal fraction of the rat brain cortex was weakly inhibited by halenaquinol. Inhibition was irreversible, dose- and time-dependent. Naphthohydroquinone fragment in structures of halenaquinol, related natural and model compounds was very important for an inhibiting effect.

STIMULATORY EFFECTS OF STARFISH SAPOGENINS (ASTERIAS AMURENSIS AND LETHASTERIAS NANIMENSIS CHELIFERA) ON MOLLUSCAN HEART (SPISULA SACHALINENSIS)

Sapogenins from the starfish Asterias amurensis and Lethasterias nanimensis chelifera, 5 alpha-pregn-9(11)-ene-3 beta,6 alpha-diol-20-one, 5 alpha-cholest-9(11)-ene-3 beta,6 alpha-diol-23-one, 5 alpha-cholesta-9(11),24(25)-diene-3 beta,6 alpha-diol-23-one, (20E)-5 alpha-cholesta-9(11),20(22)-diene-3 beta,6 alpha-diol-23-one and 24 zeta-methyl-5 alpha-cholesta-9(11),20(22)-diene-3 beta,6 alpha-diol-23-one, stimulated the contractile force of the heart of the mollusk Spisula sachalinensis at concentration of 5 x 10(-5) M. Ouabain, a specific inhibitor of Na+,K(+)-ATPase, at concentration of 5 x 10(-5) M had no effect on this physiological model. Starfish sapogenins of the cholestane series moderately inhibited rat brain cortex Na+,K(+)-ATPase and decreased Ca2+ influx into Ehrlich carcinoma cells. In contrast, pregnane asterogenin asterone did not inhibit Na+,K(+)-ATPase and increased the influx of Ca2+ into cells. These effects were not the result of cell membrane damage, because none of the compounds tested have hemolytic activity.

Molecular mobility in liquid-crystalline phase of oriented wholly aromatic copolyester as revealed by proton magnetic resonance

Broad line proton magnetic resonance (PMR) has been used for the study of molecular motion in wholly aromatic thermotropic liquid-crystalline (LC) copolyester at high temperatures up to 340°C. Specimens were thin highly oriented fibers produced from a copolymer of hydroxybenzoic acid and hydroxynaphthoic acid (HBA/HNA). In the vicinity of the thermotropic transition temperature a fine structure of PMR spectra was revealed for as-spun fibers. Annealing leads to smoothing of this structure. Theoretical spectra were calculated and compared with the experimental ones. This made it possible to obtain information on large-scale segmental motion of macromolecules in the LC phase. Heat treatment leads to retardation of the chain cooperative mobility. Dynamic inhomogeneity of the fibers at high temperatures is discussed.

Lack of orientation in the surface layer of wholly aromatic liquid-crystal polymer fibres

Abstract A comparison of band dichroism in the transmission and attenuated total reflection infra-red spectra of poly(phenyl- p -phenylene terephthalate) fibres, prepared by jet drawing, showed low molecular orientation in a surface layer of about 1 μm thickness.